CN1225675A - Detergent composition - Google Patents

Abstract

A detergent composition comprising an eazyme, a non-alkoxylated quaternary ammonium (non-AQA) surfactant and a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant.

Description

Detergent composition

Technical Field

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

Background

Because of the need for modern detergent compositions to remove various types of soils and stains from a wide variety of substrates, formulation of laundry detergents and other cleaning compositions presents a significant challenge. Thus, laundry detergents, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents and detergent compositions suitable for automatic dishwashing machines all require the proper selection and combination of ingredients for effective performance. The various detergent compositions described above generally contain one or more types of surfactants in order to loosen and remove different types of soils and stains. The review literature appears to indicate that detergent manufacturers have a wide selection of surfactants and surfactant combinations, and that in fact many components of detergents are specific chemicals that are not suitable for low-cost items such as household laundry detergents. In fact, most household cleaning products, such as household laundry detergents, still contain one or more conventional ethoxylated nonionic and/or sulfated or sulfonated anionic surfactants, and may be economically desirable and require the formulation of compositions that perform reasonably well on a variety of soils and stains and on a variety of fabrics.

Effective and rapid removal of different types of soils and stains, such as body soils, greasy/oily soils and some food stains, remains a challenge to be solved. Such soils contain triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous substances, all of which are composed to some extent of hydrophobic moieties and are very difficult to remove. After washing, the surface of the fabric often still retains a small amount of hydrophobic soils and stains. Continuous washing and wearing coupled with limited removal of hydrophobic soils, over multiple washes, will leave the soil and stain in large amounts, which further adsorbs particulate dust, resulting in yellowing of the fabric, and finally, the fabric takes on a dull appearance that consumers perceive to be unworn and should discard.

The literature shows that various nitrogen-containing cationic surfactants can be effectively used in various cleaning compositions. These materials are typically in the form of amino, amido, quaternary ammonium or imidazoline compounds, which are generally designed for specialized uses. For example, various amino and quaternary ammonium surfactants have been proposed for use in shampoo compositions, which are said to have hair styling benefits. Other nitrogen-containing surfactants are used in some laundry detergents to soften fabrics and provide antistatic benefits. However, for the most part, the commercial use of these materials is limited by the inability to produce them in large quantities. In addition, there is a limit to the possibility of precipitation of anionic active ingredients in the detergent composition and cationic surfactants due to their ionic interactions. The aforementioned nonionic and anionic surfactants remain the major surfactant components in today's laundry detergent compositions.

It has now been found that certain bis-alkoxy quaternary ammonium (bis-AQA) compounds are useful in a variety of detergent compositions to enhance the removal of various types of soils and stains, especially the hydrophobic types of soils which are common. It has now been surprisingly found that compositions containing an enzyme and a bis-alkoxy quaternary ammonium surfactant not only provide superior cleaning and whitening benefits, but also provide improved fabric care benefits, as compared to compositions containing only one of the ingredients.

The bis-alkoxy quaternary ammonium surfactants of the present invention provide significant benefits to formulators over previously known cationic surfactants. For example, the use of the bis-alkoxy quaternary ammonium surfactants of the present invention provides a significant improvement in the cleaning performance of "everyday" greasy/oily hydrophobic soils typically encountered. In addition, the use of cationic surfactants of today is often limited by the fact that the dialkoxy quaternary ammonium surfactants and anionic surfactants such as alkyl sulfates and alkyl benzene sulfonates in conventional detergent compositions can coexist with each other, while the anionic components of the detergent compositions are not present with the cationic surfactants. Low levels of bis-alkoxy quaternary ammonium surfactants (only 3ppm in the aqueous wash solution) can produce the benefits described herein. The bis-alkoxy quaternary ammonium surfactants can be formulated over a wide range of pH5-12, and the bis-AQA surfactants can be formulated as 30% (wt.) solutions, which can be pumped and therefore easily handled in production facilities. The dialkoxy quaternary ammonium surfactants having a degree of ethoxylation of greater than 5 are sometimes present in liquid form and can therefore be provided as 100% pure materials. In addition to its ease of handling, bis-AQA surfactants are available as highly concentrated solutions, which brings direct economic benefits in terms of shipping prices. Unlike some cationic surfactants known in the art, bis-alkoxy quaternary surfactants can also coexist with various fragrance ingredients.

The present invention provides a method of enhancing the removal of greasy/oily soils by combining a bis-alkoxy quaternary ammonium surfactant with a lipase. The oil/fat dirt is a mixture containing triglycerideA compound (I) is provided. During storage of soiled laundry prior to washing, the triglycerides in the soil are converted to fatty acids by the action of bacteria, and the lipase converts any remaining triglycerides to fatty acids during washing. Fatty acids in soils and hardness ions (e.g. Mg) in wash water²⁺And Ca²⁺) Interact to form insoluble magnesium/calcium fatty acid salts or calcium soaps. Calcium soap is dissolved in waterPrecipitating in the liquor to form a lime soap deposit on the fabric. Continued washing results in the accumulation of lime soap deposits, adsorption of particulate dust, interfering with soil removal, and enhancing the retention of soil residues on the washed fabric. In addition, there is a problem of degradation of the sheath around the fibers of old/worn cotton or other fibrous fabrics. The sheath degrades to form a gelatinous or amorphous cellulose gel that will also adsorb particulate dust. In addition, the cellulose gum is an ideal matrix for deposition and retention of greasy/oily hydrophobic bodysoils (e.g., on necklines and pillows). On frequent wear/washing, residual soil, lime soap deposits and dust pick-up accumulate, which causes the fabric to yellow until it becomes soiled, which the user considers unwashable and is usually discarded.

It has now been found that detergent compositions containing lipase and a bis-alkoxy quaternary ammonium surfactant have superior cleaning and whitening performance compared to compositions containing only one of the ingredients. This is believed to be because: (1) the bis-alkoxy quats reduce the production of calcium soaps, thus allowing the lipase to come into contact with soils; (2) fatty acids are effectively stripped from the soil (by the bis-alkoxy quaternary ammonium) and maximum lipase activity is maintained (high levels of fatty acids in the soil inhibit the action of the lipase).

It has now surprisingly been found that detergent compositions comprising a cellulosic enzyme (e.g. cellulase and/or endoglucanase) and a bis-alkoxy quaternary ammonium surfactant have superior cleaning and whitening benefits compared to compositions comprising only one of the components. This is a result of the effective penetration of the bis-alkoxy quaternary surfactants into the hydrophobic scale. Again, this enhances the degradation of the cellulose enzyme to the amorphous cellulose gum surrounding the fibers (which adheres soil to the fabric). As the cellulose gum dissolves, the adsorbed dust will detach from the fabric, and the original white detergent will be recovered. The combination of cellulosic enzymes and bis-alkoxy quaternary ammonium provides, in addition to cleaning benefits, better softening and fabric care than either the cationic or cellulosic enzyme alone.

It has also been found that detergent compositions containing amylase enzyme and a bis-alkoxy quaternary ammonium surfactant provide superior cleaning and whitening benefits compared to compositions containingonly one of the components. This is because the bis-alkoxy quats degrade by effectively solubilizing the soil, allowing the amylase to readily enter the sensitive soil, increasing the residual "glue" around the fiber. Along with the dissolution of the glue, the fabric recovers the original white and clean state, the adsorbed dust is separated, and other washing active ingredients are easy to play a bleaching role.

Background

US patent US5,441,541,1995 granted 8.15.8.a.mehretab and f.j.lopast, relates to anionic/cationic surfactant mixtures. UK2,040,990,1980, granted 9 months and 3 days, a.p.murphy, r.j.m.smith and m.p.brooks, relates to ethoxylated cationic components in laundry detergents.

Summary of The Invention

The invention relates to a detergent composition which comprises the following components or is prepared by mixing the following components: an enzyme, a non-alkoxy quaternary ammonium surfactant and an effective amount of a bis-alkoxy quaternary ammonium (bis-AQA) cationic surfactant having the formula:

in the formula R¹Is straight-chain, branched, or substituted C₈-C₁₈An alkyl, alkenyl, aryl, alkaryl, ether or sugar alcohol ether (glycidyl ether) moiety; r²Is C₁-C₃An alkyl group; r³And R⁴Each of which can be varied and is selected from one of hydrogen, methyl, ethyl; x is an anion; a and A' may each vary and are selected from C₁-C₄An alkoxy group; p and q can each vary and are integers between 1 and 30.

Detailed description of the invention enzymes

The composition of the present invention comprises an enzyme as an essential ingredient. The enzymes in the present detergent compositions have a variety of cleaning purposes including removal of proteinaceous, carbohydrate and triglyceride based stains from substrates, inhibition of transfer of shed dye during fabric washing, and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof, of any suitable origin such as vegetable, animal, bacterial, fungal, and yeast origin. Their selection is governed by the following factors: pH activity and/or stability optima, thermal stability, stability of active detergents, builders, etc. Bacterial or fungal enzymes are preferred in this respect, such as bacterial amylases and proteases, and fungal cellulases.

As used herein, "detersive enzyme" refers to any enzyme that has a cleaning, detersive, or other beneficial effect in a laundry, hard surface cleaning, or personal care detergent composition. Preferably the detersive enzyme is a hydrolase such as a protease, amylase and lipase. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Most preferred enzymes suitable for automatic dish washing are amylases and/or proteases.

Enzymes are typically added to detergent or detergent additive compositions in amounts effective for cleaning. An "effective cleaning amount" refers to any amount that produces a cleaning, stain removing, soil removing, whitening, deodorizing, or freshness enhancing effect on a laundry substrate (e.g., fabric, dishware). For current commercial preparations, the active enzyme ingredient is present at no more than 5mg, more typically between 0.01 and 3mg, per gram of detergent composition. In other words, the commercial enzyme preparations used in the compositions of the invention are generally present in an amount of from 0.001% to 5% by weight, preferably from 0.01% to 1% by weight. Proteases are generally used in commercial preparations in effective amounts of 0.005 to 0.1 Anson Units (AU) per gram of composition. For some detergents (e.g., automatic dishwashing machines), it may be desirable to increase the amount of active enzyme in the commercial product in order to substantially reduce the total amount of non-catalytically active material, thereby improving spotting/filming or other end effects. Higher amounts of activity are also required in highly concentrated detergent formulations.

Examples of suitable proteases are subtilisins, which are produced by specific strains of Bacillus subtilis and Bacillus licheniformis. Another suitable protease is produced by a strain of Bacillus, having the highest activity in the pH range 8-12, developed by Novo Industries A/S (hereinafter "Novo") of Denmark and developed according to ESPERASE^_And (5) selling. The preparation of this enzyme or a similar enzyme is described in GB1,243,783 to Novo. Other suitable proteases include ALCALASE sold by Novo^_And SAVINASE^_MAXATASE sold by International Bio-Synthesis, Inc. (the Netherlands)^_Protease A (see European patent application EP130,756A, published 1985 on 9.1), and protease B (see European patent application EP303,761A, published 1987 on 28.4.1987; European patent application EP130,756A, published 1985 on 9.1). Further comprising: high pH proteases obtainable from Novo in Bacillus NCIMB40338 described in International patent application WO9318140A, enzyme-added detergents described by Novo in International patent application WO9203529A, which also comprise one or more other classes of enzymes and reversible protease inhibitors; other preferred proteases include Procter&The protease described by Gamble in international patent application WO 9510591A; when required, e.g. Procter&The Gamble company, described in international patent application WO9507791, makes it possible to obtain proteases with reduced adsorption and enhanced hydrolysis; novo describes in International patent application WO9425583 recombinant trypsin-like proteases suitable for detergents according to the invention.

In particular, a particularly preferred protease is referred to as "protease D", a carbonyl hydrolase variant having an amino acid sequence not found in nature. Which is derived from a carbonyl hydrolase precursor by substitution of a plurality of amino acid residues in said carbonyl hydrolase corresponding to position +76 with different amino acids according to the code in Bacillus amyloliquefaciens subtilisin, preferably together with substitution of one or more amino acid residue positions selected from the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and/or +274, as described in U.S. patent application (serial No. 08/322,676) to "cleaning protease-containing compositions" of A.Baeck et al and U.S. patent application (serial No. 08/322,677) to "bleaching protease-containing compositions" of C.Ghosh et al, both were filed on 1994, 10/13.

Amylases suitable for the purposes of the present invention, particularly but not exclusively for automatic dishwashing machines, include the α -amylase described in British patent Specification GB1,296,839(Novo), RAPIDASE sold by International Bio-Synthesis, Inc^_And TERMAMYL sold by Novo corporation^_FUNGAMYL sold by Novo corporation^_Are particularly suitable. Enzyme engineering to improve enzyme stability (e.g.oxidative stability) is known, for example, in J.biological chem., Vol.260, No.11,1985, 6 months, 6518-6521. In certain preferred embodiments of the compositions of the present invention, amylases of increased stability, particularly improved oxidative stability, may be used in detergents (e.g., of the type used in automatic dishwashing), the reference point for stability measurements being TERMAMYL, which is commercially used in 1993^_. Preferred amylases of the invention have "stability enhancing" amylase characteristics, characterized by measurable improvements in at least one or more of the following: oxidative stability, such as hydrogen peroxide/tetraacetylethylenediamine oxidative stability in a buffer solution at pH 9-10; thermal stability, e.g., stability at typical washing temperatures (e.g., 60 ℃); alkaline stability, e.g., stability at pH8-11, measured in comparison to the reference amylase identified above. The measurement of stability can also be carried out using experimental techniques disclosed in the prior art, such as the reference disclosed in patent document WO 9402597. Amylases with enhanced stability are commercially available from Novo corporation or Genencor International. A preferred class of amylases of the invention has in common,amylases having enhanced oxidative stability compared to the reference amylase described above are preferred for use in the detergent compositions of the invention, especially bleaching detergent compositions, and more preferably oxygen bleaching detergent compositions as distinguished from chlorine bleaching.

(a) The amylase of WO9402597, published 2/3.1994, additionally stated to be a mutant in which alanine or threonine (preferably threonine) is used in place of the methionine residue at position 197 in Bacillus licheniformis α -amylase, a well-known procedureTERMAMYL of^_Homologous positional variants of similar homologous amylases, for example Bacillus amyloliquefaciens, Bacillus subtilis, or Bacillus stearothermophilus.

(b) A paper published by Genencor International at the National conference of the National Chemical Society of America 207 (America Chemical Society National Meeting), 3.13-17, 1994, entitled "antioxidative α -amylase" describes stability-enhanced amylases described herein, it is mentioned that inautomatic dishwasher detergents, a bleaching agent inactivates the α -amylase, but that an amylase with enhanced oxidative stability has been made by Genencor from Bacillus licheniformis NCIB8061 methionine (Met) was identified as the most likely residue to be modified, substituting methionine one at a time at positions 8, 15, 197, 256, 304, 366, and 438 results in the formation of specific variants, particularly important M197L and M197T, of which M197T is the most stably expressed^_And SUNLIGHT^_Stability was determined.

(c) Particularly preferred for the present invention are amylase variants described in WO9510613A with additional improvements in direct maternal thereto, available from Novo corporation, the assignee of the present invention, under the trade name DURAMYL^_. Other particularly preferred oxidative stability-enhanced amylases include WO9418314(Genencor Interna)Normal) and WO9402597 (Novo). Any other oxidative stability-enhanced amylase may also be used, for example an amylase obtained by site-directed mutagenesis from an available known chimeric, hybrid or simple mutant parent form of the amylase. Other preferred enzyme modifications may also be made, see WO9509909A (Novo).

Other amylases include those described in WO95/26397 and Novo Nordisk's co-pending application PCT/DK96/00056 specific amylases for use in the detergent compositions of the invention include α -amylase according to Phadebas^_α -amylase activity test, and has a specific activity at least higher than that of Termamyl at 25-55 deg.C and pH8-10^_Is 25% greater than the specific activity (Phadebas)^_α -Amylase Activity test see WO95/26397, pages 9-10.) additionally α -amylases having more than 80% homology to the amino acid sequences shown in the SEQ ID tables of the above documents are included, said enzymes being incorporated in the laundry detergent composition as pure enzymes, preferably in an amount of from 0.00018% to 0.060% by weight of the total composition, more preferably from 0.00024% to 0.048% by weight of the total composition.

Cellulases usable in the present invention include bacterial and fungal cellulases having an optimum pH of between 5 and 9.5. Granted on 3/6/1984 in the United states of Barbesgord et alSuitable mould cellulases derived from Humicola insolens or the Humicola strain DSM1800, or cellulases 212 produced by a mould belonging to the genus Aeromonas, and cellulases extracted from the hepatopancreas of the marine mollusk Dolabella Auricula Solander are disclosed in U.S. Pat. No.4,435,307. Suitable cellulases are also disclosed in GB-A-2,075,028, GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME^_And CELLUZYME^_(Novo) is also particularly suitable, see WO9117243 (Novo).

Suitable lipases which may be used in detergents include: lipases produced by bacteria of the genus Pseudomonas, such as Pseudomonas stutzeri ATCC19.154 (published in British patent GB1,372,034); the lipase disclosed in Japanese patent application No. 53-20487, published 24/2/1978, can be obtained from AmanoPharmaceutical co.ltd.nagoya, Japan, under the trade name lipase P "Amano" or "Amano-P". Other suitable commercial lipases include: Amano-CES, a lipase from Chromobacterium viscosum, e.g., Chromobacterium viscosum Lipolyticus NRRLB 3673, marketed by Toyo Jozo Co. Tagata Japan; chromobacterium viscosum lipase, sold by U.S. biochemical Corp. (USA) and Disoynth Co. (netherlands); and a lipase from pseudomonas gladioli. Lipolase from Humicola lanuginosa and commercially marketed by Novo (see also EP341,947)^_Enzymes are preferred lipases for use in the present invention. Stabilization of lipases and amylase variants against peroxidases is described in WO9414951A (Novo) and also in WO9205249 and RD 94359044.

Despite the numerous lipases disclosed, it has only been founduntil now that lipases from Humicola lanuginosa and lipases produced by Aspergillus oryzae as hosts are widely used as adjunct ingredients in fabric detergents, as described above, commercially available from Novo Nordisk under the trademark Lipolase^TM. In order for Lipolase to exhibit optimal detergency, Novo Nordisk has acquired a large number of Lipolase variants. Variant D96L, a lipase from native Humicola lanuginosa, as described in WO92/05249, provides a 4.4 fold increase in lard stain removal compared to the wild type lipase (at a level of 0.075-2.5mg protein per liter of comparative enzyme). Novo Nordisk is described in research disclosure (No. 35944) on 3/10 1994: the lipase variant (D96L) was added in an amount of 0.001-100mg (5.500,000 LU/liter) lipase variant per liter of wash solution. In the present invention, detergent compositions containing bis-alkoxy quaternary ammonium surfactants provide improved whiteness maintenance using low levels of D96L variant, especially D96L in amounts of 50 to 8500 LU per liter of wash solution.

The cutinases described in patent application WO8809367A to Genencor are suitable for use in the present invention.

Peroxidases are used in combination with oxygen sources, such as percarbonate, perborate, hydrogen peroxide, and the like, for "solution bleaching", or to inhibit the transfer of dyes and pigments dislodged from substrates during washing to other substrates in the wash solution. Known peroxidases include, horseradish peroxidase, ligninase, and haloperoxidase (e.g., chloro-or bromo-peroxidase). Detergent compositions containing peroxidase are disclosed in WO89099813A (publication date 10/19 (Novo) 1989) and WO8909813A (Novo).

Various enzymatic materials and methods for their incorporation into synthetic detergent compositions are also disclosed in International patent applications WO9307263A and WO9307260A by Genencor International, International patent application WO8908694A by Novo, and U.S. Pat. No. 5,3,553,139 by McCarty et al (issued on 15/1 1971). Some enzymes are also disclosed in Place et al, U.S. Pat. No. 8,4,101,457 (issued on 7/18 1978) and Hughes, U.S. Pat. No.4,507,219 (issued on 26 3/1985). Enzyme materials useful in liquid detergent formulations, and methods for their incorporation into such formulations, are disclosed in U.S. Pat. No. 5,4,261,868 to Hora et al (issued on 4/14 1981). Enzymes used in detergents can be stabilized in various ways. Enzyme stabilization techniques are disclosed and exemplified in U.S. Pat. No. 5,3,600,319 to Gedge et al (issued on 8/17 of 1971), and European patents EP 199,405, EP 200,586 to Venegas (published on 10/29 of 1986). Enzyme stabilization systems are also described in the literature, for example, in U.S. Pat. No. 3,519,570. Suitable proteases, xylanases and cellulases produced by Bacillus AC13 are described in International patent application WO9401532A (Novo). Bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactants

The second essential component of the compositions of the present invention comprises an effective amount of a bis-alkoxylated quaternary ammonium surfactant having the formula:

in the formula R¹Is a linear, branched, or substituted alkyl, alkenyl, aryl, alkane group containing from 8 to 18 carbon atoms, preferably from 8 to 16 carbon atoms, most preferably from 8 to 14 carbon atomsAryl, ether or sugar alcohol ether; r²Is an alkyl group having 1 to 3 carbon atoms, preferably methyl; r³And R⁴Each variable and selected from hydrogen (preferred), methyl, ethyl; x-is an anion, e.g. chlorine, bromine, methylsulfate, sulfurAcid radicals, which are effective in providing electrical neutrality; a and A' may each vary and are each selected from C₁-C₄Alkoxy, in particular ethoxy, propoxy, butoxy and mixed types thereof; p is 1 to 30, preferably 1 to 15, more preferably 1 to 8, most preferably 1 to 4, q is 1 to 30, preferably 1 to 15, more preferably 1 to 8, particularly preferably 1 to 4, and p and q are most preferably 1.

Bis-alkoxy quaternary ammonium (bis-AQA) compounds in which the hydrocarbyl substituent R¹Is C₈-C₁₂In particular C₈-C₁₂The rate of dissolution of the laundry detergent particles is increased compared to long chain substituted hydrocarbyl compounds, particularly under cold water conditions. Thus, the C₈-C₁₂The bis-alkoxylated quaternary ammonium surfactants of (a) may also be preferred by formulators. The amount of bis-alkoxylated quaternary ammonium surfactant used in the finished laundry detergent composition is generally from 0.1% to 5% (wt.), preferably from 0.45% to 2.5% (wt.). The weight ratio of the bis-alkoxylated quaternary ammonium surfactant to the percarbonate bleach is from 1: 100 to 5: 1, preferably from 1: 60 to 2: 1, most preferably from 1: 20 to 1: 1.

The present invention employs an "effective amount" of a bis-alkoxylated quaternary ammonium surfactant to enhance the performance of cleaning compositions containing other selected components. An "effective amount" of a bis-alkoxy quaternary ammonium surfactant as described herein is an amount sufficient to directionally or significantly enhance the cleaning effectiveness of the cleaning composition on at least some target soils and stains, at a 90% confidence level. Thus, for the composition of some food target stains, the formulator will use a sufficient amount of the bis-alkoxy quaternary ammonium to at least directionally enhance the cleaning effect on such stains. Also, in compositions for soil target soils, the formulator will use a sufficient amount of bis-alkoxy quaternary ammonium to at least directionally enhance the cleaningof the soil.

The bis-alkoxy quaternary ammonium surfactants may be used in combination with other detersive surfactants in an amount effective to achieve at least directionally enhancing cleaning performance. In the case of fabric washing compositions, the "amount" may vary depending on the type and severity of the soil and stain, and also depending on the temperature of the water during washing, the amount of water used, and the type of washing machine.

For example, in a top loading vertical shaft American automatic washing machine, water is used for washing at 45-83 liters, a washing cycle is carried out for 10-14 minutes, the water temperature is 10-50 ℃ during washing, and the amount of the dialkoxy quaternary ammonium surfactant in the washing liquid is preferably 2-50ppm, preferably 5-25 ppm. For heavy duty liquid detergents, the amount used per wash load is converted to a concentration of from 0.1% to 3.2% by weight, preferably from 0.3% to 1.5% by weight, of the dialkoxy quaternary ammonium surfactant in the product, calculated as 50-150ml per wash load. For concentrated granular laundry detergents (densities above 650g/l), the amount used per wash load is converted to a concentration of the bis-oxa-quaternary surfactant in the product of 0.2% to 5.0% by weight, preferably 0.5% to 2.5% by weight, calculated as 60-95 g. For spray-dried granular detergents (i.e. "bulk", density below 650g/l), the amount used per wash load is 80-100g converted to a concentration of the bis-alkoxy quaternary ammonium surfactant in the product of 0.1-3.5% by weight, preferably 0.3-1.5% by weight.

For example, a front loading horizontal axis omega (continent) automatic washing machine, washing with 8-15 litres of water, one wash cycle for 10-60 minutes at a water temperature of 30-95 ℃, preferably contains the bis-alkoxy quaternary ammonium surfactant in an amount of 13-900ppm, preferably 16-390ppm, in the wash liquor. For heavy duty liquid detergents, the amount used per wash load is converted to a concentration of from 0.4% to 2.64% by weight, preferably from 0.55% to 1.1% by weight, of the dialkoxy quaternary ammonium surfactant in the product, calculated as 45-270ml per wash load. For concentrated granular laundry detergents (densities above 650g/l), the amount used per wash load is converted to a concentration of from 0.5% to 3.5% by weight, preferably from 0.7% to 1.5% by weight, of the dialkoxy quaternary ammonium surfactant in the product, calculated as 40-210 g. For spray-dried granular detergents (i.e. "bulk", density below 650g/l), the amount used per wash load is converted to a concentration of from 0.13% to 1.8% by weight, preferably from 0.18% to 0.76% by weight, of the dialkoxy quaternary ammonium surfactant in the product, calculated as 140-400g per wash load.

For example, in a top-loading vertical shaft Japanese automatic washing machine, 26-52 liters of water are used in washing, one washing cycle is 8-15 minutes, the temperature of the water in washing is 5-25 ℃, and the amount of the dialkoxy quaternary ammonium surfactant contained in the washing liquid is 1.67-66.67ppm, preferably 3-6 ppm. For heavy duty liquid detergents, the amount used per wash load is converted to a concentration of from 0.25% to 10% by weight, preferably from 1.5% to 2% by weight, of the dialkoxy quaternary ammonium surfactant in the product, calculated as 20 to 30ml per wash load. For concentrated granular laundry detergents (densities above 650g/l), the amount used per wash load is converted to a concentration of from 0.25% to 10% by weight, preferably from 0.5% to 1.0% by weight, of the dialkoxy quaternary ammonium surfactant in the product, calculated as 18-35 g. For spray-dried granular detergents (i.e. "bulk", density below 650g/l), the amount used per wash load is in the range 30-40g converted to a concentration of the dialkoxy quaternary ammonium surfactant in the productof 0.25% to 10% by weight, preferably 0.5% to 1% by weight.

As can be seen from the above, the amount of bis-alkoxy quaternary ammonium used in the machine wash can vary depending on the habits and practical experience of the user, as well as the type of washing machine. Thus, one previously unrecognized advantage of bis-alkoxy quaternary ammonium surfactants in this regard is: it has the ability to at least directionally enhance cleaning performance over a wide range of soils and stains, even at relatively low levels, compared to other surfactants (typically anionic or anionic/nonionic mixtures) in existing detergents. This is unlike other compositions of the prior art, where various cationic and anionic surfactants are used in or near stoichiometry. In general, in the practice of the present invention, the weight ratio of the bis-alkoxy quaternary ammonium surfactant to anionic surfactant in the laundry detergent composition is from 1: 70 to 1: 2, preferably from 1: 40 to 1: 6, more preferably from 1: 30 to 1: 6, and even more preferably from 1: 15 to 1: 8. In a laundry detergent composition comprising anionic and nonionic surfactants, the ratio of bis-alkoxy quaternary ammonium: the weight ratio of the anionic/nonionic mixture is from 1: 80 to 1: 2, preferably from 1: 50 to 1: 8.

Various other detergent compositions comprising an anionic surfactant, an optional nonionic surfactant and specific surfactants (e.g., betaines, sultaines, amine oxides) may also be formulated using an effective amount of the bis-alkoxy quaternary ammonium surfactants of the present invention. Such compositions include, but are not limited to, dishwashing detergents (particularly liquid or gel-like) suitable for hand washing, hard surface cleaners, shampoos, personal cleansing compositions, laundry detergents, and the like. As the usage habits and practical experience of users with these detergents vary less, it is suitable to include the dialkoxy quaternary ammonium surfactants in amounts of from 0.25% to about 5% by weight, preferably from 0.45% to about 2% by weight, in these compositions. In addition, for granular and liquid laundry detergent compositions, the weight ratio of the bis-alkoxy quaternary ammonium surfactant to the other surfactants in these compositions is low, i.e. sub-stoichiometric compared to the anion. Preferably, such cleaning compositions comprise the bis-alkoxy quaternary ammonium/surfactant ratio just described above for the laundry compositions for machine use.

The bis-alkoxylated cationic surfactants of the present invention have sufficient solubility compared to other cationic surfactants known herein to allow the use of mixed surfactant systems having low levels of nonionic surfactant and containing, for example, alkyl sulfate surfactants in the system. This is a significant consideration for formulators of detergent compositions of the type: detergent compositions of conventional design for top loading automatic washing machines, especially models designed for north american use and japanese use. Generally, these compositions will comprise anionic surfactant and nonionic surfactant in a ratio of from about 25: 1 to about 1: 25, preferably from about 20: 1 to about 3: 1. Formulations of the euro-state type differ in that the ratio of anionic to nonionic surfactant is generally from about 10: 1 to about 1: 10, preferably from about 5: 1 to about 1: 1.

Preferred ethoxylated cationic surfactants of the present invention are available from Akzo Nobel Chemicals Company under the trade name ETHOQUAD. Alternatively, it can be synthesized from various reaction schemes (wherein "EO" represents-CH)₂CH₂O-unit): scheme 1

Scheme 2

Scheme 3

Scheme 4

An economical reaction scheme is as follows: scheme 5

The following parameters summarize optional and preferred reaction conditions for scheme 5. Step 1 of the reaction is preferably carried out in an aqueous phase. The reaction temperature is generally within the range of 140 ℃ to 200 ℃. The reaction pressure is 50-1000 lb/in². The alkali catalyst is preferably sodium hydroxide. The molar ratio of the reactants (amine: alkyl sulfate) is from 2: 1 to 1: 1. Preference is given to using C for the reaction₈-C₁₄Sodium alkyl sulfate. The alkylation and quaternization steps are carried out using conventional conditions and reactants.

Under some conditions, the product of scheme 5 is sufficiently soluble in the aqueous reaction phase that a gel may be formed. Although the desired product can be recovered from the gel, an alternative scheme 6 to the two-step synthesis described below would be more commercially viable. The first reaction step of scheme 6 corresponds to scheme 5 and the second reaction (ethoxylation) is preferably carried out using ethylene oxide and an acid such as hydrochloric acid to provide a quaternary ammonium surfactant. As shown below, the chlorohydrin may also be reacted to obtain the desired bis-hydroxyethyl derivative.

For reaction scheme 6, the following parameters summarize the optional and preferred conditions for the first step reaction. The first reaction step is preferably carried out in an aqueous phase. The reaction temperature is generally within the range of 100 ℃ to230 ℃. The reaction pressure is 50-1000 lb/in². Alkali, preferably sodium hydroxide, with HSO produced in the reaction₄ ^-Excess amine may also be used to react with the acid. The molar ratio of the reactants (amine: alkyl sulfate) is generally from 10: 1 to 1: 1.5, preferably from 5: 1 to 1: 1.1, and more preferably from 2: 1 to 1: 1. In the step of product recovery, the desired substituted amine is insoluble in the aqueous phase, and is easily separated, unlike the aqueous phase. The second reaction step is carried out using conventional reaction conditions. The ethoxylation and quaternization reactions to further produce the bis-alkoxy quaternary ammonium surfactants are carried out under standard reaction conditions.

Scheme 7 can be carried out under standard ethoxylation conditions using ethylene oxide, optionally, without a catalyst to obtain the monoethoxylated product.

These increased reaction schemes are listed below, where "EO" represents-CH₂CH₂An O-unit. In the reaction, an inorganic base, an organic base, or an excess of amine is used to neutralize HSO produced₄ ^-. Scheme 6

Scheme 7

The following describes some of the above reactions in addition, which are only referred to by the formulator and are not meant to be limiting. Synthesis A: preparation of N, N-bis (2-hydroxyethyl) dodecylamine

19.96g of sodium lauryl sulfate (0.06921 mol), 14.55g of diethanolamine (0.1384 mol), 7.6g of 50% by weight sodium hydroxide solution (0.095 mol) and 72g of distilled water were charged into a glass autoclave jacket. The glass sleeve is sealed and then is put into a 500ml stainless steel stirring pressure kettle at 300-400 pounds/inch²Heated to160 ℃ and 180 ℃ under nitrogen pressure for 3-4 hours. The mixture was cooled to room temperature, the liquid in the glass thimble was poured into a 250ml separatory funnel, 80ml of chloroform was added, and the mixture was separated after shaking for several minutes. And recovering the chloroform at the lower layer, and evaporating the chloroform to obtain a reaction product. Synthesis of B: preparation of N, N-bis (2-hydroxyethyl) dodecylamine

1mol of sodium dodecyl sulfate was reacted with 1mol of ethanolamine in the presence of a base in the method of the synthesis of A. Recovering the reaction product 2-hydroxyethyl dodecylamine, and reacting with 1-chloroethanol to prepare the N, N-bis (2-hydroxyethyl) dodecylamine. Synthesis of C: preparation of N, N-bis (2-hydroxyethyl) dodecylamine

19.96g of sodium dodecyl sulfate (0.06921 mol), 21.37g of ethanolamine (0.3460 mol), 7.6g of 50% by weight sodium hydroxide solution (0.095 mol), and 72g of distilled water were charged into a glass autoclave jacket. The glass sleeve is sealed and then placed into a 500ml stainless steel stirring pressure kettle, and heated to 160-180 ℃ for 3-4 hours under the nitrogen pressure of 300-400 lb/in 2. The mixture was cooled to room temperature, the liquid in the glass thimble was poured into a 250ml separatory funnel, 80ml of chloroform was added, and the mixture was separated after shaking for several minutes. And recovering the lower-layer chloroform, and evaporating the chloroform to obtain a reaction product. The reaction product reacts with 1 molar equivalent of ethylene oxide in the absence of a base catalyst at the temperature of 120-130 ℃ to obtain the required final product.

The bis-substituted amines prepared above can be ethoxylated in a standard manner and quaternized with alkyl halides in a conventional manner to obtain the bis-alkoxy quaternary ammonium surfactants of the invention.

In light of the foregoing description, the following non-limiting examples illustrate the bis-alkoxy quaternary ammonium surfactants useful in the present invention. It will be appreciated that the degree of alkyl oxidation of the bis-alkoxy quaternary ammonium surfactants of the present invention is reported on an average basis, and the following are common examples of nonionic surfactants that are typically ethoxylated, since ethoxylation typically results in a mixture of different degrees of ethoxylation. Thus, the total EO value is typically reported as a non-integer number such as "EO 2.5", "EO 3.5".

Name R¹R²ApR³A＇qR⁴Bis-alkoxy Quaternary ammonium-1C₁₂-C₁₄CH₃EO EO (see coconut methyl EO2) bis-alkoxyRadical quaternary ammonium-2C₁₂-C₁₆CH₃(EO)₂EO bis-alkoxy Quaternary ammonium-3C₁₂-C₁₄CH₃(EO)₂(EO)₂(see coconut methyl EO4) bis-alkoxy Quaternary ammonium-4C₁₂CH₃EO EO bis-alkoxy Quaternary ammonium-5C₁₂-C₁₄CH₃(EO)₂(EO)₃Bis-alkoxy-quaternary ammonium-6C₁₂-C₁₄CH₃(EO)₂(EO)₃Bis-alkoxy-quaternary ammonium-7C₈-C₁₈CH₃(EO)₃(EO)₂Bis-alkoxy Quaternary ammonium-8C₁₂-C₁₄CH₃(EO)₄(EO)₄Bis-alkoxy-quaternary ammonium-9C₁₂-C₁₄C₂H₅(EO)₃(EO)₃Bis-alkoxy Quaternary ammonium-10C₁₂-C₁₈C₃H₇(EO)₃(EO)₄Bis-alkoxy Quaternary ammonium-11C₁₂-C₁₈CH₃(propoxy) (EO)₃Bis-alkoxy quaternary ammonium-12C₁₀-C₁₈C₂H₅(Isopropoxy)₂(EO)₃Bis-alkoxy quaternary ammonium-13C₁₀-C₁₈CH₃(EO/propoxy)₂(EO)₃Bis-alkoxy quaternary ammonium-14C₈-C₁₈CH₃(EO)₁₅ ^*(EO)₁₅ ^*Bis-alkoxy quaternary ammonium-15C₁₀CH₃EO EO bis-alkoxy Quaternary ammonium-16C₈-C₁₂CH₃EO EO bis-alkoxy Quaternary ammonium-17C₉-C₁₁CH₃EO3.5 (average) Bialkoxy Quaternary ammonium-18C₁₂CH₃EO3.5 (average) Bialkoxy Quaternary ammonium-19C₈-C₁₄CH₃(EO)₁₀(EO)₁₀Bis-alkoxy quaternary ammonium-20C₁₀C₂H₅(EO)₂(EO)₃Bis-alkoxy quaternary ammonium-21C₁₂-C₁₄C₂H₅(EO)₅(EO)₃Bis-alkoxy quaternary ammonium-22C₁₂-C₁₈C₃H₇Butoxy (EO)₂

Ethoxy is optionally terminated with methyl or ethyl.

Particularly preferred bis-alkoxy quaternary ammonium compounds are of the formula:

wherein R is¹Is C₈-C₁₈Hydrocarbyl and mixtures thereof, preferably C₈、C₁₀、C₁₂、C₁₄Alkyl groups and mixtures thereof; x is any conventional anion that can create a charge balance, preferably chloride. With reference to the bis-alkoxy quaternary ammonium general structure mentioned above, since in preferred compounds R is¹Derived from coconut (C)₁₂-C₁₄Alkyl) partial fatty acid, R²Is methyl, and A_pR³And A'_qR⁴Monoethoxy groups, respectively, so the preferred compounds are "coconut MeEO 2" or "bis-alkoxy quat-1" as listed in the above table.

Other bis-alkoxy quaternary ammonium surfactants useful in the present invention include compounds having the following structural formula:

wherein R is¹Is C₈-C₁₈Hydrocarbyl, preferably C₈-C₁₄Alkyl, p and q are each independently 1-3, R²Is C₁-C₃Alkyl, preferably methyl, and X is an anion, especially chloride or bromide.

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

Particularly preferred bis-alkoxy quaternary ammonium surfactants for use in builder formulations have the formula: wherein p and/or q is an integer in the range of 10 to 15. The compounds are particularly useful in laundry hand wash detergent compositions. Non-alkoxy quaternary ammonium detersive surfactants

In addition to containing the bis-alkoxy quaternary ammonium surfactant, the compositions of the present invention preferably also contain a non-alkoxy quaternary ammonium surfactant. Non-alkoxy quaternary ammonium surfactants include essentially any anionic, nonionic or otherwise cationic surfactant. Anionic surfactants

Non-limiting examples of anionic surfactants useful in the present invention, generally at levels of from 1% to 55% by weight, include: conventional C₁₁-C₁₈Alkyl benzene sulfonates ("LAS"); primary site ("AS"), branched or random C₁₀-C₂₀An alkyl sulfonate; structural formula is CH₃(CH₂)_x(CHOSO₃ ^-M⁺)CH₃And CH₃(CH₂)_y(CHOSO₃ ^-M⁺)CH₂CH₃C of (A)₁₀-C₁₈Secondary (2,3) alkylsulfonic acid salts wherein x and (y +1) are integers of at least 7, preferably at least 9, and M is a water-soluble cation (particularly sodium); unsaturated sulfates, such as oleyl sulfate; c₁₂-C₁₈α -sulfonated fatty acid ester C₁₀-C₁₈A sulfated polyglycoside; c₁₀-C₁₈Alkyl alkoxy sulfates (' AE)_xS', in particular EO1-7 ethoxy sulfate), and C₁₀-C₁₈Alkyl alkoxy carboxylates (In particular EO1-5 ethoxy carboxylate). C₁₂-C₁₈Betaines and sulfobetaines, C₁₀-C₁₈Amine oxides may be included in the overall composition, and conventional C's may also be used₁₀-C₂₀And (3) soaps. If foam enhancement is desired, a branched chain C may be used₁₀-C₁₆And (3) soaps. Other commonly used surfactants have been listed in general textbooks. Nonionic surfactant

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

More specifically, the condensation products of primary and secondary aliphatic alcohols with 1 to 25 moles of ethylene oxide (AE) are suitable for use as nonionic surfactants in the present invention. The alkyl chain of the aliphatic alcoholmay be straight or branched, primary or secondary, and typically contains from 8 to 22 carbon atoms. The condensation products of alcohols (1 mole) whose alkyl group contains from 8 to 20 carbon atoms, preferably from 10 to 18 carbon atoms, with from 1 to 10 moles, more preferably from 2 to 7 moles, most preferably from 2 to 5 moles, of ethylene oxide are preferred. Examples of such nonionic surfactants commercially available include: tergitol, both sold by Union Carbide Corporation^TM15-S-9(C₁₁-C₁₅Condensation products of linear alcohols with 9 moles of ethylene oxide) and Tergitol^TM24-L-6 NMW(C₁₂-C₁₄Products with narrow molecular weight distribution of primary alcohols condensed with 6 moles of ethylene oxide); neodol sold by Shell Chemical Company^TM45-9(C₁₄-C₁₅Condensation products of linear alcohols with 9 moles of ethylene oxide), Neodol^TM23-3(C₁₂-C₁₃Condensation products of linear alcohols with 3 moles of ethylene oxide), Neodol^TM45-7(C₁₄-C₁₅Condensation products of linear alcohols with 7 moles of ethylene oxide) and Neodol^TM45-5(C₁₄-C₁₅Condensation products of linear alcohols with 5 moles of ethylene oxide); byProcter&Kyro sold by Gamble Company^TMEOB(C₁₃-C₁₅Condensation products of alcohols with 9 moles of ethylene oxide); and Genapol LA O3O or O5O (C) sold by Hoechest₁₂-C₁₄Condensation products of alcohols with 3 or 5 moles of ethylene oxide). In these AE nonionic surfactants, the preferred range of hydrophilic-lipophilic balance (HLB) is from 8 to 11, most preferably from 8 to 10. Condensates with propylene oxide and butylene oxide may also be used.

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

wherein R is¹Is H, or C_1-4A hydrocarbyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, or a mixture thereof; r²Is C_5-31A hydrocarbyl group; and Z is a polyhydroxyhydrocarbyl having at least 3 hydroxyl groups directly attached to the linear hydrocarbyl chain, or an alkoxylated derivative thereof. R¹Is methyl, R²Is straight chain C_11-15Alkyl radical, C_15-17Alkyl or alkenyl groups (e.g. coconut alkyl) or mixtures thereof, and Z is obtained from a reducing sugar, such as glucose, fructose, maltose, lactose, in a reductive amination reaction. Typical examples thereof include C₁₂-C₁₈And C₁₂-C₁₄N-methyl glucamide, see US 5194639 and US 5298636. N-alkoxy polyhydroxy fatty acid amides may also be used, see U.S. Pat. No. 5489393.

In the present invention, usable as the nonionic surfactant are: alkylpolysaccharides having hydrophobic groups, the hydrophobic groups of which contain 6 to 30 carbon atoms, preferably 10 to 16 carbon atoms, are disclosed in U.S. patent 4565647 to Llenado, issued on 21.1.1986; polysaccharides, such as polyglycosides whose hydrophobic groups contain 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7 saccharide units. Any reducing sugar containing 5 or 6 carbon atoms may be used, such as glucose, galactose, and the galactosyl moiety may be substituted for the glucosyl moiety (the hydrophobic group may be optionally attached to the 2-, 3-, 4-etc., thus giving a glucose or galactose different from glucoside or galactosamine). The intersaccharide linkage may be located, for example, between one position of the other saccharide unit and the 2-, 3-, 4-, and/or 6-position of the preceding saccharide unit.

Preferred alkyl polyglycosides have the following structural formula:

R²O(C_nH_2nO)_t(sugar base)_xWherein: r²Selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl group contains 10 to 18, preferably 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is 0 to 10, preferably 0; x is 1.3 to 10, preferably 1.3 to 3, more preferably 1.3 to 2.7. The glycosyl is preferably a glucose derivative. To prepare these compounds, an alcohol or alkylpolyethoxy alcohol is first prepared and then reacted with glucose or a source of glucose to form the glucoside (attachment at the 1-position). The 1-position of the other glycosyl unit can then be linked to the preceding glycosyl unit in the 2-, 3-, 4-and/or 6-position (preferably predominantly the 2-position).

In the surfactant system of the present invention, polyethylene oxide, propylene oxide and butylene oxide condensates of alkyl phenols are also suitable for use as the nonionic surfactant, with the polyethylene oxide condensates being preferred. These compounds include: condensation products of alkylphenols having 6 to 14 carbon atoms in the alkyl group, preferably 8 to 14 carbon atoms, with alkylene oxides in a linear or branched configuration. 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 nonionic surfactants of this type include: igepal sold by GAFCcorporation^TMCO-630; and by Rohm&Triton sold by Hass Company^TMX-45, X-114, X-100 and X-102. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkylphenol ethoxylates).

The hydrophobic backbone obtained by the condensation reaction of propylene oxide with propylene glycol, and then with ethylene oxide, is also suitable for use as other nonionic surfactants in the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of 1500-. By adding a polyoxyethylene moiety to this hydrophobic moiety, the water solubility of the whole molecule is generally improved and the polyoxyethylene content is 50% of the total weight of the condensation productWhile still maintaining the liquid character of the product. This corresponds to condensation with up to 40 moles of ethylene oxide. Examples of such compounds include the partial Pluronic marketed by BASF^TMA surfactant.

Among the nonionic surfactant systems of the present invention, further suitable for use as nonionic surfactants are: the condensation products of the reaction product of propylene oxide and ethylenediamine with ethylene oxide. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and has a molecular weight of typically 2500-3000. The hydrophobic moiety is condensed with ethylene oxide so that the condensation product contains 40-80% by weight of polyoxyethylene and has a molecular weight of 5000-11000. Examples of such nonionic surfactants include part Tetronic sold by BASF^TMA compound is provided. Other cationic surfactants

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

Other suitable cationic surfactants include: selected from mono C₆-C₁₆(preferably C)₆-C₁₀) Quaternary ammonium surfactants of N-alkyl or alkenyl ammonium surfactants in which the remaining N sites are substituted with methyl, hydroxyethyl or hydroxypropyl groups. Other suitable cationic ester surfactants, including choline ester surfactants, have been disclosed in U.S. Pat. Nos. 4228042, 4239660 and 4260529. Optional detergent ingredients

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

The enzyme-containing compositions of the present invention also comprise from 0.001% to 10% by weight, preferably from 0.005% to 8% by weight, and most preferably from 0.01% to 6% by weight, of an enzyme stabilizing system. The enzyme stabilizing system may be any stabilizing system compatible with the detergent enzyme. Such stabilizing systems may be provided by the other active ingredients in the formulation themselves, or may be added separately, e.g., by the formulator or by the manufacturer of the detergent ready-to-use enzyme. Such stabilizing systems may include, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acid, mixtures thereof, and the like, and may be designed to address different stability issues depending on the type and physical form of the detergent composition.

One way to achieve stability is to use water-soluble calcium and/or magnesium ions in the finished composition to provide these ions to the enzyme. Calcium ions are generally more effective than magnesium ions, and therefore calcium ions are preferred if only one cation is used. Detergent compositions in general, especially liquid detergents, contain from 1 to 30, preferably from 2 to 20, more preferably from 8 to 12 millimoles of calcium ion per liter of finished detergent composition, although variations may occur depending on factors including the diversity, type, and amount of enzymes. Preferably, water-soluble calcium and/or magnesium salts are used, including: such as calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide, and calcium acetate; calcium sulfate or the magnesium salts corresponding to the listed calcium salts can also generally be used. Of course, it may be useful to further increase the amount of calcium and/or magnesium used, for example to improve the grease removal performance of certain types of surfactants.

Another way to achieve stability is to use borate-type materials in the composition, see Severson, U.S. patent 4537706. Borate stabilizers, when used, can be present in amounts of up to 10% or more of the composition, although typically levels of boric acid or other borate compounds (e.g., borax or orthoborate) in the liquid detergent of about 3% by weight are suitable. Boronic acids such as phenylboronic acid, butylboronic acid, p-bromophenylboronic acid or the like may be substituted for the boronic acid, and the use of such boronic acid derivatives may reduce the total boron content of the detergent composition.

Certain detergent composition stabilizing systems, such as automatic dishwasher detergent compositions, may further comprise from 0% to 10% by weight, preferably from 0.01% to 6% by weight, of chlorine bleach scavengers, which are added to prevent chlorine bleach species present in many water sources from attacking and inactivating enzymes, especially under alkaline conditions. Although the chlorine content of water is low, typically in the range of 0.5ppm to 1.75ppm, the amount of chlorine that can come into contact with the enzyme in total water, for example during the washing of dishes or fabrics, is considerable, and therefore, the stability of the enzyme to chlorine during use is sometimes problematic. The use of other chlorine stabilizers, while improving efficacy, is generally not necessary because of the ability of the percarbonate to react with the chlorine bleach material. Suitable chlorine scavenger anionic materials are known and readily available. If used, it is a salt containing an ammonium cation, such as sulfite, bisulfite, thiosulfite, thiosulfate, iodide, and the like. Additionally, antioxidants such as carbamates, ascorbic acid, and the like, organic amines such asethylenediaminetetraacetic acid (EDTA) or alkali metal salts thereof, Monoethanolamine (MEA), and mixtures thereof may also be used. Likewise, the addition of a specific enzyme inhibition system allows for maximum compatibility of the different enzymes. Other conventional scavengers such as bisulfites, nitrates, chlorides, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphates, condensed phosphates, acetates, benzoates, citrates, formates, lactates, malates, tartrates, salicylates, and the like, and mixtures thereof, may be used if desired. In general, the chlorine scavenger effect can be achieved by separately listing several components having better recognized effects (e.g., hydrogen peroxide source species), and thus there is no need to separately add a chlorine scavenger unless the compound performing this function is missing to the extent desired in the enzyme-containing embodiment of the invention, even in such cases, the scavenger is added only for optimum effectiveness. In addition, the formulator will exercise the ordinary skill of the chemist to avoid the use of any enzyme scavengers or stabilizers, which are mostly incompatible with the other components if used. With respect to the use of ammonium salts, such salts can simply be mixed with the detergent composition, but tend to absorb water and/or release ammonia during storage. Thus, such materials, if present, need to be protected in granules, such as described in U.S. patent 4652392 to Baginski et al. Bleaching agent

The detergent composition may optionally comprise a bleaching agent. When present, the bleaching agent is typically present at levels of from 1% to 30%, more typically from 5% to 20% of the detergent composition, especially for laundry detergent compositions.

The bleaching agent used in the present invention may be any bleaching agent suitable for use in detergent compositions in fabric washing, hard surface cleaning or other known or to be known laundering applications. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches such as sodium perborate (e.g., sodium perborate monohydrate or tetrahydrate) may be used herein.

Another class of bleaching agents, without limitation, includes percarboxylic acid bleaching agents and salts thereof. Suitable examples of such bleaching agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxyperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. patent No. US 4483781 to Hartman, published on 20.11.1984, european patent application 0133354 to Banks, published on 20.2.2.3532 of U.S. patent application No. 740446,1985, published on 3.6.1985, and U.S. patent No. 4412934 to Chung, published on 1.11.1983. Preferred bleaching agents also include 6-nonanamido-6-oxyperoxyhexanoic acid, which has been described in U.S. Pat. No. 4634551 to Burns et al, 6.1.1987.

Peroxygen bleaches may also be used. Suitable peroxy bleach compounds include sodium carbonate peroxyhydrate and corresponding "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured and sold by DuPont) may also be used.

Preferred percarbonate bleach compositions comprise dry particles having an average particle size in the range of from 500 microns to 1000 microns, wherein no more than 10% by weight of the particles having a particle size below 200 microns and no more than 10% by weight of the particles having a particle size above 1250 microns. The percarbonate may optionally be coated with a silicate, borate or water soluble surfactant. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

Non-oxygen bleaches are also known in the art and may be used in the present invention. One class of non-oxygen bleaches of particular benefit includes photoactivated bleaches such as sulfonated zinc and/or aluminum phthalocyanines. See U.S. patent 4033718 to Holcomb et al, issued on 5.7.1977. If used, detergent compositions typically comprise from 0.025% to 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanines.

Mixtures of bleaching agents may also be used. Bleach activators

Bleach activators are preferred components in detergent compositions employing oxygen bleaches. When used, the amount is generally from 0.1 to 60%, more generally from 0.5 to 40% of the composition (containing bleach and bleach activator).

Peroxygen bleaching agents such as perborates, etc. are mixed with bleach activators in aqueous solution (i.e., during the wash process) to generate in situ peroxyacids or peracids corresponding to the bleach activators. Various non-limiting examples of bleach activators are disclosed in U.S. patent 4915854 to Mao et al, issued on 10.4.1990, and U.S. patent No. 4412934. Nonoyloxybenzene sulfonate (NOBS) and Tetraacetylethylenediamine (TAED) activators are conventional and may be used in combination. In addition, see U.S. patent No. US4634551 for other typical bleaching agents and activators that may be used in the present invention.

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

R¹N(R⁵)C(O)R²c (O) L or R¹C(O)N(R⁵)R²C (O) L wherein R¹Is an alkyl group having 6 to 12 carbon atoms; r²Is an alkylene group having 1 to 6 carbon atoms; r⁵Is H or an alkyl, aryl or alkylaryl group containing from 1 to 10 carbon atoms; l is any suitable leaving group. By leaving group is meant any group that can be displaced from the bleach activator due to nucleophilic attack of the perhydrolyzed anion on the bleach activator. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators having the above formula include: (6-octanoylaminohexanoyl) oxybenzenesulfonate, (6-nonanoylaminocaproyl) oxybenzenesulfonate, (6-decanoylaminohexanoyl) oxybenzenesulfonate, and mixtures thereof described in U.S. Pat. No.4,34551, which is incorporated herein by reference.

Another class of bleach activators includes: an activator of the benzoxazine type disclosed in U.S. patent US 4966723 to Hodge et al, granted 10, 30, 1990. Highly preferred benzoxazine type activators are:

another class of preferred bleach activators includes: acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formula:wherein R is⁶Is H or an alkyl, aryl, alkoxyaryl, or alkylaryl group containing from 1 to 12 carbon atoms. Highly preferred lactam activators include: benzoyl caprolactam, octanoyl caprolactam, 3,5, 5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5, 5-trimethylhexanoyl valerolactam, and mixtures thereof. See Sanderson, U.S. Pat. No. 3, 4545784, issued on 8/10/1985, which discloses acyl caprolactams including benzoyl caprolactam absorbed into sodium perborate. Bleaching catalyst

Bleach catalysts are optional components in the compositions of the present invention. If desired, the bleaching compound can be catalyzed by a manganese compound. Such compounds are known in the art and include: such as manganese-based catalysts disclosed in U.S. Pat. Nos. 5,246,621, 5,244,594, 5,194,416, 5,114,606 and European patent applications published under the numbers 549,271A1, 549272A1, 544,440A2, 544,490A 1. Preferred examples of these catalysts include: mn^Ⅳ ₂(u-O)₃(1,4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(PF₆)₂、Mn^Ⅲ ₂(u-O)₁(u-OAc)₂(1,4, 7-trimethyl-1, 4, 7-triazacyclononane)₂-(ClO₄)₂、Mn^Ⅳ ₄(u-O)₆(1,4, 7-triazacyclononane)₄(ClO₄)₄、Mn^ⅢMn^Ⅳ ₄(u-O)₁(u-OAc)₂- (1,4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(ClO₄)₃、Mn^Ⅳ(1,4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(OCH₃)₃(PF₆) And mixtures thereof. Other metal-based bleach catalysts include: united states of AmericaCatalysts disclosed in patents US4,430,243 and US5,114,611. The use of various complex ligands of manganese to enhance bleaching is also reported in the following U.S. patents: 4,728,455, 5,284,944, 5,246,612, 5,256,779, 5,280,117, 5,274,147, 5,153,161 and 5,227,084.

In practice, and without limitation, the compositions and methods of the present invention can be adjusted to provide about at least 0.1ppm of active bleach catalyst material in the aqueous wash liquor, and preferably from 0.1 to 700ppm, more preferably from 1 to 500ppm, of catalyst material in the wash liquor.

Cobalt bleach catalysts useful in the present invention are known, for example, as described in m.l. tobe in adv.in bionorg.mech. (1983), pages 2,1-94, basic Hydrolysis of Transition-Metal complexes. The most preferred cobalt catalysts useful in the present invention are: having the formula [ Co (NH)₃)₅OAc]Ty(wherein "OAc" denotes an acetate moiety and "Ty" is an anion), in particular cobalt penta-aminoacetic chloride, [ Co (NH)₃)₅OAc]Cl₂And [ Co (NH)]₃)₅OAc](OAc)₂、[Co(NH₃)₅OAc](PF₆)₂、[Co(NH₃)₅OAc](SO₄)、[Co(NH₃)₅OAc](BF₄)₂And [ Co (NH)]₃)₅OAc](NO₃)₂(PAC of the present invention).

These cobalt catalysts can be prepared by known methods as described in the following documents: the article by Tobe and references cited therein, U.S. Pat. No.4,810,410 to Diakun et al, published 3.7.1989, J.chem. Ed. (1989),66, (12),1043-45, the Synthesis and Characterization of organic Compounds, W.L.Jolly (Prentice Hall, (1970), pp.461-3, Inorg.chem,18, 1497-.

In practice, and without limitation, the automatic dishwasher detergent compositions and washing methods of the present invention are adapted to provide about at least 0.01ppm of active bleach catalyst material in the aqueous wash liquor, and preferably from 0.01 to 25ppm, more preferably from 0.05 to 10ppm, most preferably from 0.1 to 5ppm of bleach catalyst material in the wash liquor. To achieve this level in the wash liquor of automatic dishwashing, typical automatic dishwasher detergent compositions of the invention comprise from 0.0005 to 0.2%, preferably from 0.004 to 0.08%, by weight of the detergent composition, of a bleach catalyst, especially a manganese or cobalt catalyst. Builder

For example to facilitate control of minerals, especially Ca, in the wash water²⁺And/or Mg²⁺Or to facilitate removal of particulate soils from surfaces, the compositions of the present invention may optionally, and preferably, comprise detergency builders. Builders function by a variety of mechanisms, includingforming soluble or insoluble complexes with hard ions by ion exchange, and by forming a surface that favors the precipitation of hard ions over the surface of the article being cleaned. The amount of builder used may vary depending on the end use and physical form of the composition. The builder detergent will typically comprise at least 1% builder. Liquid formulations typically contain from 5% to 50%, preferably from 5% to 35% builder. Granular formulations typically comprise from 10% to 80%, preferably from 15% to 50% by weight of the detergent composition of builder. Lower or higher levels of builder are not excluded. For example, certain detergent additives or high surfactant formulations may be free of builders.

Suitable builders may be selected from: phosphates and polyphosphates, especially sodium salts; silicates, including water soluble and aqueous solids, but also those having chain-, layer-, or three-dimensional structures, as well as amorphous solids or unstructured liquids; carbonates, bicarbonates; sesquicarbonate and carbonate minerals other than sodium carbonate or sodium sesquicarbonate; an aluminosilicate; organic mono-, di-, tri-, and tetracarboxylic acid salts, especially water-soluble non-surfactant carboxylates in the form of sodium, potassium or alkanolammonium salts, and oligomeric or water-soluble low molecular weight polymeric carboxylates including aliphatic and aromatic types; and phytic acid may be supplemented with borates (e.g. for pH buffering purposes), or with sulfates, especially sodium sulfate, and any other fillers or carriers that may be important in producing stable surfactant-and/or builder-containing detergent compositions.

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

Phosphorus-containing detergent builders are generally preferred, as permitted by regulations, and include, but are not limited to: alkali metal, ammonium and alkanolammonium salts of polyphosphates, such as tripolyphosphates, pyrophosphates, glassy polymeric metaphosphates, and phosphonates.

Suitable silicate builders include: alkali metal silicates, in particular SiO₂∶Na₂Ratio of OThose liquid and solid alkali metal silicates in the range of 1.6: 1 to 3.2: 1, including, especially for automatic dishwashing purposes, silicates supplied by PQ Corp with a solid water ratio of 2, under the trade name BRIITESIL^_E.g. BRITESSIL H₂O; layered silicates, seeUS patent US 4664839 issued to h.p. rieck at 12.5.1987; NaSKS-6, sometimes abbreviated as "SKS-6", is a crystalline, layered, aluminum-free, delta-Na sold by the Hoechst corporation₂SiO₅The silicate in state, which is particularly preferred in granular detergents for laundry purposes, is described in DE-A-3,417,649 and DE-A-3,742,043 for the preparation thereof. Such as those having the general formula NaMSi_xO_2x+1·yH₂Other layered silicates of O, where M is sodium or hydrogen, n is from 1.9 to 4, preferably 2, y is from 0 to 20, preferably 0. layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 in the α -, β -and γ -layered silicate states, respectively.

Builders suitable for use in the present invention are also: a synthetic crystalline ion exchange material having a chain structure or a hydrate thereof and consisting of a compound represented by the following general formula in the form of an anhydride: xM₂O·ySiO₂zM 'O, where 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 to Sakaguchi et al, 1995.

Suitable carbonate builders include: alkaline earth and alkali metal carbonates are described in german patent application No. 2321001, 1973, 11/15. Sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals, such as trona or any common double salt of sodium carbonate and calcium carbonate, e.g. having the composition 2Na when anhydrous₂CO₃·Ca₂CO₃Double salts of (a), even calcium carbonates including calcite, aragonite and vaterite, especially relatively dense calcite, having a morphology with a large surface area may also be used, e.g. as seed crystals or in bulk synthetic detergents.

Aluminosilicate builders are particularly preferred in granular detergents and may also be incorporated in liquids, pastes or gels. Those aluminosilicates suitable for this purpose have the experimental formula: [ Mz (AlO)₂)z(SiO₂)v]·xH₂O, whereinz and v are integers of at least 6, the molar ratio of z to v is in the range of 1.0 to 0.5, and x is an integer of 15 to 264. Aluminosilicates can be crystalline or amorphous in structure, and can be naturally occurring or synthetic. A process for preparing aluminosilicates is disclosed in U.S. Pat. No. 3,137,669 to Krummel et al, issued 10/12/1976. The preferred synthetic crystalline aluminosilicate ion exchange materials for use herein are commercially available under the names Zeolite A, Zeolite P (B) and Zeolite X, which in any case are compatible with Zeolite P,so-called Zeolite MAP is different. Aluminosilicates in their natural form, including clinoptilolite, may also be used. The structural formula of Zeolite A is: na (Na)₁₂[(AlO₂)₁₂(SiO₂)₁₂]·xH₂O, where x is from 20 to 30, preferably 27. Dehydrated zeolites (x =0-10) may also be used. Preferred aluminosilicates have a diameter of between 0.1 and 10 microns.

Suitable organic detergent builders include: polycarboxylate compounds including water-soluble non-surfactant di-and tri-carboxylates. Preferred polycarboxylate builders have a plurality of carboxylate groups, preferably at least 3 carboxylate groups. Carboxylate builders can generally be formulated in acidic, partially neutralized, neutral or overbased forms. When used in the form of a salt, a salt of an alkali metal such as sodium, potassium and lithium, or an alkanolammonium salt is preferred. Polycarboxylate builders include ether polycarboxylates such as oxydisuccinate, see U.S. Pat. No. 3128287 to Berg, issued 4-7, 1964, and U.S. Pat. No. 3635830 to Lamberti et al, issued 1-18, 1972, and also see "TMS/TDS" builder in U.S. Pat. No. 4633071 to Bush et al, issued 5-5, 1987. Other suitable ether carboxylates include cyclic and aliphatic cyclic compounds, described in U.S. Pat. Nos. 3922679, 3835163, 4158635, 4120874, and 4102903.

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

Citrate builders, such as citric acid and its water-soluble salts, are particularly important carboxylate builders, as they areavailable from renewable resources and biodegradable, such as for liquid heavy-duty laundry detergents. Citrate salts may also be used in granular compositions, particularly in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and mixtures.

Where phosphorus-based builders can be used, and especially in the formulation of bars for hand washing, various alkali metal phosphates such as sodium tripolyphosphate, pyrophosphate and orthophosphate can be used. Phosphonate builders such as ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates (see U.S. Pat. Nos. 3159581, 3213030, 3422021, 3400148 and 3422137) may also be used to effect detergent removal.

Some detergent surfactants or their short chain analogues also contribute to the cleaning function. For a well-defined formulation, when the component has the efficacy of a surfactant, the material is generally classified as a detergentA surfactant. Preferred examples of the surfactant having a washing-assistant function are: 3, 3-dicarboxy-4-oxa-1, 6-adipate, and related compounds, are disclosed in U.S. patent 4566984 to Bush, 28, 1986. The succinic acid builder comprises C₅-C₂₀Alkyl and alkenyl succinic acids and salts thereof. Succinate builders also include: lauryl succinate, tetradecyl succinate, hexadecyl succinate, 2-dodecenyl succinate (preferred), and 2-pentadecenyl succinate. Lauryl succinate salt is described in European patent application 86200690.5/0200263 published on 5.11.1986. Fatty acids such as C₁₂-C₁₈Monocarboxylic acids may also be added to the composition as surfactant builders, either alone or in admixture with the aforementioned builders, especially citrate and/or succinate builders, to produce additional builder activity. U.S. patent 4144226 to Crutchfield et al, published 3/13 in 1979, and U.S. patent to Diehl, published 3/7 in1967Other suitable polycarboxylates are described in national patent 3308067. See also U.S. patent 3723322 to Diehl.

Other types of inorganic builder materials that can be used have the formula: (M)_x)_iCa_y(CO₃)_zWherein x and i are integers between 1 and 15, y is an integer between 1 and 10, z is an integer between 2 and 25, M_iAre cationic, at least one of which is water-soluble while satisfying the equation ∑_i=1-15(x_i×M_iOf) +2y =2z, such that the formula has a neutral or "balanced" charge. The builder is referred to herein as a "mineral builder". Bound water or anions other than carbonate may be added to maintain the overall charge balance or to be electrically neutral. The charge or valence of these anions should be added to the right of the above equation. Preferred water-soluble cations are selected from the group consisting of hydrogen, water-soluble metals, boron, ammonium, silicon and mixtures thereof, further preferred are sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, most preferred are sodium and potassium. Non-limiting examples of non-carbonate anions include: chloride, sulfate, fluoride, oxygen, hydroxide, silica, chromate, nitrate, borate, and mixtures thereof. The most simple form of builder of this type is preferably selected from Na₂Ca(CO₃)₂、K₂Ca(CO₃)₂、Na₂Ca₂(CO₃)₃、NaKCa(CO₃)₂、NaKCa₂(CO₃)₃、K₂Ca₂(CO₃)₃And mixtures thereof. The most preferred builder material described herein is Na in either of its crystalline forms₂Ca(CO₃)₂. Suitable builder types as defined above may also include any one or combination of the following natural or synthetic forms of material: acalcitonite, uraninite, offretite Y,hydrocerussite, colemanite, borokurtzite, strontianite, monocalcite, cancrinite, cerite, canasite, kainite, strontianite, Y, kalium, Ferrisurite, kainite, monetite, monocalcite, cancrinite, kenyaite, cancriniteBerkolite, Girvasite, ilmenite, canasite, Kamphaugite Y, Bischalcoho-bismuthate, Khannesite, LepersonniteGd. Picrocalcite, celytrium carbonate Y, eucryptite, colemanite, nesotaite, nesonite, Remondite Ce, savealite, uraninite, hydrocarbonatellite, sillenite, dawsonite, kalsilimanite, cuprocoite, cancrinite and Zemkorite. Preferred mineral forms include nesquehonite, kallmatite and canasite. Polymeric soil release agents

Known polymeric soil release agents, hereinafter "SRA" or "SRA's", may be optionally employed in the detergent compositions of the present invention. SRA's, if used, are generally present at 0.01% to 10.0%, preferably 0.1% to 5%, most preferably 0.2% to 3.0% by weight of the total composition.

The hydrophilic portion of the preferred SRA generally has an affinity for the surface of hydrophobic fibers, such as polyester or nylon, and the hydrophobic portion deposits on the hydrophobic fibers and remains adsorbed thereto until the end of the washing or rinsing process, thus anchoring the hydrophilic portion. This may allow subsequent stains treated with SRA to be easily removed during subsequent washing.

SRA may comprise, various charged, such as anionic or even cationic (see US4956447), as well as non-charged monomeric units and structures thereof which may be linear, branched, or even star-shaped. They include end-capping moieties that are particularly effective in controlling molecular weight, or altering physical properties, or altering surface activity characteristics. The structure and charge distribution can be adjusted to suit different fibre or fabric types and different detergent or detergent additive products.

Preferred SRA's include oligomeric terephthalates, generally prepared by a process comprising at least one transesterification/oligomerization reaction, which is commonly catalyzed by a metal catalyst, such as titanium (iv) alkoxide. Such esters, prepared by using additional monomers that can be added to 1-, 2-, 3-, 4-, or more positions of the ester structure, do not, of course, form a tightly cross-linked overall structure.

Suitable SRAs include: a sulfonated product of a substantially linear oligoester comprising an oligomeric ester backbone of terephthaloyl and oxyalkylene oxide repeat units and allyl-derived sulfonated terminal moieties covalently bonded to the backbone. This is as described in US patent US 4968451 to j.j.scheibel and e.p.gosselink, 6.11.1990: the oligoester can be prepared by the following steps: (a) ethoxylated allyl alcohol, (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1, 2-propanediol ("PG") by two transesterification/oligomerization steps, (c) reacting the product of (b) with sodium metabisulfite in water; the anionically end-capped 1, 2-propylene terephthalate/polyoxyethylene terephthalate polyester of Gosselink et al, US4,711,730, issued 12/8/1987, such as may be produced by transesterification/oligomerization of poly (ethylene glycol) methyl ether, DMT, PG, and polyethylene glycol ("PEG"); partially and wholly anionic-capped oligoesters such as oligomers of ethylene glycol ("EG"), PG, DMT, and sodium 3, 6-dioxa-8-hydroxyoctanesulfonate, from Gosselink, U.S. patent US4,721,580, granted on 26.1.1988; non-ionic end-capped block polyester oligomers such as those derived from DMT, Me-capped PEG and EG and/or PG, or a mixture of DMT, EG and/or PG, Me-capped PEG and sodium dimethyl-5-sulfoisophthalate, as in Gosselink, US4,702,857, granted on 27.10.1987; and anion (particularly sulfoaroyl) -terminated terephthalates in U.S. patent No. US4,877,896 to Maldonado, Gosselink et al, entitled 31/10/1989. The latter are typical SRAs and are useful in laundry detergents and fabric conditioning products such as: ester compositions made from the mono-sodium salt of meta-sulfobenzoic acid, PG and DMT, preferably but preferably comprising added PEG (e.g., PEG 3400).

The SRA further comprises: simple block copolymers of ethylene terephthalate or propylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate, see U.S. Pat. No. 3,959,230 to Hays, 5/25 1976 and U.S. Pat. No. 3,893,929 to Basadur, 7/8 1975; cellulose derivatives, e.g. hydroxy ether cellulose poly from DowThe compound METHOCEL; c₁-C₄Alkyl celluloses and C₄Hydroxyalkyl cellulose, see U.S. patent No. US4,000,093 to Nicol et al, issued 12/28/1976. Suitable SRAs featuring a poly (vinyl ester) hydrophobic moiety include: poly (vinyl esters) grafted onto a polyoxyalkylene skeleton, e.g. poly (C)₁-C₆Vinyl esters), preferably graft copolymers of poly (vinyl acetate). See Kud et al, European patent application 0,219,048, published on 22/4/1987. Examples of commercially available include: SOKALAN SRA's, such as SOKALAN HP-22 from BASF, Germany. Other SRAs are: the repeating units derived from polyoxyethylene glycol having an average molecular weight of 300-5000-. Examples of commercially available include: ZELCON5126 by DuPont, and mleas by ICI.

Another preferred SRA is: having the experimental structural formula (CAP)₂(EG/PG)₅(T)₅(SIP)₁Comprising terephthaloyl (T), Sulphoisophthaloyl (SIP), oxyethylene and oxy-1, 2-propenyl (EG/PG) units and preferably end-capped with an end-capping group (CAP), preferably a modified isethionate, for example in an oligomer comprising one sulphoisophthaloyl, 5 terephthaloyl and oxyethylene in a given ratio, preferably in the range of about 0.5: 1 to 10: 1Ethoxy and oxy-1, 2-propyleneoxy units, and two end-capping units derived from sodium 2- (2-hydroxyethoxy) -ethanesulfonate. The SRA also preferably comprises: from 0.5% to 20% by weight of the oligomer of a crystallization-reducing stabilizer such as: anionic surfactants such as sodium linear dodecylbenzene sulfonate or selected from the group consisting of xylene-, cumene-and toluene-sulfonates or mixtures thereof, wherein these stabilizers or modifiers are added to the synthesis reactor in the manner described in US5,415,807 issued 5.16.1995 to Gosselink, Pan, Kellett and Hall. Suitable monomers for the above SRA include: sodium 2- (2-hydroxyethoxy) -ethanesulfonate, DMT, sodium dimethyl-5-sulfoisophthalate, EG, and PG.

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

{(CAP)_x(EG/PG)_y＇(DEG)_y″(PEG)_{y_}(T)_z(SIP)_z′(SEG)_q(B)_mwherein CAP, EG/PG, PEG, T and SIP are as defined above, (DEG) represents a di (oxyalkylene) oxy unit; (SEG) represents units derived from the sulfoethyl ether of glycerol, and related partial units; (B) represents a branching unit having at least three functional groups, which thereby form ester linkages to produce a branched oligomer backbone; x is from about 1 to about 12; y' is about 0.5 to 25; y' is from about 0 to about 12; y _ is about 0-10'; y' + y "totals about 0.5 to 25; z is from about 1.5 to about 25; z' is from about 0 to about 12; z + z' totals about 1.5 to 25; q is from about 0.05 to about 12; m is from about 0.01 to about 10; and x, y ', y _, z, z', q and m represent the average number of moles of corresponding units per mole of the ester, the molecular weight of the ester being about 500-5000.

Preferred SEG and CAP monomers for the above esters include: preferred SRA esters include sodium 2- { (2- (2-hydroxyethoxy) ethoxy } ethanesulfonate ("SEG"), sodium 2- { (2- (2-hydroxyethoxy) ethoxy } ethanesulfonate ("SE 3"), and homologs thereof and mixtures thereof, and ethoxylation and sulfonation products of allyl alcohol in the presence of a suitable Ti (IV) catalyst]Ethanesulfonic acidThe product obtained by transesterification and oligomerization of sodium, DMT, sodium 2- (2, 3-dihydroxypropoxy) ethanesulfonate, EG and PG can be defined as (C)AP)₂(T)₅(EG/PG)_1.4(SEG)_2.5(B)_0.13Wherein: CAP is (Na)^+-O₃S[CH₂-CH₂O]_3.5) And B is a glyceryl unit, the EG/PG molar ratio, after complete hydrolysis, as determined by conventional gas chromatography, being about 1.7: 1.

Another class of SRA includes: nonionic terephthalates linked to polymeric ester structures using diisocyanate coupling agents, see U.S. Pat. No.4,201,824 to Violland et al and U.S. Pat. No.4,240,918 to Lagasse et al; (II) SRA having carboxylate end groups, obtained by adding trimellitic anhydride to known SRA to convert the terminal hydroxyl groups to trimellitate. By choosing the correct catalyst, trimellitic anhydride can be bonded to the end groups of the polymer through the ester of an isolated carboxylic acid of trimellitic anhydride, rather than by opening the anhydride linkage. Either nonionicor anionic SRAs may be used as starting materials, provided that they contain a hydroxyl end group which may be esterified. See Tung et al, US4,525,524. In addition, the SRA further comprises: (iii) anionic terephthalate-based SRA of the urethane-linked type, see U.S. patent No. US4,201,824 to Violland et al; (iv) poly (vinyl caprolactam), and corresponding copolymers with monomers such as vinyl pyrrolidone and/or (dimethylaminoethyl) methacrylate, including nonionic and cationic polymers, see U.S. patent nos. US4,579,681 to Ruppert et al; (V) graft copolymers obtained by grafting acrylic monomers onto sulfonated polyesters, except for the SOKALAN type from BASF corporation; these SRAs certainly have similar soil release and anti-redeposition activities to known cellulose ethers, see european patent application EP 279,134a, 1988, from Rhone-Poulenc chemie; (VI) grafts of vinyl monomers, such as acrylic acid and vinyl acetate, onto proteins (e.g.casein), see European patent application EP457,205A (1991) by BASF; (VII) polyester-polyamide SRA prepared by condensation of adipic acid, caprolactam and polyethylene glycol, which is particularly suitable for the treatment of polyamide fibres, see DE2,335,044 (1974) by Unilever N.V. company Bevan et al. Other useful SRAs are described in US4,240,918, 4,787,989, 4,525,524 and 4,877,896. Soil release/anti-redeposition agents

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

The most preferred soil removal/anti-redeposition agent is ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are further described in U.S. patent 4597898 to VanderMeer, issued on 7/1 1986. Another preferred class of soil removal/anti-redeposition agents are cationic compounds, described in European patent application 111965 to Oh and Gosselink, published on 27.6.4.1984. Other soil removal/anti-redeposition agents that can be used include: ethoxylated amine polymers described in european patent application 111984 to Gosselink, published on 27.6.4 1984; zwitterionic polymers, described in european patent application 112592 to Gosselink, published on 4.7.1984; amine oxide, described in Connor's united states patent 4548744, granted on 10/22/1985. Other soil removal/anti-redeposition agents known in the art may also be used in the present compositions. See U.S. patent 4891160 to VanderMeer, granted on month 1 and 2 of 1990, and international patent 95/32272, published on month 11 and 30 of 1995. Another preferred antiredeposition agent includes carboxymethyl cellulose (CMC) materials. Such materials are known in the art. Polymeric dispersants

In the present compositions, particularly when zeolite and/or layered silicate builders are present, it is advantageous to incorporate from 0.1% to 7% by weight of polymeric dispersant. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although other dispersants known in the art may also be used. While not being bound by theory, it is believed that the polymeric dispersing agent, in combination with other builders (including low molecular weight polycarboxylates), increases the overall detergent builder effectiveness by crystal growth inhibition, peptization of the soil particles and anti-redeposition.

Polymeric polycarboxylates can be prepared by polymerization or copolymerization of suitable unsaturated monomers, preferably in the acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconic acid, mesaconic acid, citraconic acid, and methylenemalonic acid. Suitable polymeric polycarboxylates or monomeric segments herein contain non-carboxylate groups such as vinyl methyl ether, styrene, ethylene and the like, provided that such segments do not exceed 40% by weight of the composition.

Particularly suitable polymeric polycarboxylates are derived from acrylic acid, and useful acrylic-based polymers herein are the water-soluble salts of polyacrylic acid. The average molecular weight of these polymers in the acid form is suitably 2000 to 10000, preferably 4000 to 7000, most preferably 4000 to 5000. Water-soluble salts of these acrylic polymers include, for example, alkali metal, ammonium and substituted ammonium salts. Water-soluble polymers of this type are known, for example the use of polyacrylates of this type in detergent compositions is disclosed by Diehl in us patent u.s 3308067 published 3, 7.1967.

Acrylic acid/maleic acid based copolymers may also be a preferred ingredient in the dispersant/antiredeposition agent. Such materials include water soluble salts of acrylic and maleic acid copolymers which when present in acid form have an average molecular weight of suitably 2,000 to 100,000, more preferably 5,000 to 75,000, most preferably 7,000 to 65,000. The ratio of acrylate to maleate segments in the copolymer is generally from 30: 1 to 1: 1, preferably from 10: 1 to 2: 1. Water-soluble salts of these acrylic acid/maleic acid copolymers include, for example, alkali metal salts, ammonium salts and substituted ammonium salts. Such water-soluble acrylic acid/maleic acid copolymers are also known and are described in the application numbers EP66915, 11/15, 1982 and EP193360, 9/3, 1986, which also disclose such copolymers consisting of hydroxypropyl acrylates. Other useful dispersants also include maleic/acrylic/vinyl alcohol terpolymers. These materials have also been disclosed in European patent EP193360and include acrylic acid/maleic acid/vinyl alcohol terpolymers such as 45/45/10.

Another suitable polymer is polyethylene glycol (PEG), which can exhibit dispersant properties and also act as a clay soil removal-antiredeposition agent. The molecular weight range for the above-mentioned applications is usually 500 to 100,000, preferably 1,000 to 50,000, and more preferably 1,500 to 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used, particularly in combination with zeolite builders. The average molecular weight of the dispersant such as polyaspartate is preferably 10,000. Whitening agent

Any fluorescent whitening agent or other whitening agent known in the art may be incorporated into the present detergent composition, typically at a level of from 0.01% to 1.2% by weight. Commercial optical brighteners useful in the present invention can be divided into several subclasses, including, but not limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanine, dibenzothiophene-5, 5-dioxide, pyrrole, derivatives of five and six membered heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in the production and use of Fluorescent whitening Agents (the production and Application of Fluorescent whitening Agents), author M.Zahradnik, published by John Wiley&sons.New York (1982).

A particular example of a fluorescent whitening agent useful in the compositions of the present invention is that disclosed in US4790856 filed 11/13 1988, by Wixon, the applicant. These include the PHORWHITE series of brighteners from Verona. Other whitening agents disclosed in this patent are: tinopal UNPA, Tinopal CBS and Tinopal 5BM, commercially available from Ciba-Geigy; artic White CC and Artic White CWD,2- (4-styrylphenyl) -2H-naphthol [1,2d]triazole; 4, 4' -bis (1,2, 3-triazol-2-yl) -stilbene; 4, 4' -bis (styryl) biphenyl; and aminocoumarins. Specific examples of these whitening agents include: 4-methyl-7-diethyl-aminocoumarin; 1, 2-bis (benzopyrazol-2-yl) ethylene; 1, 3-diphenylpyrazoline; 2, 5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphthol [1,2d]oxazole; and 2- (1, 2-stilbene-4-yl) -2H-naphthol [1,2d]triazole. It can also be seen in US3646015 published by Hamilton at 1972, month 2 and 29. Dye transfer inhibitors

The compositions of the present invention may also contain one or more dye transfer inhibiting agents for inhibiting the transfer of dyes between fabrics during the laundering process. Typically, such inhibitors include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanines, peroxidases, and mixtures of the foregoing. These inhibitors are generally used in amounts of 0.01% to 10%, preferably in the range of 0.01% to 5%, most preferably 0.05% to 2% by weight of the composition.

More specifically, the polyamine N-oxide polymers preferably used in the present invention contain units of the following structural formula: R-A_x-P; wherein P is a polymerizable unit to which an N-O group may be attached, or an N-O group may be part of such a unit or an N-O group may be attached to both polymerizable units; a is one of the following structures: -nc (O) -, -c (O) O-, -S-, -O-, -N =; x is 0 or 1; r is an aliphatic, ethoxylated aliphatic aromatic, heterocyclic or alicyclic group or any combination of the above groups that can be bonded to the N of the N-O group or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof. The N-O group can be represented by the following general formula:

wherein R is₁,R₂,R₃Is an aliphatic, aromatic, heterocyclic or alicyclic group or a combination thereof; x, y, z are 0 or 1; n of the N-O groups may be attached to any of the above groupsAttached to or forming part of the above groups; the amine oxide units of the polyamine N-oxides have a pKa of<10, preferably a pKa of<7, more preferably a pKa of<6.

Any polymer backbone can be used so long as the amine-oxide polymer formed is water soluble and has dye transfer inhibition. Suitable polymer backbones are for example: polyethylene, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate, and mixtures thereof. These polymers include random or block copolymers where one monomer is an amine N-oxide and the other monomer is an N-oxide. The ratio of amine to amine N-oxide in the amine N-oxide polymer is typically from 10: 1 to 1: 1,000,000. However, the number of amine oxide groups in the polyamine oxide polymer can vary with the appropriate copolymerization or the appropriate degree of N-oxidation. Polyamine oxides can be obtained at almost any degree of polymerization, and generally have an average molecular weight of 500 to 1,000,000, preferably 1,000 to 500,000, and most preferably 5,000 to 100,000. This class of preferred substances is known as "PVNO".

In the present cleaning compositions, the most suitable polyamine N-oxide is poly (4-vinylpyridine-N-oxide), having an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1: 4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferably used (classified as PVPVI class). Typically, the PVPVI has an average molecular weight of from 5,000 to 1,000,000, preferably from 5,000 to 200,000, most preferably from 10,000 to 20,000 (the average molecular weight is in the range determined by light scattering Methods, as described by Barth et al, chemical analysis, Vol.113, Modern Methods of Polymer Properties, the disclosure of which is incorporated herein by reference.) in PVPVPVPVI, the molar ratio of N-vinylimidazole to N-vinylpyrrolidone is typically from 1: 1 to 0.2: 1, preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4: 1, these copolymers may be linear or branched.

The compositions of the present invention may also contain polyvinylpyrrolidone (PVP) having an average molecular weight of 5,000 to 400,000, preferably in the range of 5,000 to 200,000, and most preferably 5,000 to 50,000. PVP is well known to those skilled in the detergent art. See, for example, EP-A-262897 and EP-A-256696 (see references herein). The PVP-containing composition may further contain polyethylene glycol (PEG) having an average molecular weight of from 500 to 100,000, preferably 1,000 to 10,000. The ratio of PEG to PVP in ppm added to the wash solution is generally from 2: 1 to 50: 1, preferably from 3: 1 to 10: 1.

The detergent compositions may optionally also incorporate from 0.005% to 5% by weight of certain types of hydrophilic fluorescent whitening agents which also inhibit dye transfer. When used, it is preferably 0.01 to 1% by weight based on the weight of the composition.

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

wherein R is₁Selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; r₂Selected from the group consisting of N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro, amino; m is a salt-forming cation, e.g. Na⁺Or K⁺。

When R is₁Is anilino, R₂Is N-2-bis-hydroxyethyl, M is a cation such as Na⁺The whitening agent is 4, 4' -bis [ (4-anilino-6- (N-2-bis-hydroxyethyl) -1,3, 5-triazin-2-yl) amino group]-2, 2' -stilbenedisulfonic acid and disodium salt. This brightener is sold by Ciba-Geigy under the trade name Tinapol-UNPA-GX. Tinapol-UNPA-GX is a preferred hydrophilic optical brightener for use in the present cleaning compositions.

When R is₁Is anilino, R₂Is N-2-hydroxyethyl-N-2-methylamino, M is a cation such as Na⁺The whitening agent is 4, 4' -bis [ (4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -1,3, 5-triazin-2-yl) amino group]2, 2' -stilbene disulfonic acid disodium salt, which is also sold by the company Ciba-Geigy under the trade name Tinapol 5 BM-GX.

When R is₁Is anilino, R₂Is morpholino, M is a cation such as Na⁺The whitening agent is 4, 4' -bis [ (4-anilino-6-morpholino-1, 3, 5-triazin-2-yl) amino group]2, 2' -stilbene disulfonic acid disodium salt, which is also sold by the company Ciba-Geigy under the trade name Tinapol AMX-GX.

The particular optical brighteners selected for use in the present invention produce a very effective dye transfer inhibiting effect when used in combination with a polymeric dye transfer inhibiting agent selected as hereinbefore described. The use of selected polymers (e.g., PVNO and/or PVPVI) in combination with selected optical brighteners (e.g., Tinapol-UNPA-GX, Tinapol 5BM-GX and Tinapol AMX-GX) in aqueous wash solutions provides better dye transfer inhibition than either alone. Without being bound by theory, it is believed that such brighteners work in this manner because they have a high affinity for fabrics in the wash liquor and therefore adhere relatively quickly to such fabrics. The degree of adhesion of the whitening agent to the fabric in the wash liquor can be determined by the "exhaustion coefficient". The exhaustion coefficient is generally the ratio of a) the brightener that is attached tothe fabric to b) the original concentration of brightener in the wash liquor. Brighteners with a relatively high exhaustion coefficient are most useful in the present invention to inhibit dye transfer.

It will of course be appreciated that other types of conventional optical brightener compounds may optionally be used in the compositions of the present invention to produce a general fabric "whitening" effect, rather than a true dye transfer inhibition. Such use is conventional and known in detergent formulations.

Chelating agents

The detergent may also optionally contain one or more iron and/or manganese chelating agents. These chelating agents may be selected from the group consisting of: aminocarboxylates, aminophosphonates, multifunctional substituted aromatic chelating agents and mixtures thereof, all of which are explained in detail below. It is believed that the advantages of these materials are due in part to their specific ability to remove iron and manganese ions from the wash liquor by forming soluble chelates, which is not to be limited by theory.

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

Amino phosphonates may also be suitable chelating agents for use in the compositions of the present invention when at least low levels of total phosphorus are permitted in the cleaning composition, including ethylenediaminetetra (methylene phosphonates) such as DEQUEST. These aminophosphonates preferably do not contain alkyl or alkenyl groups having more than 6 carbon atoms.

Also useful in the compositions of this patent are multi-functionally substituted aromatic chelating agents, see U.S.3,812,044 issued by Connor et al, 5/21, 1974. Such compounds in acid form are preferably dihydroxydisulfobenzenes, such as 1, 2-dihydroxy-3, 5-disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylenediamine disuccinate ("EDDS"), particularly the [ S, S]isomer described in U.S.4,704,233 issued by Hartman and Perkin et al, 12.3.1987.

The compositions of the present patent may also contain a water-soluble methylglycinediacetic acid (MGDA) salt (or in acid form) as a chelating agent or in combination with other insoluble co-builders, such as zeolites, layered silicates.

If such chelating agents are used, they are generally present in the cleaning compositions in an amount of from 0.1% to 15% by weight, more preferably from 0.1% to 3.0% by weight.

Foam inhibitor

Compounds which reduce or inhibit foam formation may be added to the compositions of the present invention, the foam inhibition being extremely weight intensive in the so-called "high intensity cleaning process" and in the front-loading european-style washing machines described in US4,489,455 and US4,489,574.

A wide variety of materials can be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer encyclopedia, third edition, volume 7, pages 430-447 (John Wiley&Son, 1979). A very important class of foam inhibitors comprises monocarboxylic fatty acids and soluble salts thereof. See U.S. patent 2,954,347, Wayne st.john 1960, 9, 27. Monocarboxylic fatty acids and salts thereof useful as suds suppressors generally contain a hydrocarbon chain of from 10 to 24 carbon atoms, preferably from 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium, lithium and ammonium salts and alkanolammonium salts.

The cleaning compositions may also contain non-surfactant suds suppressors. Including, for example: high molecular weight hydrocarbons such as paraffinic hydrocarbons, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic ketones containing 18 to 40 carbon atoms (e.g., sterones), and the like. Other suds suppressors include N-alkylated aminotriazines such as tri-to hexaalkylmelamines or di-to tetra alkyldiamine chlorotriazines, which are formed from cyanuric chloride with 2 or 3 moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearoyl phosphates such as monostearoyl alcohol phosphate and monostearoyl di-alkali metal (e.g., K, Na and Li) phosphates and phosphates. Hydrocarbons, such as paraffins and halogenated paraffins, can be used in liquid form. The liquid hydrocarbon is a liquid at room temperature and one atmosphere pressure, has a solidification point in the range of-40 ℃ to 50 ℃ and a minimum boiling point of not lower than 110 ℃ (one atmosphere pressure). It is also known to use waxy hydrocarbons, the melting point of which is preferably below 100 ℃. Hydrocarbons constitute a preferred class of suds suppressors in detergent compositions. Hydrocarbon foam inhibitors have been described, for example, in U.S. Pat. No. 5,4,265,779 issued to Gandolfo et al, 5.5.1981. And hydrocarbons include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons containing 12 to 70 carbon atoms. In the discussion of the foam inhibitor, the term "paraffin" is used to mean a mixture comprising true paraffins and cyclic hydrocarbons.

Another preferred class of non-surfactant suds suppressors comprises silicone suds suppressors. Such foam inhibitors include mixtures of polyorganosiloxane with silica particlesusing polyorganosiloxane such as polydimethylsiloxane, suspension or emulsion of polyorganosiloxane oil or resin, polyorganosiloxane chemisorbed or fused to silica. Silicone suds suppressors are well known in the art, see, for example, U.S. patent No. US4,265,779 issued on 5.5.1981 and european patent application No. 89307851.9 issued on 2.7.1990 in Gandolfo and Starch m.s..

Other silicone foam inhibitors are disclosed in U.S. Pat. No. 3,455,839, which is directed to compositions and methods for defoaming aqueous solutions by adding a small amount of polydimethylsiloxane fluid to the aqueous solution.

Mixtures of polysiloxanes and silanized silicas are also described, for example, in German patent application DOS 2,124,526. Silicone antifoams and foam control agents in granular detergent compositions are disclosed in U.S. Pat. No. 3,933,672 to Bartolotta et al and U.S. Pat. No.4,652,392 to Baginski et al, 24.3.1987.

Typical silicone foam inhibitors for use herein are a class of foam control agents which inhibit the amount of foam used and consist essentially of:

polydimethylsiloxane fluids having a viscosity of from 20cs to 1,500cs at 25 ℃

(ii) from about 5 to about 50 parts by weight per 100 parts by weight of (i) of a polysiloxane resin, of (CH)₃)₃SiO_1/2Unit and SiO₂Unit composition, (CH)₃)₃SiO_1/2Unit and SiO₂The ratio of units is from about 0.6: 1 to 1.2: 1; and is

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

In the preferred foam inhibitors herein, the solvent of the continuous phase consists of certain polyethylene glycol or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferably) or polypropylene glycol. The primary silicone suds suppressor is branched/crosslinked, preferably non-linear.

To further illustrate this point, typical liquid laundry suds control compositions may optionally contain from about 0.001% to about 1%, preferably from about 0.01% to about 0.7%, and most preferably from about 0.05% to about 0.5% by weight of the above-described silicone suds suppressors. These polysiloxanes comprise (1) a non-aqueous emulsion of a primary defoamer which is a mixture of the following (a), (b), (c) and (d): (a) polyorganosiloxane, (b) resinous siloxane or polysiloxane compound which produces a polysiloxane resin, (c) finely divided filler and (d) a catalyst which promotes the reaction of the mixture of (a), (b) and (c) to form silanolate; (2) at least one nonionic silicone surfactant and (3) a polyethylene glycol or polyethylene-polypropylene glycol copolymer having a solubility in water at room temperature of about 2% and being free of polypropylene glycol. Similar amounts may be used in granular composition gels and the like, see also U.S. Pat. No.4,978,471 issued to Starch on month 18, 1990 and 4,983,316 issued to Starch on month 8, 1991, Huber et al U.S. Pat. No. 5,288,431 on month 22, 1994, and Aizawa et al U.S. Pat. Nos. 4,639,489 and 4,749,740, column 1, line 46 through column 4, line 35.

The silicone suds suppressors herein preferably comprise polyethylene glycol and polyethylene/polypropylene glycol copolymers, both having an average molecular weight of less than about 1,000, more preferably between 100 and 800. The solubility of polyethylene glycol and polyethylene/polypropylene glycol copolymers herein in water at room temperature is greater than about 2% by weight, preferably greater than about 5% by weight.

Preferred solvents herein are polyethylene glycols having an average molecular weight of less than about 1,000, preferably in the range of about 100-800, and most preferably between 200 and 400; and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. The ratio by weight of polyethylene glycol to polyethylene glycol/polypropylene glycol copolymer is preferably from about 1: 1 to 1: 10, more preferably from 1: 3 to 1: 6.

The silicone foam inhibitors preferably used here do not contain polypropylene glycol, in particular polypropylene glycol with a molecular weight of 4,000. It is also preferably free of block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101.

Other useful suds suppressors for use herein include secondary alcohols (e.g., 2-alkyl alkanols and mixtures of these alcohols with silicone oils, such as the silicones disclosed in U.S. Pat. Nos. 4,798,679 and 4,075,118 and EP 150,872₁-C₁₆C of the chain₆-C₁₆An alkanol. Preferably 2-butyloctanol, commercially available from Condea under the trademark ISOFOL 12. A mixture of secondary alcohols is commercially available from Enichem under the trademark ISALCHEM 123. The foam inhibitor mixture generally contains alcohol and polysiloxane in a weight ratio of 1: 5 to 5: 1.

For all washing compositions used in automatic washing machines or dishwashers, the formation of foam should not exceed a certain range, so that it overflows the washing machine or has a negative effect on the washing mechanism of the dishwasher. The foam-suppressor is preferably used in the "foam-suppressing amount". By "foam-suppressing amount" is meant that the composition formulator selects an amount of such foam-suppressing agent that will provide adequate control of the foam. To obtain a low-foaming laundry or dish washing agent which can be used in an automatic washing machine or a dish washing machine.

The present compositions typically contain from 0% to 10% foam inhibitor. When used as suds suppressors, the monocarboxylic fatty acids and salts thereof are generally used in amounts up to 5%, preferably from 0.5% to 3%, by weight of the detergent composition, of the fatty monocarboxylic acid salt suds suppressor. Silicone suds suppressors are generally used in amounts up to 2.0% by weight of the detergent composition, although higher concentrations may also be used. This upper limit is, in fact, a practical concern since it is first of all considered to keep costs to a minimum and to keep the dosage high in efficiency in order to effectively control foaming. The silicone suds suppressor is preferably used in an amount of from 0.01% to 1%, preferably from 0.25% to 0.5%. As used herein, these weight percent values include all silicas useful in combination with polyorganosiloxanes, as well as any optional materials. The monostearyl phosphate foam inhibitors are generally used in amounts of 0.1% to 2% by weight of the composition. Hydrocarbon foam inhibitors are generally used in amounts of 0.01% to 5%, although higher concentrations can also be used. Alcohol suds suppressors typically comprise from 0.2% to 3% by weight of the finished composition.

Alkoxylated polycarboxylates

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are highly useful herein to provide additional grease removal capability. These materials are described on page 4 and later, et al, of WO 91/08281 and PCT90/01815, which are incorporated herein by reference.

From a chemical structural point of view, these materials comprise polyacrylates having one ethoxy branch per 7-8 acrylate units. The side chain has the formula- (CH)₂CH₂O)_m(CH₂)_nCH₃M is equal to 2-3 and n is equal to 6-12. The side chains are attached to the polyacrylate backbone via ester linkages, resulting in a "comb" polymer structure. The molecular weight can vary, but is typically between 2,000 and 50,000. The composition may contain 0.05 to 10% by weight ofSuch alkoxylated polycarboxylates.

Fabric softener

Various fabric softeners which undergo the entire process of laundering, especially the fine smectite clays of Storm and Nirsclal, U.S. patent No.4,062,647 issued on 1977, 12/13, and other softener clays known in the art, can be used optionally, and generally at levels of from 0.5% to 10% by weight can function as a fabric softener in the compositions of the present invention while cleaning the fabric. Clay softeners may be used with amines and cationic softeners as disclosed, for example, in U.S. patent No.4,375,416 issued by Crisp et al on 3/1 1983 and U.S. patent No.4,291,071 issued by Harris et al on 22/9 1981.

Perfume

The flavor and fragrance components that are very useful in the present compositions and processes include a wide variety of natural and synthetic chemical ingredients, including but not limited to: aldehydes, ketones, esters. Also included are various natural extracts and essences, which are complex mixtures of many ingredients, such as orange oil, lemon oil, rose juice extract, lavender, musk, patchouli, balsamine, sandalwood oil, pine oil, and cedar. Finished perfumes are typically present at levels of from 0.01% to 2% by weight of the detergent composition, and the odoriferous components may be present at levels of from 0.0001% to 90% of the finished perfume composition.

Many useful fragrance ingredients herein include, but are not limited to, 7-acetyl-1, 2,3,4,5,6,7, 8-octahydro-1, 1,6, 7-tetramethylnaphthalene, methyl ionone, gamma-methyl ionone, methyl cedryl ketone, methyl dihydrojasmonate, methyl 1,6, 10-trimethyl-2, 5, 9-cyclododecatrien-1-yl ketone, 7-acetyl-1, 1,3,4,4, 6-hexamethyltetralin, 4-acetyl-6-tert-butyl-1, 1-dimethylindane, p-hydroxy-phenyl-butanone, benzophenone,methyl- β -naphthalenone, 6-acetyl-1, 1,2,3,3, 5-hexamethylindane, 5-acetyl-3-isopropyl-1, 1,2, 6-tetramethylindane, 1-dodecanal, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexene-1-yl-1-hydroxy-1-cinnamyl-1-yl-1-hexahydro-1, 7, 6-dimethylvaleraldehyde, 2, 7-methylhexanoaldehyde, 7-hexadecyl-1, 1,2, 6-dimethylvaleraldehyde, 7-hexahydro-2, 7-1, 7-methyl-hexadecyl-1, 6-1, 7-methyl-2, 7-hexadecyl-1, 6-decalin-yl-2, 7, 6-decarenyl-methyl-carbaldehyde, 7-methyl-ethyl-2, 7-methyl-decahexenyl-2, 7-2, 4- (2, 6-methyl-ethyl-methyl-decalin-ethyl-2, 7-methyl-2, 7-ethyl-methyl-2, 7-methyl-2, 8-methyl-ethyl-methyl-decalin-ethyl-decalin-ethyl-1, 4-2, 7-2, 4-ethyl-2, 7-2, 7-ethyl-2-methyl-ethyl-2, 7-ethyl-2-ethyl-methyl-2-methyl-ethyl-2-methyl-2-ethyl-2-ethyl-decalin-ethyl-2, and condensation products of hexahydro-2.

The most suitable perfumes should be capable of maximizing the odor of finished cellulase-containing compositions, and include, but are not limited to, hexylcinnamaldehyde, 2-methyl-3- (p-tert-butylphenyl) -propionaldehyde, 7-acetyl-1, 2,3,4,5,6,7, 8-octahydro-1, 1,6, 7-tetramethylnaphthalene, benzyl salicylate, 7-acetyl-1, 1,3,4,4, 6-hexamethyltetralin, cyclohexyl p-tert-butylacetate, methyl dihydrojasmonate, β -naphthylmethyl ether, methyl- β -naphthalenone, 2-methyl-2- (p-isopropylphenyl) -propionaldehyde, 1,3,4,6,7, 8-hexahydro-4, 6,6,7,8, 8-hexamethyl-cyclopentane-gamma-2-benzopyran, dodecahydro-3 a,6,6,9 a-tetramethylnaphtho [1,2d]furan, anisaldehyde, cedrol, tricyclopentadecane acetate, tricyclodecenyl decanoate, and tricyclodecenyl anhydride.

Other fragrances include perfume oils, perfume resins and resins of various origins. Including (but not limited to): peru balsam, mastic resin, benzoin, rosa resin, nutmeg, cinnamon oil, benzoin resin, coriander oil and hybrid lavender. Still other fragrance compounds include phenethyl alcohol, terpineol, linalool, picryl acetate, geraniol, nerol, 2- (1, 1-dimethylethyl) -cyclohexanol acetate, benzyl acetate, and eugenol. A carrier, such as diethyl phthalate, may also be added to the finished fragrance composition.

Other ingredients

Various other ingredients useful in detergent compositions may be included in the present compositions, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers as required for bar compositions, and the like. If high foaming is desired, the composition will typically incorporate from 1% to 10% of a foam booster, such as an alkanolamide having from 10 to 16 carbon atoms. Monoethanol and diethanolamides of 10 to 14 carbon atoms are a typical class of these suds boosters, and it would also be beneficial to use these suds boosters with optional high foaming surfactants such as the aforementioned amine oxides, betaines and sultaines. If desired, water-soluble magnesium and/or calcium salts, such as MgCl, may also be added₂、MgSO₄、CaCl₂、CaSO₄Generally, the amount added is 0.1% to 2% to produce more foam and enhance grease removal.

Various optional detergent ingredients may be added to the composition to adsorb onto the porous hydrophobic material, which is then further stabilized by coating the hydrophobic material with a hydrophobic coating. The detergent ingredients are preferably mixed with the surfactant prior to adsorption onto the porous substrate. In use, the detergent component is released from the matrix into the aqueous wash solution to perform a washing function.

To elaborate this technique, a protease solution containing 3% to 5% of an ethoxylated alcohol (EO7) nonionic surfactant having 13 to 15 carbon atoms was mixed with porous hydrophobic silica (trademark SIPERNAT D10, DeGussa). Typically, the enzyme/surfactant solution weighs 2.5 times the weight of the silica gel. The obtained powder was dispersed in a silicone oil (various silicone oils having a viscosity of 500 to 12,500 can be used) by stirring. The resulting silicone oil dispersant is emulsified or otherwise added to the final detergent base. By this means, the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, optical brighteners, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid laundry detergents.

Liquid detergent compositions may contain water and other liquid solvents as carriers. Low molecular weight primary or secondary alcohols, such as methanol, ethanol, propanol, and isopropanol, are well suited. Preferably, the surfactant is dissolved with a monohydric alcohol, but polyols such as those containing 2 to 6 carbon atoms and 2-6 hydroxyl groups (e.g., 1, 3-propanediol, ethylene glycol, glycerol, and 1, 2-propanediol) may also be used. These carriers may be present in an amount of from 5% to 90%, typically 10% to 50%.

The cleaning compositions are preferably formulated for use in aqueous cleaning operations with the wash water having a pH of from 6.5 to 11, more preferably from 7.5 to 10.5, and the liquid dishwashing formulation preferably has a pH of from 6.8 to 9.0. Laundry detergents are generally at pH 9-11. Methods for controlling the pH at the suggested values include the use of buffers, bases, acids, and the like, as is well known to those skilled in the art.

Production of granules

The bis-alkoxylated cation of the present invention is added to the mixer mixture and then conventionally spray dried to help remove any remaining malodorous short chain amine contaminants that may be present. In such cases, formulators have devised a blend of granules containing the alkoxylated cationic surfactant for use in, for example, high density granular detergents, preferably where the granular composition is not strongly alkaline. The preparation of high density (greater than 650g/L) granules is described in detail in US patent 5,366,652. The resulting granules are effective at pH9 or below 9 to avoid the off-flavors of impure amines. This can be achieved by adding small amounts of acidic substances such as boric acid, citric acid or the like or suitable pH buffers to the particles. In another approach, perfume components may also be used as described herein to mask possible problems with amine odors.

Examples

In the following examples, the abbreviations for the various ingredients used in the compositions have the following meanings.

Anionic surface of alkylbenzenesulfonate having an average LAS chain length of 11.5 carbon atoms

Active agent, preferably sodium salt

Primary alkylsulfate anions having an average AS chain length of 14 to 15 carbon atoms

Surfactants, preferably sodium salts

Ethoxylation of 12-15 carbon atoms with NI average EO9 ethoxylation degree

Alcohols (nonionic surfactant)

SKS-6 layered silicates, e.g. Hoechst

Copolymer sodium salt of copolymer of acrylic acid and maleic acid

Zeolite A of zeolite 1 to 10 μm

PEG4000 polyethylene glycol; average molecular weight is 4000

NOBS nonanoyloxy benzene sulfonate bleach activators

PB-1 sodium perborate monohydrate

Protease washing enzymes which decompose proteins as described above; including BIOSAM3.0

Detergent enzymes foramylase hydrolysis of starch

SRA-1 soil release agent; methyl cellulose; molecular weight of 13000 or so, and

degree of substitution 1.8-1.9

Soil release agent in SRA-2 US 5415807

Brightener X Tinopal CBS _ X; stilbene biphenyl disulfonate;

Ciba-Geigy

whitening agent Y Tinopal UNPA-GX; cynauric chloride/diaminostilbenes;

Ciba-Geigy

foam control agent silica/silicone foam inhibitor

The following examples are illustrative of the present invention and are not intended to limit or define the scope thereof. All parts, percentages and ratios are expressed as weight percent unless otherwise indicated.

Granular detergents are as in examples a and B below.

Example A

Weight percent (%) ppm of the component

Surface active agent

LAS 21.47 143.20

AS 6.55 43.69

NI 3.30 22.01

CocoMeEO2^*0.473.13 alkaline builder

SKS-6 3.29 21.94

Copolymer 7.1047.36

Zeolite 8.4056.03

PEG4000 0.19 1.27

Sodium carbonate 17.84118.99

Silicate (2.0R) 11.4076.04

Whitening agent

NOBS 4.05 27.01

PB-1 3.92 26.15

Enzyme

Protease 0.855.67

Amylase 1.208.00 others

SRA-1 0.26 1.73

SRA-2 0.26 1.73

Whitening agent X0.211.40

Whitening agent Y0.100.67

Hydrophobic silica 0.302.00

Foam inhibitor 0.171.13

Sodium sulfate 5.1434.28

Fragrance 0.251.67

The surfactant AQA-1(CocoMeEO2) in the example can be used in equal amount of AQA-2 in the case of 100667.00 dosage-20 g/30L total amount of water and miscellaneous 3.2821.88

-any one of AQA-22 or other AQA surfactants herein.

Example B Components weight percent (%) ppm surfactant

LAS 21.47 143.20

AS 6.55 43.69

NI 3.30 22.01

CocoMeEO2^*0.473.13 alkaline builder

SKS-6 3.29 21.94

Copolymer 7.1047.36

Zeolite 8.4056.03

PEG4000 0.19 1.27

Sodium carbonate 19.04127.00

Silicate (2.0R) 11.4076.04

Whitening agent

NOBS 4.05 27.01

PB-1 3.92 26.15

Enzyme

Protease 0.855.67

Others

SRA-1 0.26 1.73

SRA-2 0.26 1.73

Whitening agent X0.211.40

Whitening agent Y0.100.67

Hydrophobic silica 0.302.00

Foam inhibitor 0.171.13

Sodium sulfate 5.1434.28

Fragrance 0.251.67

Moisture and miscellaneous items 3.2821.88

Total amount 100667.00

In this example the bis-AQA-1 (CoCoMeEO2) surfactant may be replaced with an equivalent amount of one of bis-AQA-2 to bis-AQA-22 or other bis-AQA surfactants.

The following examples illustrate the results of laboratory procedures and tests conducted on a variety of soils and stains using compositions within the scope of the present invention, and it will be seen from the data that the cleaning power on a wide variety of fabrics is improved on a wide variety of soils and stains.

Procedure for Performance testing

Preparation of samples

The preparation of the sample essentially comprises the following steps:

1. preparation of premixed LAS + AS.

2. Preparation of premixed LAS + AS + cationic surfactant.

3. Preparation of a number of nonionic (AE) surfactants.

4. Preparation of builder solution

5. Preparation of particulate matter.

Surfactant (b):

surfactant weight^*gms% active Wash concentration (ppm)

LAS 78.85 44.50 143.20

AS 34.55 31.00 43.70

Cationic surfactant 01.9040.003.10

AE 19.44 100.00 22.00

Actual weight and percent Activity

The preparation steps of the product for performance detection are as follows:

step I:

the surfactants were weighed and mixed as follows

1. Called 78.85gm LAS.

2. Again 34.55gm AS was added to the same beaker.

3. 498.10ml of distilled water was added to the mixture of LAS and AS.

4. Pre-mix LAS and AS until completely dissolved and heat at 40 ℃ for about 30 minutes until completely dissolved.

Step II:

1. 01.90gm of the cationic surfactant of the present invention was added to the same beaker containing LAS and AS solutions in a pre-mix.

2. The total volume of the solution at this time was 500 ml.

This 500ml surfactant mixture was effectively washed 5 times using 100ml of this batch per wash. When 49 liters of tap water was added to this 100ml solution, the respective washing concentration of each surfactant was determined.

Step III:

1. individually called 19.44gm AE.

2. To AE 900ml of distilled water was added.

3. This 900ml solution was effectively washed 18 times.

4. 50ml of this solution was used for each wash.

Step IV:

silicate salt: 148.32gm in every 900ml of distilled water; 50ml of this solution was used for each wash.

Copolymer (b): 92.88gm in every 900ml of distilled water; 50ml of this solution was used for each wash.

Particulate matter: each granular component was weighed out and placed in the same beaker separately.

Sequence of addition to the washing machine:

the components were added with stirring in the following order:

1. silicate (2.0R).

2. Copolymers (as described above).

3. A particulate material.

Where the agitation is stopped (to avoid foaming upon addition of surfactant).

LAS + AS + cationic surfactant solution.

AE solution.

Stir for 15 seconds.

Hardness: there was no additional hardness added at tap water hardness.

Carrying: usually, 2.4Kg or less of the washed load is used.

Shirt made of cotton (1)

Old T-shirt (from the panel of a panel reader) (3)

Big T-shirt (11)

DKPE T-shirt (1)

P/C pants (2)

Cotton shorts (1)

DKPE is a polyester knit.

DMO is dirty motor oil.

Test results I are shown below, which show the properties of the compositions according to the invention using coconut MeEO2 plus LAS, AS mixture. Test result II shows the performance of using coconut MeEO10 plus LAS/AS compared to coconut MeEO 2/LAS. Performance in the tests was measured for various soils, i.e. body soils, builder sensitive soils, bleach sensitive soils, surfactant sensitive soils and socks. The terms "bis", "EO 10" herein indicate two polyethylene oxide chains having a total average of 10 ethylene oxide units in the molecule, typically (but not limited to) about 5 per chain.

Test results I

With LAS and AS (total anion system) and

coconut MeO2 cationic surfactant was premixed

Fouling test I test II average

Old collar-0.02-0.27-0.15

Inlay collar 0.77S 0.73S 0.75

Cuff-0.170.330.08

filth-0.10.17S 0.04

Body filth (average) 0.120.240.18

Clay C/D1.03S 0.7S 0.87

Clay DKPE 0.7S-0.020.34

Sensitive to builders

Fouling (average) 0.870.340.61

Spinach 0.330.560.45

Coffee 0.210.42S 0.32

Sensitive to bleaching agents

Fouling (average) 0.270.490.38

Meat paste 0.84S 1.08S 0.96

Curry 1.14S 1.11S 1.13

Smoked meat oil 0.10.160.13

DMO 0.44 -0.34 0.05

Sensitive to surfactants

Perceived soil (average) 0.630.50.57

Average (including socks) 0.390.380.39

Socks (front) 0.320.35A 0.34

Socks (rear) 0.080.64A 0.36

Socks (. delta. -0.240.280.02)

Test results I

Coconut MeEO2 cationic surfactant and LAS separate mixed soil test I test II average old collar 0.27-0.73-0.23 collar-0.040.150.06 cuff-0.35-0.25-0.30 filth 0.130.51S 0.32 body filth (average) 0.00-0.08-0.04 clay C/D0.590.79S 0.69 clay DKPE 0.040.660.35 builder sensitive soil (average) 0.320.730.53 spinach 0.070.580.33 coffee 0.240.240.24 bleach sensitive soil (average) 0.160.410.29 meat paste-0.1-0.08-0.09 curry 0.10.540.32 smoked meat oil-0.53-0.02-0.28 DMO-0.220.05-0.09 surfactant sensitive soil (average) -0.190.12-0.04 average (including sock before) 0.040.190.12 sock (before) 0.33-0.070.13 sock (after) 0.7S-0.050.33 sock (delta) 0.360.020.19

Test results II

Coconut MeEO2 cationic surfactant and LAS + AS Mixed soil test I test II average old collar 0.48-0.020.23 inserted collar 0.020.060.04 cuff 0.330.250.29 filth-0.280.11-0.09 body soil (average) 0.140.100.12 clay C/D0.75S 0.440.60 clay DKPE 0.27-0.47-0.10 detergent sensitive soil (average) 0.51-0.020.25 spinach 0.000.330.17 coffee 0.380.82S 0.60 detergent sensitive soil (average) 0.190.580.39 meat sauce 0.050.96S 0.51 curry 0.420.91S 0.67 bacon oil 0.23-0.070.08 DMO 0.31-0.130.09 surfactant sensitive soil (average) 0.250.420.34 sock (front) 0.140.230.19 sock (back) -0.190.48S 0.15 sock (delta) -0.320.25-0.04.04 detergent sensitive soil (average) 0.250.420.34 sock (front)

Test results II coconut MeE10 cationic surfactant and LAS were separately premixed to soil used collar 0.17 collar insert-0.52 cuff 0.19 soil-0.17 personal soil (average) -0.08 clay C/D-0.34 clay DKPE 0.09

Builder sensitive soil (on average) -0.13

Spinach 0.06

Coffee 0.08

Bleach sensitive soil (average) 0.07

Meat paste-0.20

Curry-0.38

Smoked meat oil-0.33

DMO -0.33

Surfactant-sensitive soil (average) -0.31

Average (including socks) -0.11

Socks (front) 0.42S

Socks (rear) 0.64S

Socks (. delta.) 0.22

The following examples are illustrative of this patent and are not meant to limit or define its scope. All parts, percentages and ratios used herein are expressed as weight percent unless otherwise indicated.

In the following examples, the abbreviations for the various ingredients used in the compositions have the following meanings.

LAS straight chain C₁₂Sodium alkyl benzene sulfonate

TAS tallow alkyl sodium sulfate

C45AS C_14-15Linear alkyl sodium sulfate

CxyEzS C_1x-C_1yCondensation of branched sodium alkyl sulfates with z moles of ethylene oxide

C45E7 C_14-15Predominantly linear primary alcohols with an average of 7 moles of ethylene oxide

Condensation of

C25E3 C_12-15Condensation of branched primary alcohols with an average of 3 moles of ethylene oxide

C25E5 C_12-15Condensation of branched primary alcohols with an average of 5 moles of ethylene oxide

Coconut EO 2R₁N⁺(CH₃)(C₂H₄OH)₂Wherein R is₁Is C_12-14

Soap straight chain alkylcarboxy derived from 80/20 tallow coconut oil mixture

Sodium salt

TFAA C_16-18Alkyl N-methylglucamides

TPKFA C_12-14Full cut fatty acid overhead fraction

STPP anhydrous sodium tripolyphosphate

Zeolite a hydrated sodium aluminosilicate of molecular formula Na₁₂(AlO₂SiO₂)₁₂·27H₂O，

The size of the primary particles is 0.1-10 μm

Crystalline layered silicate delta-Na of NaSKS-6₂Si₂O₅

Citric acid Anhydrous citric acid

Carbonate anhydrous sodium carbonate with particle size of 200-

Bicarbonate anhydrous sodium bicarbonate with particle size of 400-

Silicate amorphous sodium Silicate (SiO)₂∶Na₂O=2.0)

Anhydrous sodium sulfate

Citrate trisodium citrate dihydrate, Activity 86.4%, particle distribution

425-850μm

MA/AA 1: 4 maleic acid/acrylic acid copolymer with an average molecular weight of 70,000

CMC sodium carboxymethyl cellulose

Protease proteolytic enzyme, activity 4KNPU/g, trade name Savinase,

NOVO Industries A/S

Alcalase proteolytic enzyme, activity 3AU/g, NOVOIndustries A/S

Sell it

The cellulase hydrolyzes the cellulase with the activity of 1000 CEVU/g,

sold under the trade name Carezyme, NOVO Industries A/S

Amylase hydrolysis of Amylase with an Activity of 60 KNU/g, trade name Termamy

160T, NOVO Industries A/S

Lipase hydrolyzes lipase with activity of 100 KLU/g, trade name Lipolase,

NOVO Industries A/S

Endoglucanase, activity 3000 EVU/g, NOVO Industries

Sale of A/S

PB4 sodium perborate tetrahydrate, general formula NaBO₂.3H₂O.H₂O₂

PB1 anhydrous sodium perborate bleach of the general formula NaBO₂.H₂O₂

Percarbonate sodium percarbonate of the general formula 2NaCO₃.3H₂O₂

Nobs sodium nonanoyloxybenzenesulfonate

TAED tetraacetylethylenediamine

NACA-OBS (6 nonanoylaminocaproyl) oxybenzenesulfonate

DTPMP diethylene triamine penta (methylene phosphonate)

Cobalt catalyst pentamine cobalt (III) acetate salt

Manganese catalyst Mn^Ⅳ ₂(m-o)₃(1,4, 7-trimethyl-1, 4, 7-triazacyclo

Nonane)₂-(PF₆)₂Such as US 5246621 and 5244594

The above-mentioned

Photosensitizers of sulfonated zinc phthalocyanines encapsulated in bleached dextrin-soluble polymers

Brightener disodium 14, 4' -bis (2-sulfostyryl) biphenyl

Brightener 24, 4' -bis (4-anilino-6-morpholino-1, 3,5-

Triazin-2-yl) amino) 1, 2-stilbene-2, 2' -disulfonic acid bis

Sodium salt

HEDP 1, 1-HYDROXYETHYL DIPHOSPHONIC ACID

PVNO polyvinylpyridine N-oxide

Copolymers of PVPVI polyvinylpyrrolidone and vinylimidazole

SRA1 sulfobenzoyl end-capped with oxyethylene oxy and p-phenylene groups

Esters of diacyl skeletons

SRA2 diethoxylated poly (1, 2-propylene terephthalate) Breit Block

Segmented polymers

Polysiloxane antifoam polydimethylsiloxane foam control agents and silicon as dispersing agent

Ratio of the alkylene oxide to the foam control agent to the dispersing agent

Is 10: 1 to 100: 1

In the following examples, all contents are expressed as weight percent (%) of the composition

Example 1

Detergent formulations were prepared according to the invention wherein A and C were phosphorus-containing detergent compositions and B was a zeolite-containing detergent composition.

A B C

Blown powder

STPP 24.0 - 24.0

Zeolite A-24.0-

C45AS 8.0 5.0 11.0

MA/AA 2.0 4.0 2.0

LAS 6.0 8.0 11.0

TAS 1.5 - -

Coconut MeEO2^*1.5 1.0 2.0

Silicate 7.03.03.0

CMC 1.0 1.0 0.5

Whitening agent 20.20.20.2

Soap 1.01.01.0

DTPMP 0.40.40.2 sprayed thereon

C45E7 2.5 2.5 2.0

C25E3 2.5 2.5 2.0

Silicone antifoaming agent 0.30.30.3

Dry additive of spice 0.30.30.3

Carbonate 6.013.015.0

PB4 18.0 18.0 10.0

PB1 4.0 4.0 0

TAED 3.0 3.0 1.0

Photoactivated bleaching agent 0.020.020.02

Protease 1.01.01.0

Lipase 0.40.40.4

Dry-mixed sodium sulfate 3.03.05.0 of amylase 0.250.300.15

Equilibrium (moisture&miscellaneous) 100.0100.0100.0 concentration (g/L) 630670670 the surfactant AQA-1 (coconut MeEO2) in this example can be replaced by an equivalent amount of any of bis AQA-2-bis AQA-22 or other bis AQA surfactants herein.

Example II the following bleach-free detergent compositions are especially useful for washing colored laundry

Def blown powder

Zeolite A15.015.02.5

Sodium sulfate 0.05.01.0

LAS 2.0 2.0 -

Coconut MeEO2^*1.0 1.0 1.5

DTPMP 0.4 0.5 -

CMC 0.4 0.4 -

MA/AA 4.04.0-agglomerates

C45AS - - 9.0

LAS 6.0 5.0 2.0

TAS 3.0 2.0 -

Silicate 4.04.0-

Zeolite A10.015.013.0

CMC - - 0.5

MA/AA - - 2.0

Carbonate 9.07.07.0 is sprayed thereon

Fragrance 0.30.30.5

C45E7 4.0 4.0 4.0

C25E32.02.02.0 Dry additives

MA/AA - - 3.0

NaSKS-6 - - 12.0

Citrate 10.0-8.0

Bicarbonate 7.03.05.0

Carbonate 8.05.07.0

PVPVI/PVNO 0.5 0.5 0.5

Alcalase 0.5 0.3 0.9

Lipase 0.40.40.4

Amylase 0.60.60.6

Cellulase 0.60.60.6

Silicone defoamer 5.05.05.0 dry additive

Sodium sulphate 0.09.00.0 equilibrium (moisture&miscellaneous) 100.0100.0100.0 concentration (g/L) 700700850 the surfactant bis AQA-1 (coconut MeEO2) in this example may be replaced by an equivalent amount of any one of bis AQA-2-bis AQA-22 or other bis AQA surfactants herein.

Example III

The following are detergent formulations prepared according to the present invention.

GhI blown powder

Zeolite A30.022.06.0

Sodium sulfate 19.05.07.0

MA/AA 3.0 3.0 6.0

LAS 13.0 11.0 21.0

C45AS 8.0 7.0 7.0

Coconut MeEO2^*1.0 1.0 1.0

Silicate-1.05.0

Soap-2.0

Whitening agent 10.20.20.2

Carbonate 8.016.020.0

DTPMP-0.40.4 was sprayed thereon

C45E7 1.0 1.0 1.0

Dry additives

PVPVI/PVNO 0.5 0.5 0.5

Protease 1.01.01.0

Lipase 0.40.40.4

Amylase 0.10.10.1

Cellulase 0.10.10.1

NOBS - 6.1 4.5

PB1 1.0 5.0 6.0

Sodium sulphate-6.0-equilibria (moisture&miscellaneous) 100.0100.0100.0 the surfactant bis AQA-1 (coconut MeEO2) in this example may be replaced by an equivalent amount of any one of bis AQA-2-bis AQA-22 or other bis AQA surfactants herein.

EXAMPLE IV the following are high density and bleach-containing detergent formulations prepared according to this patent

J K L blown powder

Zeolite A15.015.015.0

Sodium sulfate 0.05.00.0

LAS 3.0 3.0 3.0

Coconut MeEO2^*1.0 1.5 1.5

DTPMP 0.4 0.4 0.4

CMC 0.4 0.4 0.4

MA/AA 4.02.02.0 agglomerates

LAS 5.0 5.0 5.0

TAS 2.0 2.0 1.0

Silicate 3.03.04.0

Zeolite A8.08.08.0

Carbonate 8.08.04.0 is sprayed thereon

Fragrance 0.30.30.3

C45E7 2.0 2.0 2.0

C25E32.0 Dry additive

Citrate 5.0-2.0

Bicarbonate-3.0-

Carbonate 8.015.010.0

TAED 6.0 2.0 5.0

PB1 13.0 7.0 10.0

Molecular weight 5,000,000

Poly (ethylene oxide) -0.2

Bentonite Clay- -10.0

Protease 1.01.01.0

Lipase 0.40.40.4

Amylase 0.60.60.6

Cellulase 0.60.60.6

Silicone defoamer 5.05.05.0 dry additive

Sodium sulphate 0.03.00.0 equilibrium (moisture&miscellaneous) to 100.0100.0100.0 concentration (g/L) 850850850 the surfactant bis AQA-1 (coconut MeEO2) in this example may be replaced by an equivalent amount of any of AQA-2-bis AQA-22 or other AQA surfactants herein.

Example v the following is a high density detergent composition made according to the present invention:

m N blown powder

Zeolite A2.52.5

Sodium sulfate 1.01.0

Coconut MeEO2^*1.51.5 agglomerates

C45AS 11.0 14.0

Zeolite A15.06.0

Carbonate 4.08.0

MA/AA 4.0 2.0

CMC 0.5 0.5

DTPMP 0.40.4 sprayed thereon

C25E3 5.0 5.0

Dry additive of spice 0.50.5

HEDP 0.5 0.3

SKS-6 13.0 10.0

Citrate 3.01.0

TAED 5.0 7.0

Percarbonate 15.015.0

SRA1 0.3 0.3

Protease 1.41.4

Lipase 0.40.4

Cellulase 0.60.6

Amylase 0.60.6

Silicone antifoaming agent 5.05.0

Whitening agent 10.20.2

Brightener 20.2-equilibrium (water&miscellaneous) to 100.0100.0 concentration (g/L) 850850 the surfactant bis AQA-1 (coconut MeEO2) in this example may be replaced by an equivalent amount of any one of bis AQA-2-bis AQA-22 or other bis AQA surfactants herein.

Example VI the following is a liquid detergent composition made according to the present invention

O P Q R SLAS 10.013.09.02.015.0C 25AS 4.010.02.08.010.0C 25E3S 1.0.0-3.0-C25E75.57.011.02.0-TFAA-3.5-coconut MeEO2^*0.51.02.01.53.0 TPKFA 2.0-13.02.0-rapeseed fatty acid- - -5.0-citric acid 2.03.01.01.51.0 dodecene/tetradecene succinic acid 12.010.0- -15.0 oleic acid 4.02.01.0-1.0 ethanol 4.04.07.02.07.01, 2-propylene glycol 4.04.02.07.06.0 monoethanolamine- - -5.0-triethanolamine- -8- -NaOH adjusted to pH 8.08.07.67.78.0 ethoxylated tetraethylenepentamine 0.5-0.50.2-DTPMP 1.01.00.51.02.0 SRA 20.3-0.20.1-PVNO- -0.1- -protease 0.50.50.40.25-Alcalase- - -15 lipase-0.10-0.01-amylase 0.250.250.60.50.25 cellulase- - -0.05-endoenzyme- - -0.10-boric acid 0.10.2-2.01.0 sodium formate- -1.0- -Calcium chloride-0.015-0.01-Bentonite Clay- -4.0 suspended Clay SD 3- -0.6 balance (moisture)&Miscellaneous items) to 100100100100100

The surfactant bis AQA-1 (coconut MeEO2) in this example may be replaced by an equivalent amount of any one of bis AQA-2-bis AQA-22 or other bis AQA surfactants herein.

Any of the granular detergent compositions provided herein can be compressed into detergent tablets by known tabletting methods.

Heavy duty liquid detergent compositions, particularly heavy duty liquid detergents for laundering laundry, comprise a non-aqueous carrier matrix. The mode of their production will be described in detail below. Such non-aqueous compositions may also be prepared in another manner disclosed in the following patents: US 4753570; 4767558, respectively; 4772413, respectively; 4889652, respectively; 4892673, respectively; GB-A-2158838; GB-A-2195125; GB-A-2195649; US 4988462; US 5266233; EP-A-225654 (6/16/87); EP-A-510762 (10/28/92); EP-A-540089 (5/5/93); EP-A-540090 (5/5/93); US 4615820; EP-A-565017 (10/13/93); EP-A-030096(6/10/81), the above patent being incorporated by reference. Such compositions can contain various particulate cleaning ingredients (e.g., the whitening agents previously described) stably suspended therein, and thus, such non-aqueous compositions comprise a liquid phase, with or without a solid phase being preferred. All of which are also described in detail in the cited documents and below. For the manufacture of other laundry detergent compositions, the AQA surfactants are added to the compositions at the levels and in the manner of addition described above. Liquid phase

The liquid phase is generally present in an amount of from 35% to 99% by weight of the detergent composition, preferably in an amount of from 50% to 95%, most preferably from 45% to 75%. The liquid phase of the detergent compositions essentially comprises a relatively high concentration of an anionic surfactant in combination with a non-aqueous liquid diluent.

(A) Essential anionic surfactants

Anionic surfactants, which are used primarily as essential components in the nonaqueous liquid phase, are selected from the alkali metal salts of alkyl benzene sulphonic acids in which the alkyl group contains from 10 to 16 carbon atoms and is present in a linear or branched configuration (see US2220099 and US2477383, incorporated herein by reference). Particularly preferred anionic surfactants are sodium or potassium linear alkyl benzene sulphonates (LAS) wherein the alkyl group contains on average 11 to 14 carbon atoms. Sodium LAS salts containing 11 to 14 carbon atoms are most preferred.

The nonaqueous liquid diluent forms the second essential ingredient in the nonaqueous phase in which the alkylbenzene sulfonate anionic surfactant is soluble. To form the structured liquid phase to meet the requirements of suitable phase stability and acceptable rheology, the anionic alkylbenzene sulfonate surfactant is typically present in the liquid phase in an amount of from 30% to 65% by weight, more preferably from 35% to 50% by weight of the nonaqueous liquid phase of the invention. The use of anionic surfactant at these concentrations corresponds to an anionic surfactant concentration in the total composition of from 15% to 60% by weight of the composition, with a preferred range of from 20% to 40%.

(B) Non-aqueous liquid diluents to form the liquid phase of the cleaning composition, the above-described alkylbenzene sulfonate anionic surfactant is combined with a non-aqueous liquid diluent. The diluent contains two essential components, one is a liquid alcohol alkoxylate and the other is a non-aqueous, low polarity organic solvent.

I) alkoxylated alcohols

The alkoxylated fatty alcohol is an essential component of the liquid diluent used to form the composition, and is itself a nonionic surfactant, corresponding to the general formula:

R¹(C_mH_2mO)_nOH wherein R¹Is C₈-C₁₆Alkyl groups of (a); m is 2 to 4; n is 2 to 12. R¹Preferably a primary or secondary alkyl group, containing from 9 to 15 carbon atoms, preferably from 10 to 14 carbon atoms; the alkoxylated fatty alcohols are preferably ethoxylates, having from 2 to 12 ethylene oxide units per molecule, preferably from 3 to 10 ethylene oxide units per molecule.

The alkoxylated fatty alcohol component of the liquid diluent will generally have a hydrophilic-hydrophobic balance (HLB) in the range of from 3 to 17, with 6 to 15 being preferred and 8 to 15 being most preferred.

Examples of alkoxylated fatty alcohols which are one of the main components of the nonaqueous liquid diluents useful in the compositions of the present invention include alkoxylated fatty alcohols made from alcohols of 12 to 15 carbon atoms and containing 7 moles of ethylene oxide, such materials being sold by the Shell company under the trade names Neodol25-7 and Neodol 23-6.5. Other useful Neodols include Neodol 1-5, which isan ethoxylated fatty alcohol having an alkyl chain of an average of 11 carbon atoms and 5 moles of ethylene oxide; neodol 23-9, which is an ethoxylated primary alcohol containing 9 moles of ethylene oxide and 12-13 carbon atoms; neodol 91-10, which is an ethoxylated primary alcohol containing 10 moles of ethylene oxide and 9-11 carbon atoms, is also sold by Shell chemical company under the Dobanol name. Dobanol 91-5 is an ethoxylated fatty alcohol containing an average of 5 moles of ethylene oxide and 9-11 carbon atoms; dobanol 25-7 is an ethoxylated fatty alcohol containing an average of 7 moles of ethylene oxide and 12-15 carbon atoms per molecule.

Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol115-S-9, both of which are linear ethoxylated secondary alcohols sold by Union Carbide. The former is a mixed ethoxylated product of a linear ethoxylated secondary alcohol of 11 to 15 carbon atoms with 7 moles of ethylene oxide, and the latter is similar to the former except that 9 moles of ethylene oxide are reacted.

Other types of ethoxylated alcohols suitable for use in the present compositions are high molecular weight nonionic surfactants such as Neodol 45-11, which is an ethylene oxide polycondensate of a similar higher aliphatic alcohol containing 14 to 15 carbon atoms and 11 moles of ethylene oxide groups per mole, a product also marketed by Shell chemical company.

In the present nonaqueous compositions, the alkoxylated alcohol, which is an essential component of the liquid diluent, generally comprises from 1% to 60% of the liquid phase components, with from 5% to 40% being the preferred range and from 5% to 30% being the most preferred. These concentrations of alkoxylated alcohol in the liquid phase correspond to concentrations thereof in the total composition ranging from 1% to 60% by weight, with 2% to 40% being the preferred range and 5% to 25% being the most preferred. Ii) nonaqueous, low-polarity organic solvent

The second essential component of the liquid diluent which is part of the liquid phase of the cleaning composition is comprised of a non-aqueous, low polarity organic solvent. The "solvent" herein comprises the non-surface active carrier or diluent portion of the liquid phase. While some of the essential and/or optional ingredients of the composition are actually dissolved in the "solvent" containing liquid phase, other ingredients will be dispersed in the "solvent" containing liquid phase as particulate matter. Thus, "solvent" is not meant to require that the solvent be capable of dissolving virtually all of the components of the cleaning composition to which it is added.

The non-aqueous organic substance used as the solvent herein means a liquid having low polarity. For the purposes of the present invention, a "low polarity" liquid means that there is little, if any, dissolving power for one of the preferred particulate materials used in the present compositions. By preferred particulate material is meant a peroxygen whitening agent, sodium perborate or sodium percarbonate. Therefore, relatively polar solvents such as ethanol cannot be used. Suitable low polarity solvents for use in the nonaqueous liquid cleaning compositions include alkylene glycols having 4 to 8 carbon atoms which are not linked, alkylene glycol lower alkyl ethers, low molecular weight polyethylene glycols, low molecular weight methyl esters and amides.

One preferred type of nonaqueous, low polarity solvent for use in the composition consists of an unbranched branched or straight chain alkylene glycol of 4 to 8 carbon atoms. Such materials include hexanediol (4-methyl-2, 4-pentanediol), 1, 6-hexanediol, 1, 3-butanediol, and 1, 4-butanediol. Hexylene glycol is most suitable.

Another preferred type of nonaqueous, low polarity solvent foruse in the present invention comprises mono-, di-, tri-, or tetra-C_2-3Alkylene glycol mono C_2-6An alkyl ether. Specific examples are diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether. Among them, diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are particularly suitable. Such compounds are commercially available under the trade names Dowanol, Carbitol and Cellosolve.

Another preferred type of nonaqueous, low polarity solvent for use in the present invention comprises low molecular weight polyethylene glycols (PEGs), which have a molecular weight of at least 150, preferably 200-600.

Still another preferred non-polar, non-aqueous solvent comprises lower molecular weight methyl esters of the formula R¹-C(O)-OCH₃Wherein R is¹From 1 to 18. Examples of suitable low molecular weight methyl esters are methyl acetate, methyl propionate, methyl octanoate and methyl dodecanoate.

Of course, the nonaqueous, low polarity organic solvent employed should be compatible with and non-reactive with other components, such as the bleach and/or activator used in the liquid detergent composition. Such a solvent component is generally used in an amount ranging from 1% to 70%, preferably from 10% to 60%, most preferably from 20% to 50% by weight of the liquid phase. These concentrations of organic solvent used in the liquid phase correspond to concentrations thereof in the total composition of from 1% to 50%, with 5% to 40% being the preferred range, and preferably from 10% to 30%. Iii) ratio of alkyl hydric alcohol to solvent

The weight ratio of alkoxylated alcohol to organic solvent in the liquid diluent may be used to modify the rheology of the finally-formed cleaning composition. Typically, this ratio will range from 50: 1 to 1: 50, preferably from 3: 1 to 1: 3. Iv) concentration of liquid diluent

The total amount of liquid diluent in the nonaqueous liquid phase of the present invention with respect to the concentration of alkylbenzene sulfonate anionic surfactant mixture is determined by the type and amount of the other components of the composition and the desired properties of the composition. Typically, the liquid diluent comprises from 35% to 70%, preferably in the range of from 50% to 65% of the nonaqueous liquid phase of the composition, which corresponds to a concentration of the nonaqueous liquid diluent in the total composition of from 15% to 70%, preferably in the range of from 20% to 50%. Solid phase

The nonaqueous detergent composition also desirably includes from 1% to 65% by weight, preferably from 5% to 50% by weight, of solid phase particulate material dispersed and suspended in the liquid phase. Typically such particles are in the range of 0.1 to 1500 μm, preferably 5 to 200 μm.

The particulate material as used herein can comprise one or more particulate detergent ingredients which are substantially insoluble in the non-aqueous liquid phase of the cleaning composition and the types of particulate material which can be utilised are described in more detail below:

preparation and use of detergent compositions

The non-aqueous liquid detergent compositions of the present invention may be prepared by mixing the necessary and optional ingredients in any convenient order and by mixing, for example by stirring. The components are combined to form a phase stable composition. In a typical preparation process of such a composition, the essential and certain preferred optional components are mixed in a specific order under certain conditions.

In the first step of this typical manufacturing process, the composition is formed by mixing and heating the two essential components of the alkylbenzene sulfonate anionic surfactant and the non-aqueous diluent at 30 ℃ to 100 ℃.

In the second step, the heated mixture formed above is maintained at 40 ℃ to 100 ℃ for 2 minutes to 20 hours with some shear agitation. Optionally, a vacuum may be applied to the mixture at this time. The second step is to completely dissolve the anionic surfactant in the nonaqueous liquid phase.

In a third step, the liquid phase mixture is cooled to a temperature of from 0 ℃ to 35 ℃ in order to form a structured, surfactant-containing liquid base into which the particulate material of the detergent composition is introduced and dispersed.

In the fourth step, the particulate material is added while maintaining the liquid base under shear agitation to mix the particulate material with the liquid base. When more than one particulate material is added, it is preferred to follow a certain order of addition. For example, while maintaining shear agitation, substantially all of the optional surfactant solid particles ranging in size from 0.2 to 1000 microns can be added. After all optional surfactant particles are added, substantially all organic builder particles, such as citrate and/or fatty acids and/or an alkalinity source, such as sodium carbonate, can be added while continuing to maintain the mixture under shear agitation, at which point other solid phase optional ingredients can be added to the mixture. Agitation of the mixture is continued and, if necessary, can be enhanced to form a homogeneous dispersion of the insoluble solid phase particles in the liquid phase.

Highly preferred peroxygen bleach granules can be added to the composition after some or all of the foregoing solid materials have been added to the agitated mixture, while still maintaining the mixture under agitation. The required stability of the peroxygen bleach can be obtained by adding the peroxygen bleach after the last or after all or most of the other ingredients, especially after the alkaline source granules. If enzyme granules are to be added, they are preferably added last to the nonaqueous liquid phase matrix.

In the final step, after all of the particulate material has been added, the mixture is continued to be stirred for a sufficient time to form a composition having the desired viscosity and phase stability characteristics. Often this involves stirring for a period of 1 to 30 minutes.

As a variation of the above-described composition preparation steps, one or more solid components may be pre-mixed with a minor amount of one or more liquid components and added to the agitated composition as a blended slurry, whereby minor amounts of the alkoxylated alcohol and/or the non-aqueous low polarity solvent and the organic builder material and/or the inorganic alkaline particles and/or the bleach activator particles may be separately pre-mixed and added to the agitated mixture as a slurry. The addition of these pre-mixed pulps is to precede the addition of the peroxygen bleach and/or the enzyme granules, which may themselves form part of a mixed pulp formed in a similar manner.

The compositions of the present invention, prepared as described above, can be used to form aqueous cleaning solutions for use in washing or bleaching fabrics. Generally, such aqueous washing/bleaching solutions are formed by adding an effective amount of such compositions to water, preferably in conventional automatic washing machines for fabric cleaning. The aqueous washing/bleaching liquor thus formed is preferably contacted with the fabric to be washed or bleached under agitation.

An effective amount of a liquid detergent for addition to water to form an aqueous based wash/bleach liquor comprises an amount sufficient to form from 500 to 7,000ppm of the composition in aqueous solution. The detergent composition added to the aqueous wash/bleach liquor is preferably from 800 to 3,000 ppm.

Example VII

A non-aqueous liquid bleach-containing laundry detergent having the composition set forth in Table I is prepared, although not limited thereto.

TABLE 1 weight percent (%) weight percent range of components (%) liquid phase C₁₂Sodium Linear alkyl benzene sulfonate (LAS) 25.318-35C_12-145 ethylene oxide units 13.610-20 ethoxylated alcohol

Hexanediol 27.320-30

Perfume 0.40-1.0

bis-AQA-1^*2.0 1-3.0

Solid phase

Protease 0.40-1.0

Anhydrous trisodium citrate 4.33-6

Sodium perborate 3.42-7

Sodium Nonanoyloxybenzenesulfonate (NOBS) 8.02-12

Sodium carbonate 13.95-20

0.90-1.5% of diethyl triaminepentaacetic acid (DTPA)

Whitening agent 0.40-0.6

Foam inhibitor 0.10-0.3

Secondary component balance-

Coconut meeo2. bis-AQA-1 may be replaced by bis-AQA surfactants 2-22 or other bis-AQA surfactants.

This composition was prepared by first mixing AQA and LAS, then adding hexylene glycol and ethoxylated alcohol, and holding together at 54 ℃ (130 ° F) for 1/2 hours. The mixture was cooled to 29 deg.C (85 deg.F) at which time the other ingredients were added. The resulting composition was stirred at 29 ℃ (85 ° F) for 1/2 hours.

The resulting composition is a stable, anhydrous, heavy duty liquid laundry detergent which can produce very high soil removal capability when used in ordinary laundry operations.

The following examples a and B further illustrate the invention in relation to a laundry bar soap.

Example VIII

Content (%) range of component (C) (%)

A B

C₁₂-C₁₈Sulfate 15.7513.500-25

LAS 6.75 - 0-25

Na₂CO₃15.00 3.00 1-20

DTPP¹0.70 0.70 0.2-1.0

Bentonite clay-10.00-20

Sokolan CP-5²0.40 1.00 0-2.5

bis-AQA-1³2.0 0.5 0.15-3.0

TSPP 5.00 0 0-10

STPP 5.00 15.00 0-25

Zeolite 1.251.250-15

Sodium laurate-9.000-15

SRA-1 0.30 0.30 0-1.0

Protease-0.120-0.6

Amylase 0.12-0-0.6

Lipase-0.100-0.6

Cellulase-0.150-0.3

- - - -balance⁴----

1. Diethylenetriamine penta (phosphonic acid) sodium salt

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

3. -AQA-1 may be replaced by equivalent amounts of the bis-AQA surfactants bis-AQA-2 to-AQA-22 or other bis-AQA surfactants.

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

Example IX

The following hand washing detergent compositions according to the present invention were prepared by mixing the components in the following weight percentages of the components listed below.

A B C DLAS 15.0 12.0 15.0 12.0TFAA 1.0 2.0 1.0 2.0C25E5 4.0 2.0 4.0 2.0AQA-9^*2.0 3.0 3.0 2.0STPP 25.0 25.0 15.0 15.0MA/AA 3.0 3.0 3.0 3.0CMC 0.40.40.40.4 DTPMP 1.01.61.61.6 carbonate 2.02.05.05.0 bicarbonate- -2.02.0 silicate 7.07.07.07.0 protease 1.0-1.01.0 amylase 0.40.40.4-lipase 0.120.12-0.12 photosensitization bleaching agent 0.30.30.30.3 sulfate 2.22.22.22.2 PB14.05.44.02.3NOBS 2.63.12.51.7 SRA10.30.30.70.3 whitening agent 10.150.150.150.15 balance miscellaneous/water to 100100.0100.0100.0100.0AQA-9^*: may be replaced by any of the AQA surfactants described herein. Preferred AQA surfactants in this example are AQAs containing from 10 to 15 ethoxy groups; such as AQA-10, AQA-16.

The above examples illustrate the compositions of the present invention for laundering fabrics. While the following examples will illustrate other types of detergent compositions according to the invention, the invention is not limited to these examples.

Modern high-performance hand dishwashing agents contain ingredients which impart specific performance attributes to the product, such as degreasing capability, high sudsing, mildness and good hand. Such ingredients for use with the bis-AQA surfactants include, for example, amine oxide surfactants, betaine and/or sulphobetaine surfactants, alkyl sulphate and alkyl ethoxy sulphate surfactants, liquid carriers, especially water and water/propylene glycol mixtures, natural oils, such as lemon oil. In addition, good hand-washing liquid and/or gel dishwashing agents may also contain Ca²⁺,Mg²⁺Or Ca²⁺/Mg²⁺Mixtures capable of providing enhanced detergency, particularly when used with washing mixtures containing bis-AQA surfactants in combination with amine oxides, alkyl sulphates and alkyl ethoxy sulphates. Ca²⁺Or Mg²⁺Or mixed with Ca²⁺/Mg²The source is generally 0.01% by weight of the composition4%, preferably 0.02% -2%. Various water soluble ion sources include, for example, sulfate, chloride, and acetate salts. Furthermore, these compositions may also contain nonionic surfactants, especially polyhydroxy fatty acid amides and alkylpolyglucosides, of which the members containing from 12 to 14 carbon atoms (coconut alkyl) are preferred. A particularly preferred nonionic surfactant for use in dishwashing liquid for water washing is C_12-14N-methylglucamides, preferably amine oxides including C_12-14Dimethyl amine oxide, alkyl sulphates and alkyl ethoxy sulphates are as described above and such surfactants are typically used in dishwashing liquid in amounts of 3-50% of the finished product. The formulation of dishwashing liquid compositions has been described in detail in various patent publications, including U.S. Pat. No. 5,5378409, U.S.5576310 and U.S.5417893, which are incorporated by reference.

Modern automatic dishwashing agents may contain bleaching agents such as a source of hypochlorous acid; perborate, percarbonate, or persulfate bleaches; enzymes, such as proteases, lipases and amylases, or mixtures thereof; rinse aids, especially nonionic surfactants; builders, including zeolites and phosphate builders; low foaming detersive surfactants, particularly ethylene oxide/propylene oxide condensates, such compositions are usually in particulate or gel form. When used in the form of a gel, various gelling agents known in the literature can be used.

The following examples further illustrate the invention with respect to hand dishwashing liquids.

Example X

Content (%) range of component (C) (%)

bis-AQA-1^*2.0 0.15-3

C_12-13Ammonium alkyl sulfate 7.02-35

C_12-14Ethoxylated (1) sulfate 20.55-35

Coconut amine oxide 2.62-5

betaine/Tetronic 704^_0.87-0.10 0-2(mix)

Ethoxylated alcohol C₈E₁₁5.0 2-10

Ammonium xylene sulfonate 4.01-6

Ethanol 4.00-7

Ammonium citrate 0.060-1.0

Magnesium chloride 3.30-4.0

Calcium chloride 2.50-4.0

Ammonium sulfate 0.080-4.0

Hydrogen peroxide 200ppm 0-300ppm

Perfume 0.180-0.5

Maxatase^_Protease 0.500-1.0

Water and minor components- -balance-

^*Can be replaced by-AQA-2 to bis-AQA-22 or other bis-AQA surfactants

^**Coconut alkyl betaines

The following examples A and B further illustrate the present invention in relation to a phosphate-containing granular automatic dishwashing agent.

Example XI

% based on the weight of the active substance

Ingredient A B

STPP (waterless)¹31 26

Sodium carbonate 2232

Silicate (% SiO)₂) 9 7

Surfactant (nonionic) 31.5

NaDCC bleaching agent²2 -

bis-AQA-1^*0.5 1.0

Sodium perborate-5

TAED - 1.5

Savinase(Au/g) 0.1 0.04

Termamyl(Amu/g) 0.5 0.5

Sulfate salt 2525

Perfume/minor ingredients to 100%

1 sodium tripolyphosphate

2 Dichlorocyanuric acid sodium salt

^*The bis-AQA-1 may be replaced by bis-AQA-2 to bis-AQA-22

Example XII

The following examples further illustrate the invention in relation to a liquid-gel automatic dishwashing or other detergent having high detergency.

% active ingredient based on weight of active ingredient AB C D E F G citric acid 16.516.516.516.516.51010 sodium/potassium carbonate- -2525251515 bis-AQA-1^*0.50.70.50.50.40.60.7 dispersant (480N) 4444444 HEDP/SS-EDDS 220-2221.51.5 benzoyl peroxide 888881.51.5 butylated hydroxytoluene 0.050.050.050.050.050.050.05 (BHT) surfactant 2.52.51.51.51.51.51.5 boric acid-444444 sorbitol-666666 Savinase 24L- -0.20.53-0.53-suspended Savinase 16L-0.53-0.53 Maxamyl/termamyl 0.54-0.311.01.0-suspended temamamyl-0.54-0.310.31 water-equilibrium- -

^*The bis-AQA-1 (coconut MeEO2) may be replaced by equivalent amounts of bis-AQA-2 to bis-AQA-22 or other bis-AQA surfactants.

Various gelling agents such as CMC and clay may be used in the composition to provide various viscosities and hardnesses depending on the requirements of the formulator.

Example XIII

Mixtures of bis-AQA surfactants that can replace the bis-AQA surfactants listed in any of the above examples are exemplified below. As noted above, the use of such mixtures can provide various beneficial properties and/or provide cleaning compositions suitable for use in various conditions of use. Preferred in such mixtures are bis-AQA surfactants differing by at least 1.5, preferably by from 2.5 to 20 ethylene oxide units in a weight ratio of from 10: 1 to 1: 10, examples of which are not limited to those set forth in the following table.

Proportion of the Components (by weight)

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

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

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

bis-AQA-1 + bis-AQA-5

+ bis-AQA-201: 1

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

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

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

Mixtures of bis-AQA surfactants with corresponding cationic surfactants containing only one ethoxylated chain may also be used herein. Thus, for example, moleculesOf the formula R¹N⁺CH₃[EO]_X[EO]_YX^-And R¹N⁺(CH₃)₂[EO]_zX^-Mixtures of ethoxylated cationic surfactants of (a) wherein R is a member of the group¹And X As mentioned above, the (X + y) or z of one cationic surfactant may be from 1 to 5, preferably from 1 to 2, and the (X + y) or z of the other cationic surfactant is from 3 to 100, preferably from 10 to 20, most preferably from 14 to 16. Such compositions are capable of producing higher detergency (particularly in the context of laundering fabrics) under a wider range of water hardness conditions than the cationic surfactants of the present invention alone. It has been found that shorter ethylene oxide cationic surfactants (e.g., EO2) improve the detergency of anionic surfactants in soft water, whereas longer ethylene oxide cationic surfactants (e.g., EO15) improve the hardness tolerance of anionic surfactants, thereby improving the detergency of anionic surfactants in hard water. Conventional wisdom in the washing arts suggests that builders can optimize the "window" of performance of anionic surfactants. However, until now, it has not been possible to expand this "window" to substantially contain varying conditions of water hardness.

Example XIV

The following examples illustrate perfume formulations (a-C) prepared according to the present invention, which are incorporated into any of the above examples of bis-AQA containing detergent compositions. The components and amounts are listed in the table below.

(% by weight)

Perfume Components A B C

Hexyl cinnamic aldehyde 10.0-5.0

2-methyl-3- (p-tert-butylphenyl) -propionaldehyde 5.05.0-

7-acetyl-1, 2,3,4,5,6,7, 8-octahydro-1, 1,6,7-

Tetramethylnaphthalene 5.010.010.0

Benzyl salicylate 5.0-

7-acetyl-1, 1,3,4,4, 6-hexamethyltetralin 10.05.010.0

P- (tert-butyl) cyclohexyl acetate 5.05.0-

Methyl dihydrojasmonate-5.0-

β -naphthyl methyl ether-0.5-

Methyl- β -naphthalenone-0.5-

2-methyl-2- (p-isopropyl-phenyl) -propanal-2.0-

1,3,4,6,7, 8-hexahydro-4, 6,6,7,8, 8-hexamethyl

-cyclopenta-gamma-2-benzopyran-9.5-

Dodecahydro-3 a,6,6,9 a-tetramethy

Naphtho [1,2d]furan-0.1

Anisaldehyde-0.5

Coumarin-5.0

Cedrol- -0.5

Vanillin-5.0

3.0-10.0 parts of cyclopentyl decalactone

Tricyclodecenyl acetate-2.0

Labdanum resin- -2.0

Tricyclodecenyl propionate-2.0

Phenylethanol 20.010.027.9

Terpineol 10.05.0-

Linalool 10.010.05.0

Linalyl acetate 5.0-5.0

Geraniol 5.0-

Nerol-5.0-

2- (1, 1-Dimethylethyl) -cyclohexanol acetate 5.0-

Orange oil, cold pressing-5.0-

Benzyl acetate 2.02.0-

Orange terpene-10.0-

Eugenol-1.0-

Diethyl phthalate-9.5-

Lemon oil, cold pressing-10.0

Total amount 100.0100.0100.0

The above-described perfume compositions (normally present at levels up to about 2% by weight of the total detergent composition) are incorporated or sprayed into various bis-AQA surfactant-containing washing (including bleaching) compositions as disclosed herein to ensure enhanced deposition and/or retention of the perfume or its individual ingredients onto the surface to be cleaned (bleached).

Claims (24)

1. A detergent composition comprising or prepared by admixing: an enzyme, a non-alkoxy quaternary ammonium surfactant and an effective amount of a bis-alkoxy quaternary ammonium cationic surfactant of the formula:

in the formula R¹Is straight-chain, branched, or substituted C₈-C₁₈Alkyl, alkenyl, aryl, alkaryl, ether with a glycosyl ether moiety; r²Is C₁-C₃An alkyl group; r³And R⁴Independently varied and selected from one of hydrogen, methyl, ethyl; x is an anion; a and A' independently vary and are each C₁-C₄An alkoxy group; p and q can vary independently and are integers between 1 and 30.

2. The composition of claim 1, wherein the enzyme is selected from lipases.

3. The composition of claim 1 or 2, wherein the enzyme is a protease.

4. A composition according to any one of claims 1 to 3, wherein the enzyme is a cellulase.

5. A composition according to any one of claims 1 to 4 wherein the enzyme is an endogenous glucanase.

6. A composition accordingto any one of claims 1 to 5, wherein the enzyme is an amylase.

7. A composition according to any one of claims 1 to 6, wherein the enzyme is a peroxidase.

8. The composition of claim 1 or 7, additionally comprising an enzyme stabilizer.

9. A composition according to any one of claims 1 to 8, which is made by mixing a non-alkoxy quaternary ammonium surfactant and an alkoxy quaternary ammonium cationic surfactant.

10. A composition according to any one of claims 1 to 9 wherein the non-alkoxy quaternary ammonium surfactant is an anionic surfactant.

11. A composition according to any one of claims 1 to 10 wherein the ratio of the bis-alkoxy quaternary ammonium cationic surfactant to the non-alkoxy quaternary ammonium surfactant is from 1: 8 to 1: 15.

12. The composition of any one of claims 1 to 11 wherein R of the bis-alkoxy quaternary ammonium surfactant¹Is C₈-C₁₈Alkyl radical, R²Is methyl, A and A' are ethoxy and propoxy, respectively, and p and q are integers from 1 to 8.

13. The composition of any one of claims 1 to 12 wherein R of the bis-alkoxy quaternary ammonium surfactant¹Is C₈-C₁₈Alkyl radical, R²Is methyl, A and A' are ethoxy and propoxy, respectively, and p and q are integers between 1 and 4.

14. The composition according to any one of claims 1to 13, wherein p and q in the formula of the cationic bis-alkoxy quaternary ammonium surfactant are integers of 10 to 15.

15. A composition according to any one of claims 1 to 14 comprising two or more bis-alkoxy quaternary ammonium surfactants, or a mixture comprising one bis-alkoxy quaternary ammonium surfactant and one mono-ethoxylated cationic surfactant.

16. A composition according to any one of claims 1 to 15 comprising a mixture of two or more non-alkoxylated quaternary ammonium surfactants and two or more bis-alkoxylated quaternary ammonium surfactants.

17. A composition according to any one of claims 1 to 16 which is substantially free of bleach.

18. The composition of any one of claims 1 to 17 in the form of a granule, a stick, an aqueous liquid, a non-aqueous liquid, or a tablet.

19. A method for removing soils and stains by contacting said soils and stains with a detergent composition according to any of claims 1 to 18 or an aqueous phase comprising said detergent composition.

20. The method of claim 19 for removing enzyme sensitive soils, greasy/oily soils or surfactant sensitive soils from fabrics.

21. The method of claim 19 or 20, performed by hand.

22. A method according to any one of claims 19 to 21, carried out in a washing machine.

23. A method for enhancing depositionand longevity of a perfume or perfume ingredient onto a fabric or other surface, comprising contacting said surface with a perfume or perfume ingredient in the presence of a bis-alkoxy quaternary ammonium surfactant.

24. The method of claim 23, conducted using a detergent composition comprising a bis-alkoxy quaternary ammonium surfactant in combination with a perfume or perfume component.