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

Field of Invention

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

Background of the Invention

Formulation of laundry detergents and other cleaning compositions presents formidable challenges due to the need for today's detergent compositions to remove various types of soils and stains on a variety of soil carriers. Thus, to achieve effective efficacy, laundry detergents, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents, and detergent compositions suitable for automatic dishwashing all require judicious selection and selection of ingredients. combination. 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 reviewed literature seems to indicate that detergent manufacturers can choose from a wide range of surfactants and combinations of surfactants, when in fact many ingredients in detergents are specific chemicals unsuitable for low-priced items such as household laundry detergent. In fact, most household cleaning products, such as household laundry detergents, still contain one or more traditional ethoxylated nonionic and/or sulfated or sulfonated anionic surfactants, possibly due to economic considerations and needs to formulate 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, grease/oily soils and some food stains remains an unsolved challenge. This soil contains triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous substances, all of which are composed of hydrophobic parts to some extent and are very difficult to remove. After laundering, small amounts of hydrophobic soils and stains often remain on the surface of fabrics. Continuous washing and wearing coupled with limited removal of hydrophobic soils, over multiple washes, will result in a substantial buildup of soils and stains, which further absorb particulate dust, resulting in yellowing of the fabric, and finally, the fabric appears unwearable and unsuitable to the consumer. A dull look that should be discarded.

The literature shows that a variety of nitrogen-containing cationic surfactants can be used effectively in a variety of cleaning compositions. These materials are typically in the form of amino, amido, quaternary ammonium or imidazoline compounds, which are usually designed for specific applications. For example, various amino and quaternary ammonium surfactants have been suggested for use in shampoo compositions and are said to have hair beautifying benefits. Other nitrogen-containing surfactants are used in some laundry detergents to soften fabrics and have an antistatic effect. However, for the most part, the commercial use of these substances is limited by the inability to produce large quantities. In addition, it is also limited by the possible precipitation of anionic active ingredients in detergent compositions and cationic surfactants due to their ionic interactions. The aforementioned nonionic and anionic surfactants are still 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 used in various detergent compositions to enhance the removal of various types of soils and stains, especially common hydrophobic types of soils. It has now been surprisingly found that compositions comprising enzymes and dialkoxyquat ammonium surfactants not only provide superior cleaning and whitening benefits but also provide improved care of fabrics compared to compositions containing only one of these ingredients function.

The bisalkoxyquat surfactants of the present invention provide formulators with significant benefits over previously known cationic surfactants. For example, the use of the bis-alkoxyquat surfactants of the present invention provides significant improvements in the cleaning performance of "everyday" greasy/oily hydrophobic soils commonly encountered. In addition, dialkoxy quaternary ammonium surfactants and anionic surfactants such as alkyl sulfates and alkylbenzene sulfonates in common detergent compositions can coexist with each other, while anionic components in detergent compositions are The use of today's cationic surfactants is generally limited due to their incompatibility with cationic surfactants. Low levels of dialkoxyquat surfactants (as little as 3 ppm in the aqueous wash solution) can produce the benefits described herein. The bis-alkoxy quaternary ammonium surfactant can be formulated in a wide range between pH 5-12, and the bis-AQA surfactant can be formulated as a 30% (wt.) solution that can be pumped, Therefore, it is easy to handle in production equipment. Dialkoxylated quaternary ammonium surfactants with a degree of ethoxylation above 5 are sometimes present in liquid form and, therefore, are available as 100% pure material. In addition to its easy-to-handle properties, bis-AQA surfactants are available in highly concentrated solutions, which confers an immediate economic benefit in the cost of shipping. Unlike some cationic surfactants known in the prior art, dialkoxy quaternary ammonium surfactants can also coexist with various fragrance ingredients.

The present invention provides a method for enhancing the removal ability of greasy/oily soils by combining dialkoxy quaternary ammonium surfactants with lipase. Grease/oily dirt is a mixture that contains triglycerides. During the storage of dirty clothes before washing, the triglycerides in the dirt are converted into fatty acids by the action of bacteria, and lipase can convert any remaining triglycerides into fatty acids during the washing process. The fatty acids in the soil interact with the hardness ions (such as Mg ²⁺ and Ca ²⁺ ) in the wash water to form insoluble magnesium/calcium fatty acid salts or calcium soaps. The calcium soap precipitates from the aqueous solution, forming a calcium soap deposit on the fabric. As a result of continuous washing, calcium soap deposits will accumulate, absorb particulate dust, affect the removal of dirt, and enhance the residue of dirt on the washed fabric. Additionally, there is a problem of sheath degradation around the fibers of old/worn cotton or other fibrous fabrics. The sheath degrades to form a gelatinous or amorphous cellulose gum, which will also attract particulate dust. Additionally, the cellulose gum is an ideal substrate for the deposition and retention of greasy/oily hydrophobic body soil, such as on necklines and pillowcases. Frequent wear/washing, accumulation of residual soil, calcium soap deposits and attracted dust will cause the fabric to turn yellow until the fabric becomes soiled, deemed impossible by the user and usually discarded.

It has now been found that detergent compositions containing lipase and a dialkoxyquat surfactant provide superior cleaning and whitening benefits compared to compositions containing only one of these ingredients. It is believed that this is because: (1) the dialkoxyquats reduce the production of calcium soaps, thereby allowing lipase to come into contact with the soil; (2) the fatty acids are effectively stripped from the soil (via the dialkoxyquats). ), to maintain maximum lipase activity (the high content of fatty acids in the dirt inhibits the action of lipase).

Surprisingly, it has now been found that detergent compositions containing cellulosic enzymes (such as cellulase and/or endogenous glucanase) and dialkoxy quaternary ammonium surfactants are more effective than those containing only one of them Compared with the composition of , it has excellent cleaning and whitening effects. This is a result of the effective penetration of the dialkoxy quaternary ammonium surfactants into hydrophobic body soils. Also, this enhances the cellulosic enzymes to degrade the amorphous cellulose gum around the fibers (which adheres the soil to the fabric). As the cellulose glue dissolves, the adsorbed dust will be separated from the fabric, and the original whiteness will be restored. Mixed systems of cellulosic enzymes and dialkoxyquats, in addition to their cleaning benefits, soften and care for fabrics better than either the cation alone or the cellulosic enzymes alone.

It has also been found that detergent compositions comprising an amylase and a dialkoxyquat surfactant provide better cleaning and whitening benefits than compositions comprising only one of these ingredients. This is because the dialkoxy quaternary ammonium makes the amylase easy to enter into the sensitive dirt by effectively solubilizing the dirt, and improves the remaining "glue" around the fiber to degrade. As the glue dissolves, the fabric returns to its original whiteness, the adsorbed dust is detached, and other detergent active ingredients are prone to bleaching.

Background technique

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

Invention Summary

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

In the formula, R ¹ is a linear, branched, or substituted C ₈ -C ₁₈ alkyl, alkenyl, aryl, alkaryl, ether or sugar alcohol ether (glycityl ether) moiety; R ² is C ₁ -C ₃ alkyl; R ³ and R ⁴ can each change and be selected from one of hydrogen, methyl, ethyl; X is an anion; A and A' can each change and be selected from C ₁ -C ₄ alkane Oxygen; p and q can each vary and be an integer between 1-30.

                                     

The composition of the present invention contains enzymes as an essential ingredient. The enzymes in the present detergent compositions serve a variety of cleaning purposes, including removal of protein-based, carbohydrate-based and triglyceride-based stains from substrates, inhibiting the transfer of leached dyes from fabrics during laundering, and for Restoration of the fabric. 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 factors such as pH activity and/or stability optimum, thermostability, active detergent stability, and builders. Bacterial or fungal enzymes are preferred in this respect, such as bacterial amylases and proteases, and fungal cellulases.

As used herein, "detergency enzyme" refers to any enzyme having a cleaning, stain removal or other beneficial effect in a laundry, hard surface cleaning or personal care detergent composition. Preferred detersive enzymes are hydrolases, such as proteases, amylases and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Most preferred enzymes suitable for automatic dishwasher washing are amylases and/or proteases.

Enzymes are usually added to detergent or detergent additive compositions in a detergency effective amount. By "cleaning effective amount" is meant any amount capable of producing a cleaning, stain removing, soil removing, whitening, deodorizing or freshness enhancing effect on a wash substrate (eg fabrics, dishes). As far as current commercial products are concerned, each gram of detergent composition contains no more than 5 mg of active enzyme components, more generally between 0.01-3 mg. In other words, the content of commercial enzyme preparations used in the composition of the present invention is generally 0.001%-5% by weight, preferably 0.01%-1% by weight. Proteases are generally used in commercial preparations in effective amounts of 0.005-0.1 Anson Units (AU) per gram of composition. For some detergents (e.g., automatic dishwashing machines), the amount of active enzyme in a commercial product may be increased appropriately in order to substantially reduce the total amount of non-catalytically active material, thereby improving spotting/filming or other end results . In highly concentrated detergent formulations, higher active levels are also required.

Examples of suitable proteases are subtilisins, which are produced by certain strains of Bacillus subtilis and Bacillus licheniformis. Another suitable protease is produced by a Bacillus strain which is most active in the pH range of 8-12, developed and marketed as ^ESPERASE® by Novo Industries A/S of Denmark (hereinafter "Novo"). The preparation of this enzyme or similar enzymes is described in GB 1,243,783 to Novo. Other suitable ^proteases include ^ALCALASE® and ^SAVINASE® sold by Novo, MAXATASE® sold by International Bio-synthetics, Inc. (Netherlands), Protease A (see European Patent Application EP130,756A, published January 9, 1985), and Protease B (see European Patent Application EP303,761A, published April 28, 1987; European Patent Application EP130,756A, published January 9, 1985). Also included: Novo's high pH protease obtained from Bacillus sp. NCIMB40338 described in International Patent Application WO9318140A, Novo's enzymatic detergent described in International Patent Application WO9203529A, which also contains one or more other types of enzymes and reversible protease inhibitors; other preferred proteases include Procter &Gamble's proteases described in International Patent Application WO9510591A; when needed, as Procter & Gamble described in International Patent Application WO9507791, can obtain Proteases that adsorb and enhance hydrolysis; Novo in International Patent Application WO9425583 describes recombinant trypsin-like proteases suitable for detergents according to the invention.

In particular, a particularly preferred protease is referred to as "Protease D", which is a carbonyl hydrolase variant having an amino acid sequence not found in nature. It is derived from the carbonyl hydrolase precursor by substitution in the carbonyl hydrolase corresponding to position +76 with a different amino acid according to the encoding in Bacillus amyloliquefaciens subtilisin A plurality of amino acid residues, preferably accompanied by the group consisting of +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, One or more of the amino acid residue positions +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and/or +274 Instead, this is described in U.S. Patent Applications (Serial No. 08/322,676) entitled "Protease-Containing Cleaning Compositions" by A. Baeck et al., and "Protease-Containing Bleaching Compositions" by C. Ghosh et al. In the U.S. patent application (serial number 08/322,677), the filing date of both is October 13, 1994.

Suitable amylases of the present invention, particularly but not limited to automatic dishwashing machine purposes, include: the alpha-amylase described in British patent specification GB1,296,839 (Novo), sold by International Bio-Synthetics, Inc. RAPIDASE ^_ , and TERMAMYL ^_ sold by the company Novo, FUNGAMYL ^_ sold by the company Novo are particularly suitable. Enzyme engineering to improve enzyme stability (such as oxidative stability) is known, see for example J. Biological Chem., Vol.260, No. 11, June 1985, pp. 6518-6521. In certain preferred embodiments of the compositions of the present invention, amylases with improved stability, especially amylases with improved oxidative stability, may be used in detergents (e.g. of the type used in automatic dishwashing), which The reference point for the measurements was TERMAMYL ^_ commercially used in 1993. Those amylases preferred in the present invention are characterized as "stability-enhanced" amylases, characterized by a measurable improvement in at least one or more of the following, when used in minimal amounts: Oxidative stability, e.g. Oxidation stability to hydrogen peroxide/tetraacetylethylenediamine in a buffer solution of -10; thermal stability, such as stability at normal washing temperatures (such as 60°C); alkali stability, such as pH8-11 conditions These stability measurements are compared to the reference amylases identified above. Stability measurements can also be performed using experimental techniques disclosed in the prior art, such as references disclosed in patent document WO9402597. Stability-enhanced amylases are commercially available from Novo Corporation or Genencor Intrenational. A preferred class of amylases of the present invention has the commonality that they are derived by site-directed mutagenesis from one or more Bacillus amylases, particularly Bacillus α-amylases, regardless of whether one, Two or more amylase strains are immediate precursors. Amylases having enhanced oxidative stability compared to the reference amylases described above are preferred for use in detergent compositions of the present invention, especially in bleaching detergent compositions, more preferably for use in oxygen as distinguished from chlorine bleaching. in bleaching detergent compositions. These preferred amylases include:

(a) The amylase in the patent WO9402597 published on February 3, 1994, which is additionally described as a mutant in which alanine or threonine (preferably threonine) is used to replace Bacillus licheniformis α - the methionine residue at position 197 in amylases, known as ^TERMAMYL_ , similar to homologous position variants of homologous amylases such as Bacillus amyloliquefaciens, Bacillus subtilis or Bacillus stearothermophilus.

(b) Paper presented by Genencor International at C. Mitchinson's 207th American Chemical Society National Meeting, March 13-17, 1994, entitled "Antioxidant Alpha-Amylases" Stability-enhanced amylases described in . It is mentioned that in automatic dishwashing detergents, bleach can inactivate alpha-amylases, but amylases with enhanced oxidative stability have been prepared by Genencor from Bacillus licheniformis NCIB8061. Methionine (Met) was identified as the most likely residue to be modified. Substitution of methionines one at a time at positions 8, 15, 197, 256, 304, 366, and 438 resulted in specific variants, notably M197L and M197T, with the M197T variant being the most stably expressed variant . Stability was determined with ^CASCADE_ and ^SUNLIGHT_ .

(c) Particularly preferred in the present invention is the amylase variant described in the patent document WO9510613A with additional improvements in the direct parent, which can be purchased from the patent assignee Novo Company under the trade name DURAMYL ^_ . Other particularly preferred oxidative stability-enhanced amylases include those described in patent documents WO9418314 (Genencor International) and WO9402597 (Novo). Any other oxidative stability-enhanced amylase may also be used, such as amylases obtained by site-directed mutagenesis from available known chimeric, hybrid or simple mutant parent forms of amylases. Other preferred enzyme modifications can also be carried out, see patent document WO9509909A (Novo).

Other amylases include those described in WO95/26397 and Novo Nordisk's co-pending application PCT/DK96/00056. The specific amylase used in the detergent composition of the present invention comprises the α-amylase with following characteristics: by Phadebas ^_ α-amylase activity test and measure, at temperature 25-55 ℃, under the condition of pH8-10, its specific activity At least 25% greater than the specific activity of Termamyl ^® (Phadebas ^® α-amylase activity test see WO95/26397 pages 9-10). Also included are α-amylases with more than 80% homology to the amino acid sequence shown in the SEQ ID table of the above-mentioned literature. These enzymes are added to laundry detergent compositions in the form of pure enzymes, preferably in an amount of 0.00018%-0.060% of the total weight of the composition, more preferably 0.00024%-0.048% of the total weight of the composition.

Cellulases useful in the present invention include bacterial and fungal cellulases which have an optimum pH between 5-9.5. Suitable fungal cellulases derived from Humicola insolens or Humicola strain DSM1800, or cellulose produced by fungi belonging to the genus Aeromonas, are disclosed in U.S. Patent No. 4,435,307 issued March 6, 1984 to Barbesgoard et al. Enzyme 212, and cellulase extracted from the hepatopancreas of the marine mollusk Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2,075,028, GB-A-2,095,275 and DE-OS-2,247,832. CAREZYME ^® and CELLUZYME ^® (Novo) are also particularly suitable, cf. WO9117243 (Novo).

Suitable lipases that detergents can use include: lipases produced by bacteria of the genus Pseudomonas, such as those produced by Pseudomonas stutzeri ATCC19.154 (British Patent GB1,372,034 disclosure); February 1978 The lipase in Japanese Patent Application No. 53-20487 laid open on the 24th is commercially available from Amano Pharmaceutical Co. Ltd. Nagoya, Japan under the trade name Lipase P "Amano" or "Amano-P". Other suitable commercial lipases include: Amano-CES, lipase from Chromobacter viscosus, e.g. Chromobacter viscosus var. lipolytica NRRLB 3673, sold by Toyo Jozo Co. Tagata Japan; Chromobacter viscosus lipase, USBiochemical Corp. (USA) and Disoynth Co. (Netherlands); and lipase from Pseudomonas gladioli. ^LIPOLASE® enzyme from Humicola lanuginosa and sold commercially by Novo (see also EP341,947) is a preferred lipase for use in the present invention. Stabilization of lipase and amylase variants against peroxidase is described in WO9414951A (Novo), see also WO9205249 and RD94359044.

Despite numerous published lipases, only lipases derived from Humicola lanuginosa and Aspergillus oryzae hosts have been found to be widely used as additional ingredients in fabric detergents, as mentioned above, commercially available from Novo Nordisk under the trademark Lipolase ^™ . In order for Lipolase to exhibit the best decontamination ability, Novo Nordisk has obtained a large number of Lipolase variants. As described in WO92/05249, the variant D96L of the lipase of natural Humicola lanuginosa, compared with the wild-type lipase, the effect of lard stain removal has been improved by 4.4 times (compared by dosage of 0.075-2.5mg protein/liter enzyme). Novo Nordisk described in Research Disclosure (No. 35944) March 10, 1994: Lipase variant (D96L) added in an amount of 0.001-100 mg (5.500,000 LU/liter) of lipase variant per liter of wash solution . In the present invention, detergent compositions containing dialkoxy quaternary ammonium surfactants using low levels of D96L variants can provide improved whiteness maintenance, especially when D96L is used in an amount of 50-8500 LU/liter washing solution.

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

Peroxidases are used in combination with oxygen sources such as percarbonate, perborate, hydrogen peroxide, etc. They are used for "solution bleaching", or inhibiting the release of dyes and pigments from the substrate during washing Transfer to other substrates in wash solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidase (eg, chloro- or bromo-peroxidase). Peroxidase-containing detergent compositions are disclosed in WO89099813A (published October 19, 1989, Novo) and WO8909813A (Novo).

Various enzymatic materials and methods for their incorporation into synthetic detergent compositions are also described in Genencor International's International Patent Application WO9307263A and WO9307260A, Novo's International Patent Application WO8908694A, and McCarty et al. US Patent No. 3,553,139 (1971 Authorized on January 15). Some enzymes are also disclosed in US Patent No. 4,101,457 to Place et al. (issued July 18, 1978) and US Patent No. 4,507,219 to Hughes (issued March 26, 1985). Enzyme materials useful in liquid detergent formulations, and methods for their incorporation into such formulations, are disclosed in US Patent 4,261,868 (issued April 14, 1981) to Hora et al. Enzymes for use in detergents can be stabilized in a variety of ways. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 3,600,319 to Gedge et al. (issued August 17, 1971), and European Patents EP 199,405, EP 200,586 to Venegas (published October 29, 1986). Enzyme stabilization systems have also been described in the literature, eg US Patent No. 3,519,570. Suitable proteases, xylanases and cellulases produced by Bacillus sp. AC13 are described in International Patent Application WO9401532A (Novo). Bis-Alkoxylated Quaternary Ammonium (bis-AQA) Cationic Surfactant

A second essential component of the compositions of the present invention includes an effective amount of a bis-alkoxylated quaternary ammonium surfactant having the following structural formula:

In the formula, ^R is a linear, branched, or substituted alkyl, alkenyl, aryl group containing 8-18 carbon atoms, preferably 8-16 carbon atoms, most preferably 8-14 carbon atoms , alkaryl, ether or sugar alcohol ether; R ² is an alkyl group containing 1-3 carbon atoms, preferably methyl; R ³ and R ⁴ can each change and be selected from hydrogen (preferred), methyl, ethyl ; X- is an anion, such as chlorine, bromine, methyl sulfate, sulfate, which can effectively provide electrical neutrality; A and A' can be varied and each selected from C ₁ -C ₄ alkoxy, especially Ethoxy, propoxy, butoxy and their mixed types; p is 1-30, preferably 1-15, more preferably 1-8, most preferably 1-4, q is 1-30, preferably 1 -15, more preferably 1-8, especially preferably 1-4, most preferably p and q are 1.

Bis-alkoxyquaternary ammonium (bis-AQA) compounds in which the hydrocarbyl substituent R ¹ is C ₈ -C ₁₂ , especially C ₈ -C ₁₂ , compared to long-chain hydrocarbyl-substituted compounds, especially under cold water conditions , can increase the dissolution rate of laundry detergent granules. Therefore, the C ₈ -C ₁₂ bis-alkoxylated quaternary ammonium surfactants may also be preferred by formulators. The bis-alkoxylated quaternary ammonium surfactants are generally used in the finished laundry detergent composition at a level of from 0.1% to 5% (wt.), preferably from 0.45% to 2.5% (wt.). The weight ratio of bis-alkoxylated quaternary ammonium surfactant to 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 "effective amounts" of bis-alkoxylated quaternary ammonium surfactants to enhance the performance of cleaning compositions containing other optional ingredients. As used herein, an "effective amount" of a dialkoxyquaternary ammonium surfactant is that which is sufficient, at a 90% confidence level, to directionally or significantly improve the detergency of the cleaning composition on at least some of the target soils and stains dosage. Thus, for some food target stain compositions, the formulator will use a sufficient amount of the dialkoxyquat to at least directionally improve the cleaning performance on these stains. Likewise, in a composition for an earth target soil, the formulator will use a sufficient amount of the dialkoxyquat to at least directionally improve the cleaning effect on that soil.

The dialkoxy quaternary ammonium surfactants can be used in combination with other detersive surfactants in an amount effective to obtain at least a directional improvement in cleaning performance. In the case of fabric laundering compositions, the "use level" can vary depending on the type and severity of soils and stains, the temperature of the water used in the wash, the amount of water used and the type of washing machine.

For example, a top-feeding vertical shaft American (country) automatic washing machine uses 45-83 liters of water for washing, a washing cycle of 10-14 minutes, and a water temperature of 10-50°C during washing. The amount of ammonium surfactant is 2-50 ppm, preferably 5-25 ppm. For the heavy-duty liquid detergent, the usage amount of each washing load is calculated with 50-150ml, and the concentration of converted bis-alkoxy quaternary ammonium surfactant in the product is 0.1%-3.2% (weight), preferably It is 0.3%-1.5% (weight). For concentrated granular laundry detergents (with a density above 650g/l), the amount used for each wash load is calculated as 60-95g, and the concentration of converted bis-kangyl quaternary ammonium surfactants in the product is 0.2%- 5.0% by weight, preferably 0.5%-2.5% by weight. For spray-dried granular detergents (i.e. "loose type", with a density below 650g/l), the amount used per wash load is calculated on the basis of 80-100g, converted to bis-alkoxy quaternary ammonium surfactants in the product Concentration in 0.1%-3.5% (weight), preferably 0.3%-1.5% (weight).

For example, for a front-feeding type horizontal axis European (European) automatic washing machine, 8-15 liters of water is used for washing, and a washing cycle is 10-60 minutes, and the water temperature is 30-95°C during washing. The amount of quaternary ammonium surfactant is 13-900 ppm, preferably 16-390 ppm. For the heavy-duty liquid detergent, the usage amount of each washing load is calculated with 45-270ml, and the concentration of converted bis-alkoxy quaternary ammonium surfactant in the product is 0.4%-2.64% (weight), preferably It is 0.55%-1.1% (weight). For concentrated granular laundry detergent (with a density above 650g/l), the loading amount per wash is calculated as 40-210g, and the concentration of bis-alkoxy quaternary ammonium surfactant in the product is 0.5%- 3.5% by weight, preferably 0.7%-1.5% by weight. For spray-dried granular detergents (i.e. "loose type", density below 650g/l), the use amount per wash load is calculated on the basis of 140-400g, converted to bis-alkoxy quaternary ammonium surfactant in the product Concentration in 0.13%-1.8% (weight), preferably 0.18%-0.76% (weight).

For example, top-feeding vertical shaft Japanese-style automatic washing machine, washing water 26-52 liters, a washing cycle 8-15 minutes, washing water temperature 5-25 ° C, the washing liquid contains bis-alkoxy quaternary ammonium surfactant The amount is 1.67-66.67 ppm, preferably 3-6 ppm. For the heavy-duty liquid detergent, the usage amount of each washing load is calculated with 20-30ml, and the concentration of converted bis-alkoxy quaternary ammonium surfactant in the product is 0.25%-10% (weight), preferably It is 1.5%-2% (weight). For concentrated granular laundry detergents (density above 650g/l), the loading amount per wash is calculated as 18-35g, and the concentration of bis-alkoxy quaternary ammonium surfactant in the product is 0.25%- 10% by weight, preferably 0.5%-1.0% by weight. For spray-dried granular detergents (i.e. "loose type", with a density below 650g/l), the amount used per wash load is calculated on the basis of 30-40g, converted to bis-alkoxy quaternary ammonium surfactants in the product Concentration in 0.25%-10% (weight), preferably 0.5%-1% (weight).

As can be seen from the above, the amount of dialkoxyquat used in machine washing can vary according to the habits and practical experience of the user, as well as the type of washing machine. Thus, in this regard, a previously unrecognized advantage of dialkoxyquats is that they are compatible with other surfactants (typically anionic or anionic/nonionic mixtures) in existing detergents. Compared, even at relatively low usage levels, it has the ability to at least directionally improve the cleaning effect on various soils and stains. This differs from other compositions of the prior art in which the various cationic and anionic surfactants are used at or near stoichiometric amounts. Generally, in the practice of the present invention, the weight ratio of dialkoxy 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, more preferably from 1:15 to 1:8. In laundry detergent compositions comprising anionic and nonionic surfactants, the weight ratio of dialkoxyquaternary ammonium:anionic/nonionic mixture is from 1:80 to 1:2, preferably from 1:50 to 1:2 8.

Various other detergent compositions comprising an anionic surfactant, an optional nonionic surfactant and specific surfactants (such as betaines, sultaines, amine oxides) may also be used in an effective amount The bisalkoxy quaternary ammonium surfactant of the present invention is formulated. These compositions include, but are not limited to, dishwashing detergents suitable for hand washing (especially liquid or gel forms), hard surface cleaners, shampoos, personal cleansing compositions, laundry detergents, and the like. Since users have little variation in the usage habits and practical experience of these detergents, it is suitable for these compositions to include dialkoxy quaternary ammonium surfactants in an amount from 0.25% to about 5% (by weight), preferably 0.45% to about 2% by weight. Additionally, for granular and liquid laundry detergent compositions, the weight ratio of dialkoxyquat surfactants to other surfactants in these compositions is low, ie, substoichiometric compared to anions. Preferably such cleaning compositions comprise the bisalkoxyquat/surfactant ratios described immediately above for machine laundry compositions.

Compared with other cationic surfactants known herein, the bisalkoxylated cationic surfactants of the present invention have sufficient solubility that they can be used in combination with mixed surfactant systems in which non- The level of ionic surfactants is low and the system contains surfactants such as alkyl sulfates. This is an important consideration for formulators of detergent compositions of the following types: Detergent compositions of traditional design for top-loading automatic washing machines, especially those designed for use in North America and those used in Japan . Generally, these compositions will contain anionic and nonionic surfactants in a ratio of from about 25:1 to about 1:25, preferably from about 20:1 to about 3:1. The formulations of European models are different, and the ratio of anionic surfactant to nonionic surfactant is generally from about 10:1 to about 1:10, preferably about 5:1 to about 1:1.

方案2

方案3

方案4 Preferred ethoxylated cationic surfactants of the invention are available from Akzo Nobel Chemicals Company under the tradename ETHOQUAD. Alternatively, it can also be synthesized from the following various reaction schemes (where "EO" denotes _{a -CH2CH2O-} unit): Scheme 1

Scenario 2

Option 3

Option 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 the aqueous phase. The reaction temperature is generally in the range of 140-200°C. The reaction pressure is 50-1000 ^psi . As the base catalyst, sodium hydroxide is preferably used. The molar ratio of reactants (amine:alkyl sulfate) is from 2:1 to 1:1. The reaction is preferably carried out using sodium C ₈ -C ₁₄ alkyl sulfates. 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 to form a gel. Although the product of interest could be recovered from the gel, an alternative to the two-step synthesis described below in Scheme 6 would be more feasible commercially. The first step reaction of Scheme 6 is consistent with Scheme 5, and the second step reaction (ethoxylation) is preferably carried out using ethylene oxide and an acid such as hydrochloric acid, which will result in a quaternary ammonium surfactant. As shown below, chloroethanol can also be reacted to give the desired bishydroxyethyl derivative.

For Reaction Scheme 6, the following parameters summarize the optional and preferred conditions for the first step reaction. The first step reaction is preferably carried out in aqueous phase. The reaction temperature is generally in the range of 100-230°C. The reaction pressure is 50-1000 ^psi . The base, preferably sodium hydroxide, reacts with the HSO ₄ ^- generated in the reaction, and excess amine can 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, more preferably from 2:1 to 1:1. In the step of product recovery, the desired substituted amine is insoluble in the aqueous phase, which is different from the aqueous phase and is easy to separate. The second step reaction is carried out using conventional reaction conditions. The further ethoxylation and quaternization reactions to yield the bis-alkoxyquat surfactant were carried out under standard reaction conditions.

Scheme 7 can optionally use ethylene oxide under standard ethoxylation conditions to obtain monoethoxylated products without a catalyst.

方案7

These additional reaction schemes are listed below, where "EO" denotes _{a -CH2CH2O-} unit. During the reaction, an inorganic base, an organic base, or an excess of amine is used to neutralize the generated HSO ₄ ^- . Option 6

Option 7

The following additionally introduce several kinds of above-mentioned reactions, which are only for the reference of formulators, and are not limited. Synthesis A: Preparation of N,N-bis(2-hydroxyethyl)dodecylamine

A glass autoclave jacket was charged with 19.96 g sodium lauryl sulfate (0.06921 moles), 14.55 g diethanolamine (0.1384 moles), 7.6 g sodium hydroxide 50% by weight solution (0.095 moles), and 72 g distilled water. After sealing the glass casing, put it into a 500ml stainless steel stirred pressure kettle, and heat it to 160-180° C. for 3-4 hours under 300-400 ^psi nitrogen pressure. The mixture was cooled to room temperature, the liquid in the glass sleeve was poured into a 250ml separating funnel, 80ml of chloroform was added, and the mixture could be separated after shaking for a few minutes. The chloroform in the lower layer is recovered, and the reaction product can be obtained after the chloroform is evaporated. Synthesis B: Preparation of N,N-bis(2-hydroxyethyl)dodecylamine

In the presence of a base, 1 mole of sodium lauryl sulfate reacts with 1 mole of ethanolamine in the same way as in Synthesis A. The reaction product 2-hydroxyethyl dodecylamine is recovered, and then reacted with 1-chloroethanol to prepare N,N-bis(2-hydroxyethyl)dodecylamine. Synthesis C: Preparation of N,N-bis(2-hydroxyethyl)dodecylamine

A glass autoclave jacket was charged with 19.96 g sodium lauryl sulfate (0.06921 moles), 21.37 g ethanolamine (0.3460 moles), 7.6 g sodium hydroxide 50% by weight solution (0.095 moles), and 72 g distilled water. After sealing the glass casing, put it into a 500ml stainless steel stirred pressure kettle, and heat it to 160-180° C. for 3-4 hours under 300-400 psi nitrogen pressure. The mixture was cooled to room temperature, the liquid in the glass sleeve was poured into a 250ml separating funnel, 80ml of chloroform was added, and the mixture could be separated after shaking for a few minutes. The lower layer of chloroform is recovered, and the reaction product can be obtained after the chloroform is evaporated. In the presence of an alkali-free catalyst, the reaction product is reacted with 1 molar equivalent of ethylene oxide under the condition of 120-130° C. to obtain the desired final product.

The disubstituted amine prepared above can be ethoxylated in a standard manner, and then quaternized with an alkyl halide in a conventional manner to obtain the bis-alkoxy quaternary ammonium surfactant of the present invention.

According to the foregoing description, the dialkoxy quaternary ammonium surfactants used in the present invention are illustrated as non-limiting examples below. It should be understood that the degree of alkyl oxidation of the dialkoxyquat surfactants herein is reported as an average value, and the following are common examples of nonionic surfactants that are typically ethoxylated, since ethoxylated The reaction generally produces a mixture of different degrees of ethoxylation. Therefore, the total EO value is usually recorded as a non-integer number such as "EO2.5", "EO3.5".

Name R ¹ R ² ApR ³ A'qR ⁴ Dialkoxyquat-1 C ₁₂ -C ₁₄ CH ₃ EO EO (see coconut methyl EO2) Dialkoxyquat-2 C ₁₂ -C ₁₆ CH ₃ (EO) ₂ EO bis-alkoxyquat-3 C ₁₂ -C ₁₄ CH ₃ (EO) ₂ (EO) ₂ (see coconut methyl EO4) bis-alkoxy quat-4 C ₁₂ CH ₃ EO EO bis Alkoxyquat-5 C _{12 -C 14} CH ₃ (EO) ₂ (EO) 3dialkoxyquat-6 _{C 12} -C ₁₄ CH ₃ (EO) ₂ (EO) 3dialkoxyquat Ammonium-7 C ₈ -C ₁₈ CH ₃ (EO) ₃ (EO) ₂ -dialkoxyquat-8 C ₁₂ -C ₁₄ CH ₃ (EO) ₄ (EO) ₄ -dialkoxyquat-9 C ₁₂ -C ₁₄ C ₂ H ₅ (EO) ₃ (EO) ₃ Dialkoxyquat-10 C ₁₂ -C ₁₈ C ₃ H ₇ (EO) ₃ (EO) ₄ Dialkoxyquat - 11 C ₁₂ -C ₁₈ CH ₃ (propoxy) (EO ₎ 3dialkoxyquat _- 12C ₁₀ -C ₁₈ C ₂ H ₅ (isopropoxy) ₂ (EO) 3dialkoxyquaternium - 13 C ₁₀ -C ₁₈ CH ₃ (EO/Propoxy) ₂ (EO) ₃ Dialkoxyquat-14 C ₈ -C ₁₈ CH ₃ (EO) ₁₅ ^* (EO) ₁₅ ^* Dialkoxyquat Ammonium-15 C ₁₀ CH ₃ EO EO Dialkoxyquat-16 C ₈ -C ₁₂ CH ₃ EO EO Dialkoxyquat-17 C ₉ -C ₁₁ CH ₃ -EO3.5 (Average) Dialkyl Oxyquat-18 C ₁₂ CH ₃ -EO3.5 (Average) Dialkoxyquat-19 C ₈ -C ₁₄ CH ₃ (EO) ₁₀ (EO) ₁₀ Dialkoxyquat-20 C ₁₀ C ₂ H ₅ (EO) ₂ (EO) 3-21 C ₁₂ -C ₁₄ C ₂ H _{5 (} EO) ₅ (EO) _3-22 C ₁₂ -C ₁₈ C ₃ H ₇ Butoxy (EO) ₂

*Ethoxy groups are optionally terminated with methyl or ethyl groups.

Particularly preferred bis-alkoxy quaternary ammonium compound structural formula is as follows:

Wherein R ¹ is C ₈ -C ₁₈ hydrocarbon group and mixed groups thereof, preferably C ₈ , C ₁₀ , C ₁₂ , C ₁₄ alkyl and mixed groups thereof; X is any conventional anion that can produce charge balance, preferably chloride ion . With reference to the above-mentioned bis-alkoxy quaternary ammonium general structure, since in the preferred compound, R ¹ is derived from coconut (C ₁₂ -C ₁₄ alkyl) partial fatty acid, R ² is methyl, and A _p R ³ and A' _q R ⁴ are monoethoxy groups respectively, so this preferred compound is exactly " coconut MeEO2 " or " bis-alkoxy quaternary ammonium-1 " listed in the table above.

Other dialkoxy quaternary ammonium surfactants useful in the present invention include compounds having the formula:

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

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

Particularly preferred bisalkoxyquat ammonium surfactants for use in builter formulations have the formula wherein p and/or q are integers in the range 10-15. The compounds are particularly useful in laundry handwash detergent compositions. Non-alkoxylated quaternary ammonium detergent 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-alkoxylated quaternary ammonium surfactants include essentially any anionic, nonionic or other cationic surfactant. anionic surfactant

Non-limiting examples of anionic surfactants generally used in the present invention at levels of 1% to 55% by weight include: conventional C ₁₁ -C ₁₈ alkylbenzene sulfonates ("LAS"); primary ("AS"), branched or random C ₁₀ -C ₂₀ alkyl sulfonates; the structural formulas are CH ₃ (CH ₂ ) _x (CHOSO ₃ ^- M ⁺ )CH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ ^- M ⁺ ) C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfonates of CH ₂ CH ₃ , wherein x and (y+1) are integers of at least 7, preferably at least 9, and M is water soluble Cations (especially sodium); unsaturated sulfates such as oleyl sulfate; C ₁₂ -C ₁₈ α-sulfonated fatty acid esters; C ₁₀ -C ₁₈ sulfated polyglycosides; C ₁₀ -C ₁₈ alkyl alkoxylates alkyl sulfates ("AE _x S", especially EO1-7 ethoxysulfates), and _C10 - _C18 alkyl alkoxy carboxylates (especially EO1-5 ethoxy carboxylates). C ₁₂ -C ₁₈ betaines and sultaines, C ₁₀ -C ₁₈ amine oxides may be included in the overall composition, conventional C ₁₀ -C ₂₀ soaps may also be used. Branched C ₁₀ -C ₁₆ soaps can be used if suds building is desired. Other commonly used surfactants have been listed in common textbooks. nonionic surfactant

Non-limiting examples of nonionic surfactants useful herein, typically at levels of 1% to 55% by weight, include: alkoxylated alcohols (AE's), alkylphenols, polyhydroxy fatty acid amides (PFAA's), s), alkyl polyglycosides (APG's), C ₁₀ -C ₁₈ glyceryl ethers.

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 alcohol can be straight or branched, primary or secondary, and generally contains 8 to 22 carbon atoms. Its alkyl group contains 8-20 carbon atoms, preferably 10-18 carbon atoms (1 mole) and 1-10 moles, more preferably 2-7 moles, most preferably 2-5 moles of epoxy Condensation products of ethane are preferred. Examples of such nonionic surfactants that are commercially available include: Tergitol ^™ 15-S-9 (a condensation product of a C ₁₁ -C ₁₅ linear alcohol with 9 moles of ethylene oxide), both sold by Union Carbide Corporation; and Tergitol ^™ 24-L-6 NMW (a narrow molecular weight distribution product of the condensation of a C ₁₂ -C ₁₄ primary alcohol with 6 moles of ethylene oxide); Neodol ^™ 45-9 (C ₁₄ -C ₁₅ Condensation product of linear alcohol with 9 moles of ethylene oxide), Neodol ^TM 23-3 (condensation product of C ₁₂ -C ₁₃ linear alcohol with 3 moles of ethylene oxide), Neodol ^TM 45-7 (C ₁₄ - Condensation product of C ₁₅ linear alcohol with 7 moles of ethylene oxide) and Neodol ^TM 45-5 (condensation product of C ₁₄ -C ₁₅ linear alcohol with 5 moles of ethylene oxide); sold by Procter & Gamble Company Kyro ^TM EOB (condensation product of C ₁₃ -C ₁₅ alcohol with 9 moles of ethylene oxide); and Genapol LA O3O or O5O (condensation product of C ₁₂ -C ₁₄ alcohol with 3 or 5 moles of ethylene oxide) sold by Hoechest product). In these AE nonionic surfactants, the preferred range of hydrophilic-lipophilic balance (HLB) is 8-11, most preferably 8-10. Condensates with propylene oxide and butylene oxide can also be used.

Another preferred nonionic surfactant that can be used in the present invention is a polyhydroxy fatty acid amide of the following structural formula:

Wherein R ¹ is H, or C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixed group thereof; R ² is C _5-31 hydrocarbyl; and Z is at least a straight-chain hydrocarbyl chain A polyhydroxyl hydrocarbon group having 3 hydroxyl groups, or an alkoxylated derivative thereof. R ¹ is a methyl group, R ² is a straight chain C _11-15 alkyl, C _15-17 alkyl or alkenyl (such as coconut alkyl) or a mixed group thereof, and Z is a reducing sugar such as glucose, fructose , maltose and lactose are obtained in the reductive amination reaction. Typical examples thereof include C ₁₂ -C ₁₈ and C ₁₂ -C ₁₄ N-methylglucamides, see US Pat. Nos. 5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides may also be used, see US Pat. No. 5,489,393.

In the present invention, what can also be used as nonionic surfactants are: alkyl polysaccharides with hydrophobic groups disclosed in U.S. Patent No. 4,565,647 of Llenado authorized on January 21, 1986, whose hydrophobic groups contain 6- 30 carbon atoms, preferably 10-16 carbon atoms; polysaccharides, such as polyglycosides whose hydrophobic groups contain 1.3-10, preferably 1.3-3, most preferably 1.3-2.7 sugar units. Any reducing sugar containing 5 or 6 carbon atoms can be used, such as glucose, galactose, and the galactosyl moiety can be replaced by a glucosyl moiety (hydrophobic groups can be optionally attached to 2-, 3-, 4- Allelically, this gives glucose or galactose as distinct from glucoside or galactose). Intersaccharide linkages may be located, eg, between a position on another sugar unit and the 2-, 3-, 4- and/or 6-position of the previous sugar unit.

Preferred alkyl polyglycosides have the following structural formula:

R ² O(C _n H _2n O) _t (glycosyl) _x wherein: R ² is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixed groups thereof, wherein the alkyl group Contains 10-18, preferably 12-14 carbon atoms; n is 2 or 3, preferably 2; t is 0-10, preferably 0; X is 1.3-10, preferably 1.3-3, more preferably 1.3-2.7. The sugar group is preferably a glucose derivative. To prepare these compounds, the alcohol or alkylpolyethoxylated alcohol is first prepared and then reacted with glucose or a source of glucose to form the glucoside (attached at the 1-position). The 1-position of the further glycosyl unit can then be linked to the 2-, 3-, 4- and/or 6-position (mostly preferably the 2-position) of the preceding glycosyl unit.

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

The hydrophobic skeleton obtained by the condensation reaction of propylene oxide and propylene glycol, and then condensed with ethylene oxide, its products are also suitable as other nonionic surfactants in the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of 1500-1800 and is insoluble in water. By adding polyoxyethylene moieties to this hydrophobic moiety, it is generally possible to increase the water solubility of the entire molecule while maintaining the liquid character of the condensation product up to a polyoxyethylene content of 50% by weight of the total condensation product. This corresponds to condensation with up to 40 moles of ethylene oxide. Examples of such compounds include some of the Pluronic ^™ surfactants sold by BASF.

Also suitable as nonionic surfactants in the nonionic surfactant system of the present invention are: the reaction product of propylene oxide with ethylenediamine and the condensation product of ethylene oxide. The hydrophobic portion of these products consists of the reaction product of ethylenediamine with excess propylene oxide, usually having a molecular weight of 2500-3000. The hydrophobic 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 some of the Tetronic( ^TM) compounds sold by BASF. Other cationic surfactants

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

Other suitable cationic surfactants include: quaternary ammonium surfactants selected from mono C ₆ -C ₁₆ (preferably C ₆ -C ₁₀ ) N-alkyl or alkenyl ammonium surfactants, wherein the remaining N sites Substituted by methyl, hydroxyethyl or hydroxypropyl groups. Other suitable cationic ester surfactants, including choline ester surfactants, are disclosed in US Patent Nos. 4,228,042, 4,239,660 and 4,260,529. optional detergent ingredients

Other various ingredients that can be optionally used in the composition of the present invention are described below, but are not limited thereto. enzyme stabilization system

The enzyme-containing composition of the present invention also comprises 0.001% to 10% by weight, preferably 0.005% to 8% by weight, most preferably 0.01% to 6% by weight of an enzyme stabilizing system. The enzyme stabilization system can be any stabilization system compatible with the wash enzyme. This stabilizing system can be provided by the other active ingredients in the formulation themselves, or it can be added separately, for example by the formulator or by the manufacturer of detergent backup enzymes. Such stabilizing systems can include, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acids, mixtures thereof, etc., and can be tailored 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, so if only one cation is used, calcium ions are preferred. Usually detergent compositions, especially liquid detergents, contain 1-30, preferably 2-20, more preferably 8-12 millimoles of calcium ions per liter of final detergent composition, although it may be Factors including diversity, type and dosage vary. Water-soluble calcium and/or magnesium salts are preferably used, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; calcium sulfate or The corresponding magnesium salts of the listed calcium salts. Of course, further increases in calcium and/or magnesium levels are useful, for example to improve the degreasing performance of certain classes of surfactants.

Another way to achieve stability is to use borates in the composition, see US Patent 4,537,706 to Severson. Borate stabilizers, when used, may comprise up to 10% or more of the composition, although, typical liquid detergents contain boric acid or other borate compounds (such as borax or orthoborate) at about 3% by weight is suitable. Substituted boronic acids such as phenylboronic acid, butylboronic acid, p-bromophenylboronic acid or the like can be used instead of boric acid. In addition, the use of such substituted boronic acid derivatives can reduce the total boron content of detergent compositions.

The stabilizing system of some detergent compositions, such as the washing composition for automatic dish washing machine, may further comprise 0-10% (weight), preferably 0.01%-6% (weight) of chlorine bleach scavenger, its addition Prevents chlorine bleach species present in many water sources from attacking and inactivating enzymes, especially under alkaline conditions. Although the chlorine content in water is relatively low, generally in the range of 0.5ppm-1.75ppm, but, for example, in the washing process of tableware or fabrics, the amount of chlorine in total water that can be contacted with enzymes is quite large. Therefore, when using Chlorine stability of the enzymes in the process is sometimes problematic. Due to the ability of percarbonate to react with chlorine bleaching substances, the use of other chlorine stabilizers, although improved, is generally unnecessary. Suitable chlorine scavenger anionic species are known and readily available. If used, it is a salt comprising an ammonium cation, such as sulfite, bisulfite, thiosulfite, thiosulfate, iodide, and the like. In addition, antioxidants such as carbamates, ascorbic acid, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or alkali metal salts thereof, monoethanolamine (MEA) and mixtures thereof may also be used. Similarly, adding a specific enzyme inhibitor system can make different enzymes have the greatest compatibility. Other conventional scavengers such as bisulfites, nitrates, chlorides, hydrogen peroxide sources such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, and phosphates can be used if desired , condensed phosphates, acetates, benzoates, citrates, formates, lactates, malates, tartrates, salicylates, etc., and mixtures thereof. In general, the chlorine scavenger effect can be accomplished by several components listed separately with better recognized efficacy (such as hydrogen peroxide source substances), so there is no need to add chlorine scavenger separately unless this function is completed The compound is absent to the desired extent in the enzyme-containing embodiments of the invention, and even in this case, the scavenger is added only for optimum effect. Furthermore, the formulator will use the ordinary skill of a chemist to avoid the use of any enzyme scavengers or stabilizers, which, if used, are mostly incompatible with the other components. With regard to the use of ammonium salts, such salts can be simply mixed with detergent compositions, but tend to absorb water and/or release ammonia during storage. Therefore, such materials, if present, need to be protected in the particles, such as described in US Patent 4,652,392 to Baginski et al. bleach

The detergent compositions optionally contain a bleaching agent. Bleaching agents, when present, will generally be present at levels of from 1% to 30%, more typically from 5% to 20%, of detergent compositions, 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 laundering, hard surface cleaning or other known or to become known laundering applications. These include oxygen bleaches as well as other bleaches. Perborate bleaches such as sodium perborate (eg sodium perborate monohydrate or tetrahydrate) can be used here.

Another class of bleaches of non-limiting use includes percarboxylic acid bleaches and their salts. Suitable examples of such bleaching agents include magnesium monoperoxyphthalate hexahydrate, magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxybutyric acid, and dodecanedioic acid diperoxide . U.S. Patent 4,483,781 to Hartman, published November 20, 1984, U.S. Patent Application 740,446, filed June 3, 1985 by Burns et al., European Patent Application 0133354, published February 20, 1985 to Banks et al., and Such bleaching agents are disclosed in US Patent 4,412,934, Chung et al., issued November 1, 1983. Preferred bleaching agents also include 6-nonylamino-6-oxyperoxyhexanoic acid described in US Patent 4,634,551, Burns et al., January 6,1987.

Peroxygen bleach can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and the corresponding "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (eg, OXONE, manufactured and sold by DuPont) may also be used.

Preferred percarbonate bleaches comprise dry particles having an average particle size in the range of 500 microns to 1000 microns, with not more than 10% by weight of particles having a particle size of less than 200 microns and not more than 10% by weight of particles having a particle size of greater than 1250 microns (weight). The percarbonate is optionally coated with silicates, borates or water soluble surfactants. Percarbonate is available through various commercial sources such as FMC, Solvay and Tokai Denka.

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

A bleach mixture can also be used. bleach activator

Bleach activators are a preferred ingredient in detergent compositions employing oxygen bleaches. When used, they are generally used in amounts of 0.1-60%, more typically 0.5-40%, of the composition (comprising bleach and bleach activator).

In aqueous solution (that is, during the washing process), peroxygen bleaches, such as perborate, etc., are mixed with bleach activators to generate in situ peroxyacids or peracids corresponding to the bleach activators. Various non-limiting examples of bleach activators are disclosed in US Patent 4,915,854, Mao et al., issued April 10, 1990, and in US Patent 4,412,934. Nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are commonly used and can also be used in combination. Additionally, see U.S. Patent No. 4,634,551 for other typical bleaches and activators that may be used in the present invention.

Highly preferred amido-derived bleach activators have the formula:

R ¹ N(R ⁵ )C(O)R ² C(O)L or R ¹ C(O)N(R ⁵ )R ² C(O)L wherein R ¹ is an alkane containing 6-12 carbon atoms R ² is an alkylene group containing 1-6 carbon atoms; R ⁵ is H or an alkyl, aryl or alkaryl group containing 1-10 carbon atoms; L is any suitable leaving group . By leaving group is meant any group which is displaceable from the bleach activator by nucleophilic attack of the bleach activator by the perhydrolysis anion. A preferred leaving group is phenylsulfonate.

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

Another class of bleach activators includes the benzoxazine-type activators disclosed in US Patent 4,966,723, issued October 30,1990 to Hodge et al. Very preferred benzoxazine-type activators are:

Another preferred class of bleach activators includes: acyl lactam activators, especially acyl caprolactams and acyl valerolactams having the formula: Wherein R is H or an ^alkyl , aryl, alkoxyaryl, or alkaryl group containing 1-12 carbon atoms. Highly preferred lactam activators include: benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, caproyl caprolactam, undecylenoyl caprolactam, benzoyl valerolactam Lactam, octanoyl valerolactam, caproyl valerolactam, undecylenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam, and mixtures thereof. See US Patent 4,545,784, Sanderson, issued October 8, 1985, which discloses acyl caprolactams including benzoyl caprolactam absorbed into sodium perborate. bleach catalyst

Bleach catalysts are an optional ingredient in the compositions of the present invention. The bleaching compounds can be catalyzed by manganese compounds if desired. Such compounds are known in the art and include, for example, manganese as disclosed in US Patent Nos. base catalyst. Preferred examples of these catalysts include: Mn ^Ⅳ ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^Ⅲ ₂ (uO ) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ -(ClO ₄ ) ₂ 、Mn ^Ⅳ ₄ (uO) ₆ (1, 4,7-triazacyclononane) ₄ (ClO ₄ ) ₄ 、Mn ^Ⅲ Mn ^Ⅳ ₄ (uO) ₁ (u-OAc) ₂ -(1,4,7-trimethyl-1,4,7 -Triazacyclononane) ₂ (ClO ₄ ) ₃ , Mn ^Ⅳ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (OCH ₃ ) ₃ (PF ₆ ), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in US Patent Nos. 4,430,243 and 5,114,611. The use of various manganese complex ligands for bleach enhancement is also reported in the following US patents: 4,728,455, 5,284,944, 5,246,612, 5,256,779, 5,280,117, 5,274,147, 5,153,161 and 5,227,084.

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

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

These cobalt catalysts can be prepared by known methods as described in the Tobe article and references cited therein, US Patent 4,810,410, Diakun et al., J. Chem, published March 7, 1989. Ed.(1989),66,(12),1043-45, The Synthesis and Characterization of Inorganic Compounds,W.L.Jolly(Prentice Hall,(1970),pp.461-3,Inorg.Chem,18,1497-1502(1979 ), Inorg Chem., 21, 2881-2885 (1982), Inorg. Chem., 18, 2023-2025 (1979), Inorg. Synthesis, 173-176 (1960) and Journal of Physical Chemistry, 56, 22-25 (1952).

In practice, and without limitation, the automatic dishwashing detergent compositions and cleaning methods of the present invention are adapted to provide about at least 0.01 ppm active bleach catalyst material in the aqueous wash liquor, and preferably in the wash liquor 0.01-25 ppm, more preferably 0.05-10 ppm, most preferably 0.1-5 ppm bleach catalyst material. To achieve this level in automatic dishwashing liquors, typical automatic dishwasher detergent compositions according to 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 Is a manganese or cobalt catalyst. builder

For example, in order to facilitate the control of the minerals in the washing water, especially the hardness of Ca ²⁺ and/or Mg ²⁺ , or to facilitate the removal of particulate dirt on the surface, the composition of the present invention may optionally, and preferably, contain detergent additives. lotion. Builders work by various mechanisms, including forming soluble or insoluble complexes with hardness ions by ion exchange, and by forming a surface that is more conducive to the precipitation of hardness ions than the surface of the item being cleaned. The level of builder will vary depending on the end use and physical form of the composition. Built detergents generally contain at least 1% builder. Liquid formulations generally contain from 5% to 50%, preferably from 5% to 35%, of builder. Granular formulations generally comprise from 10% to 80%, preferably from 15% to 50%, by weight of the detergent composition, of builder. Lower or higher levels of builders are not excluded. For example, some detergent additives or high-surfactant formulations can be built without builders.

Suitable builders may be selected from: salts of phosphates and polyphosphates, especially sodium salts; silicates, including water-soluble and aqueous solids, and including those with chain-, layer-, or three-dimensional structures and amorphous solids or unstructured liquids; carbonates, bicarbonates; sesquicarbonates and carbonate minerals other than sodium carbonate or sodium sesquicarbonate; aluminosilicates; organic mono-, Di-, tri-, and tetracarboxylates, especially water-soluble non-surfactant carboxylates in the form of sodium, potassium, or alkanolammonium salts, and oligomers or water-soluble Low molecular weight polymeric carboxylates; and phytic acid. These materials can be supplemented with borates (e.g. for pH buffering purposes), or with sulfates, especially sodium sulfate, and any other filler or carrier, which Fillers or carriers may be important in producing stable surfactant-containing and/or builder-containing detergent compositions.

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

Phosphorus-containing detergent builders are generally preferred whenever regulations permit, including, but not limited to: alkali metal, ammonium, and alkanolammonium salts of polyphosphates, such as tripolyphosphate, pyrophosphate, glassy polyphosphate Phosphates and phosphonates.

Suitable silicate builders include: alkali metal silicates, especially those liquid and solid alkali metal silicates having a _SiO2 : _Na2O ratio in the range of 1.6:1 to 3.2:1, including, especially for For automatic dishwashing purposes, silicates with a water content ratio of 2 in the solid state supplied by PQ Corp under the trade name ^BRITESIL_ , such as BRITESIL H ₂ O; phyllosilicates, see HPRieck, authorized 12 May 1987 Described in U.S. Patent US 4664839; NaSKS-6, sometimes simply referred to as "SKS-6", is a crystalline layered aluminum-free delta-Na ₂ SiO ₅ state silicate sold by the Hoechst company, which is used in laundry It is particularly preferred in granular detergents, see the preparations in DE-A-3,417,649 and DE-A-3,742,043. Other phyllosilicates such as having the general formula _{NaMSixO 2x+1} yH ₂ O can also be used or optionally used in the present invention, wherein: M is sodium or hydrogen, n is 1.9-4, preferably 2, y 0-20, preferably 0. Hoechst's phyllosilicates include: NaSKS-5, NaSKS-7, and NaSKS-11 in the α-, β-, and γ-phyllosilicate states, respectively. Other silicates can also be used, such as magnesium silicate, which can be used as a crisping agent in the granules, as a stabilizer for bleaches, and as a component in suds control systems.

Builders suitable for use in the present invention are also synthetic crystalline ion-exchange materials with a chain structure or hydrates _thereof , and are composed of the following general formula: _{xM2O.ySiO2.zM'O} , wherein M is Na and/or K, M' is Ca and/or Mg, y/x is 0.5-2.0, and z/x is 0.005-1.0, as described in US 5,427,711 issued to Sakaguchi et al. in 1995.

Suitable carbonate builders include the alkaline earth and alkali metal carbonates described in German Patent Application No. 2321001, published November 15,1973. Sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals, such as trona or any common double salt of sodium carbonate and calcium carbonate, if anhydrous, have the composition 2Na ₂ CO ₃ ·Ca ₂ CO ₃ , even calcium carbonate including calcite, aragonite, and vaterite, especially the relatively dense form of calcite with a large surface area, can also be used, for example, as seeds or in block synthetic detergents.

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

Suitable organic detergent builders include polycarboxylate compounds including water-soluble non-surfactant dicarboxylates and tricarboxylates. 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 salt form, alkali metal salts such as sodium, potassium and lithium, or alkanolammonium salts are preferred. Polycarboxylate builders include ether polycarboxylates such as oxydisuccinates, see U.S. Patent 3,128,287, Berg, issued April 7, 1964, and U.S. Patent 3,635,830, Lamberti et al., issued January 18, 1972 , see also "TMS/TDS" builders in US Patent 4,633,071, Bush et al., issued May 5,1987. Other suitable ether carboxylates include cyclic and aliphatic cyclic compounds described in US Patent Nos. 3,922,679, 3,835,163, 4,158,635, 4,120,874 and 4,102,903.

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

Citrate builders, such as citric acid and its water-soluble salts, are particularly important carboxylate builders, eg, in liquid heavy duty laundry detergents, because of their availability from renewable resources and biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and mixtures.

Where phosphorus-based builders can be used, and particularly in the formulation of bars for hand washing, the various alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders, such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see U.S. Patent Nos. 3,159,581, 3,213,030, 3,422,021, 3,400,148, and 3,422,137), can also be used. Can play the effect of descaling.

Some detergent surfactants or their short chain analogues also have a builder function. For stated formulations, when ingredients have surfactant properties, these materials are generally classified as detersive surfactants. The preferred example of the surfactant with builder function is: 3,3-dicarboxy-4-oxa-1,6-hexanedioate, and related compounds thereof, in the U.S. Patent of Bush authorized on January 28, 1986 4566984 as disclosed. Succinic acid builders include _C5 - _C20 alkyl and alkenyl succinic acids and salts thereof. Succinate builders also include: Laurylsuccinate, Myristylsuccinate, Cetylsuccinate, 2-Dodecenylsuccinate (preferred), 2-Pentadecenylsuccinate . Lauryl succinates are described in European Patent Application 86200690.5/0200263, published November 5, 1986. Fatty acids such as C ₁₂ -C ₁₈ monocarboxylic acids can also be added alone, or mixed with the aforementioned builders, especially citrate and/or succinate builders, as surfactant builders. Creates additional builder activity. Other suitable polycarboxylates are described in US Patent 4,144,226, Crutchfield et al., issued March 13, 1979, and in US Patent 3,308,067, Diehl, issued March 7, 1967. See also US Patent 3,723,322 to Diehl.

Other types of inorganic builder materials that can be used have the formula: (M _x ) _i Ca _y (CO ₃ ) _z where x and i are integers between 1-15 and y is an integer between 1-10 , z is an integer between 2-25, M _i is a cation, at least one of which is water-soluble, and satisfies the equation ∑ _i =1-15 (valence of x _i ×M _i )+2y=2z at the same time, so the structural formula Has a neutral or "balanced" charge. Builders are referred to herein as "mineral builders". Bound water or anions other than carbonate may be added to keep the overall charge balanced or neutral. The charge or valence of these anions should be added to the right side of the above equation. Preferred water-soluble cations are selected from hydrogen, water-soluble metals, boron, ammonium, silicon and mixtures thereof, more preferably sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, most preferably sodium and potassium. Non-limiting examples of non-carbonate anions include: chloride, sulfate, fluoride, oxygen, hydroxide, silica, chromate, nitrate, borate, and mixtures thereof. Builders of this type in their simplest form are preferably selected from Na ₂ Ca(CO ₃ ) ₂ , K ₂ Ca(CO ₃ ) ₂ , Na ₂ Ca ₂ (CO ₃ ) ₃ , NaKCa(CO ₃ ) ₂ , NaKCa ₂ (CO ₃ ) ₃ , K ₂ Ca ₂ (CO ₃ ) ₃ and mixtures thereof. The most preferred builder material described herein is _Na2Ca ( _CO3 ) ₂ in any of its crystalline forms. Suitable builder types as defined above may also include, any one or combination of the following substances in natural or synthetic form: acaciasite, sorbite, zeolite Y, zeolite , carbon boron magnesium calcium stone, yellow carbon strontium soda stone, hydropotassium calcium carbonate calcium stone, cannonite, stone ceronite, carbon silica soda calcium stone, potassium cannonite, yttrium strontium carbon city Y, carbon potassium calcium calcium stone, Ferrisurite, Sulfur Potassium Calcium Stone, Carbon Boron Manganite, Monoclinic Soda Calcite, Girvasite, Ilmenite, Sulphur Carbon Calcium Manganite, Kamphaugite Y, Fluorocarbonate Bismuth Calcium Stone, Khanneshite, LepersonniteGd, Li Caxia Stone, barium yttrium yttrium ore Y, micro-alkali cannonite, carbon tellurite, Nicarbon soda limestone, Nicarbon soda limestone, Remondite Ce, Potassium cannonite, plate carbonite, soda calcium carbonate, Pallonite, Soda-Mallonite, Sulfurite, Cooperite, Cacryptite, and Zemkorite. Preferred mineral forms include nilmanite, sorrelite and sorrelite. polymeric soil release agent

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

The hydrophilic portion of the preferred SRA generally has an affinity with the surface of a hydrophobic fiber, such as polyester or nylon, and the hydrophobic portion deposits on the hydrophobic fiber and remains adsorbed thereto until the end of the washing or cleaning process, thus anchoring the hydrophilic portion . This allows subsequent stains treated with SRA to be easily removed in subsequent wash cycles.

SRAs may comprise, variously charged, eg anionic or even cationic (see US Pat. No. 4,956,447), as well as uncharged monomeric units and may be linear, branched, or even star-shaped in structure. They include capping moieties that are particularly effective in controlling molecular weight, or altering physical properties, or altering surface active properties. The structure and charge distribution can be tuned for different fiber or fabric types and different detergent or detergent additive products.

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

Suitable SRAs include: the sulfonation products of substantially linear oligoesters, an oligoester backbone comprising terephthaloyl groups and oxyalkylene oxygen repeating units and allyl-derived sulfonate covalently bonded to the backbone. end part. This is just as described in U.S. Patent No. 4,968,451 of J.J. Scheibel and E.P.Gosselink granted on November 6, 1990: the oligoester can be prepared by: (a) ethoxylated allyl alcohol, (b) ) react the product of (a) with dimethyl terephthalate ("DMT") and 1,2-propanediol ("PG") through two steps of transesterification/oligomerization, (c) The product of (b) is reacted with sodium metabisulfite in water; anion-terminated 1,2-propylene terephthalate polyester/ Polyoxyethylene terephthalate polyesters, such as may be produced by transesterification/oligomerization of poly(ethylene glycol) methyl ether, DMT, PG and polyethylene glycol (“PEG”); 1988 Gosselink's U.S. Patent No. 4,721,580, issued March 26, partially and entirely anionically terminated oligoesters such as ethylene glycol ("EG"), PG, DMT, and 3,6-dioxa-8-hydroxyoctane Oligomers of Sodium Oxide; Non-ionic end-capped block polyester oligomers in US Pat. or from mixtures of DMT, EG and/or PG, Me-terminated PEG, and sodium dimethyl-5-sulfoisophthalate; and U.S. Patent 4,877,896 to Maldonado, Gosselink et al., issued Oct. 31, 1989 Anion (especially sulfaroyl) terminated terephthalates in . The latter is a typical SRA used in laundry detergents and fabric conditioning products, e.g. made from the monosodium salt of m-sulfobenzoic acid, PG and DMT, preferably but preferably containing added PEG (eg PEG 3400) ester composition.

SRA also includes: Simple block copolymers of ethylene or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see 25 May 1976 US Patent No. 3,959,230 issued to Hays and US Patent No. 3,893,929 issued to Basadur on July 8, 1975; cellulose derivatives such as the hydroxyether cellulose polymer METHOCEL from Dow; C ₁ -C ₄ alkyl fibers and _C4 hydroxyalkylcelluloses, see US Patent No. 4,000,093, issued December 28, 1976 to Nicol et al. Suitable SRAs characterized by poly(vinyl ester) hydrophobic moieties include: poly(vinyl esters) grafted onto polyoxyalkylene backbones, such as poly(C ₁ -C ₆ vinyl esters), preferably poly(vinyl acetate) ) of graft copolymers. See European Patent Application 0,219,048, published April 22, 1987 by Kud et al. Commercially available examples include: SOKALAN SRA's such as SOKALAN HP-22 from BASF, Germany. Other SRAs are: repeating units derived from polyoxyethylene glycol with an average molecular weight of 300-5000 containing 10-15% by weight ethylene terephthalate and 80-90% by weight terephthalic acid Poly(oxyethylene) esters are polyesters. Commercially available examples include: ZELCON5126 from DuPont, and MILEASET from ICI.

Another preferred SRA is an oligomer having the experimental formula (CAP) ₂ (EG/PG) ₅ (T) ₅ (SIP) ₁ containing terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1,2-propenyl (EG/PG) units and are preferably capped with a capping group (CAP), preferably a modified isethionate, e.g. In an oligomer, which contains a sulfoisophthaloyl group, 5 terephthaloyl groups, a given ratio (preferably about 0.5:1-10:1) of oxyethyleneoxy and oxy-1 , a 2-propyleneoxy unit, and two capping units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate. The SRA also preferably comprises: 0.5%-20% by weight of the oligomer to reduce crystallization stabilizers, for example: anionic surfactants such as sodium dodecylbenzene sulfonate or selected from xylene-, Cumene- and toluene-sulfonates or mixtures thereof, wherein these stabilizers or modifiers are in the manner described in US Pat. into the synthesis reactor. Monomers suitable for the above SRA include: sodium 2-(2-hydroxyethoxy)-ethanesulfonate, DMT, sodium dimethyl-5-sulfoisophthalate, EG and PG.

Another preferred class of SRAs are oligoesters comprising: (1) a backbone comprising (a) at least one selected from dihydroxysulfonate or polyhydroxysulfonate, one having at least three functional groups to form ester linkages to Units producing a branched oligomer backbone, and mixed units thereof; (b) at least one terephthaloyl unit; and (c) at least one unsulfonated unit that is 1,2-oxyalkyleneoxy; and (2) are selected from the group consisting of nonionic capping units, anionic capping units (e.g. alkoxylated, preferably ethoxylated isethionate, alkoxylated propanesulfonate, alkoxylated propanedisulfonate salts, alkoxylated phenol sulfonates, sulfaroyl derivatives, and mixtures thereof). Such esters preferably have the empirical formula:

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

Preferred SEG and CAP monomers for the above esters include: sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate (“SEG”), 2-{(2-(2-hydroxyethoxy)ethoxy Sodium ethanesulfonate ("SE3") and its homologues, and mixtures thereof, and ethoxylation and sulfonation products of allyl alcohol. Preferred SRA esters of this type include: In the presence of a catalyst, sodium 2-{(2-(2-hydroxyethoxy)ethoxy}ethanesulfonate and/or 2-[2-{(2-(2-hydroxyethoxy)ethoxy) }Ethoxyl] sodium ethanesulfonate, DMT, 2-(2,3-dihydroxypropoxy) sodium ethanesulfonate, EG and PG are obtained by transesterification and oligomerization, which can be defined as (CAP) ₂ (T) ₅ (EG/PG) _1.4 (SEG) _2.5 (B) _0.13 , where: CAP is (Na ^+- O ₃ S[CH ₂ -CH ₂ O] _3.5 )-, and B is a Glyceryl units, after complete hydrolysis the EG/PG molar ratio measured by conventional gas chromatography was about 1.7:1.

Another type of SRA includes: (I) non-ionic terephthalates using diisocyanate coupling agents to link polymer ester structures, see US Patent No. 4,201,824 by Violland et al. and US Patent No. 4,240,918 by Lagasse et al.; (II) SRA with 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 trimellitic anhydride, an ester of an isolated carboxylic acid, rather than by opening the anhydride linkage. Both nonionic and anionic SRAs can be used as starting materials as long as they contain hydroxyl end groups that can be esterified. See U.S. Patent 4,525,524 by Tung et al. In addition, SRAs also include: (III) urethane-linked anionic terephthalate-based SRAs, see U.S. Patent No. 4,201,824 by Violland et al.; (IV) poly(vinyl caprolactam), and Corresponding copolymers of monomers such as vinylpyrrolidone and/or (dimethylaminoethyl) methacrylate, including nonionic and cationic polymers, see U.S. Patent No. 4,579,681 to Ruppert et al.; (V) except BASF Corporation Graft copolymers obtained by grafting acrylic monomers onto sulfonated polyesters, other than the SOKALAN type; these SRAs certainly have similar soil release and anti-redeposition activities to known cellulose ethers, See Rhone-Poulenc Chemie. Company's European patent application EP 279,134A in 1988; (VI) grafts of vinyl monomers, such as grafts of acrylic acid and vinyl acetate grafted to proteins (such as casein), See European patent application EP457,205A (1991) of BASF Company; (VII) polyester-polyamide SRA prepared by condensation of adipic acid, caprolactam and polyethylene glycol, which is particularly suitable for processing polyamide fibers, see DE 2,335,044 (1974) of Bevan et al., Unilever N.V. Company. Other useful SRAs are described in US 4,240,918, 4,787,989, 4,525,524 and 4,877,896. Soil removal/anti-redeposition agent

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

The most preferred soil release/anti-redeposition agent is ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are further described in US Patent 4,597,898, VanderMeer, issued July 1,1986. Another class of preferred soil release/antiredeposition agents are the cationic compounds described in European Patent Application 111965, Oh and Gosselink, published June 27,1984. Other soil release/anti-redeposition agents that may be used include: ethoxylated amine polymers, described in European Patent Application 111984, Gosselink, published June 27, 1984; zwitterionic polymers, described in Jul. 1984 described in European Patent Application 112,592, Gosselink, published 4; Other soil removal/anti-redeposition agents known in the art may also be used in the present compositions. See US Patent 4,891,160, VanderMeer, issued January 2, 1990, and International Patent 95/32,272, published November 30, 1995. Another preferred anti-redeposition agent includes carboxymethylcellulose (CMC) materials. These materials are known in the art. polymeric dispersant

In the present compositions, especially when zeolite and/or layered silicate builders are present, it can be advantageous to include from 0.1% to 7% by weight of polymeric dispersants. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although other dispersants known in the art can also be used. Although bound by theory, it is believed that polymeric dispersants, when combined with other builders, including low molecular weight polycarboxylates, increase The effect of builders throughout the detergent.

Polymeric polycarboxylates can be prepared from suitable unsaturated monomers, preferably in the acid form, by polymerization or copolymerization. Unsaturated monomeric acids which 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. Here polymeric polycarboxylates or monomeric segments containing non-carboxylate groups such as vinylmethyl ether, styrene, ethylene etc. are suitable provided that such segments do not constitute more than 40% by weight of the composition.

Particularly useful polymeric polycarboxylates are derived from acrylic acid. Acrylic acid-based polymers useful herein are the water-soluble salts of polyacrylic acid. The average molecular weight of these polymers in acid form is suitably 2000-10000, preferably 4000-7000, most preferably 4000-5000. Water-soluble salts of these acrylic acid polymers include, for example, alkali metal, ammonium and substituted ammonium salts. Water soluble polymers of this type are known, for example Diehl, U.S. Patent 3,308,067, issued March 7, 1967, discloses the use of polyacrylates of this type in detergent compositions.

Acrylic/maleic based copolymers are also a preferred ingredient in the dispersant/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic and maleic acids suitably having an average molecular weight in the acid form of 2,000-100,000, more preferably 5,000-75,000, most preferably 7,000-65,000. The ratio of acrylate moieties to maleate moieties in the copolymer is usually from 30:1 to 1:1, preferably 10:1 to 2:1. Water-soluble salts of these acrylic acid/maleic acid copolymers include, for example, alkali metal, ammonium and substituted ammonium salts. Such water-soluble acrylic acid/maleic acid copolymers are also known and described in application numbers EP66915, published on November 15, 1982, and EP193360, published on September 3, 1986, which also disclose such Copolymer composed of hydroxypropyl acrylate. Other useful dispersants include maleic acid/acrylic acid/vinyl alcohol terpolymers. These materials are also disclosed in European patent EP193360 and include for example 45/45/10 acrylic acid/maleic acid/vinyl alcohol terpolymers.

Another suitable polymer is polyethylene glycol (PEG). PEG exhibits dispersant properties and at the same time acts as a clay soil removal-anti-redeposition agent. The molecular weight range for the above application is usually 500-100,000, preferably 1,000-50,000, most preferably 1,500-10,000.

Polyaspartate and polyglutamate dispersants can also be used, especially in combination with zeolite builders. The average molecular weight of the dispersant such as polyaspartate is preferably 10,000. brightener

Any fluorescent whitening agent or other whitening agents known in the art can be incorporated into the detergent composition, usually in an amount of 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) stilbenes, pyrazolines, coumarins, carboxylic acids, methinecyanines, thiofluorene-5,5-dioxide compounds, pyrroles, derivatives of five- and six-membered heterocycles and other miscellaneous agents. Examples of the above-mentioned brightening agents are disclosed in "The Production and Application of Fluorescent Brightening Agents" (The Production and Application of Fluorescent Brightening Agents), by M. Zahradnik, published by John Wiley & Sons. New York (1982).

Specific examples of optical brighteners useful in the compositions of the present invention are consistent with those disclosed in US Patent 4,790,856, published November 13, 1988, to Wixon. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners 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 amino Coumarin. Specific examples of these brighteners include: 4-methyl-7-diethyl-aminocoumarin; 1,2-bis(benzopyrazol-2-yl)ethene; 1,3-diphenylpyridine oxazoline; 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. See also US3646015, Hamilton, February 29,1972. dye transfer inhibitor

One or more dye transfer inhibiting agents may also be included in the compositions of the present invention to inhibit the transfer of dyes from fabric to fabric during laundering. Typically, such inhibitors include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures of the foregoing . When used, these inhibitors generally comprise 0.01% to 10% by weight of the composition, preferably in the range of 0.01% to 5%, most preferably in the range of 0.05% to 2%.

More specifically, the polyamine N-oxide polymers preferably used in the present invention contain units of the formula: RA _x -P; where P is a polymerizable unit to which an NO group can be attached, or an NO group Can be part of this unit or the NO group can be linked to two 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, which can be bonded to the N of the NO group or NO groups are part of these groups. Preferred polyamine N-oxides in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof. The NO group can be represented by the following general formula:

Wherein R ₁ , R ₂ , R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y, z are 0 or 1; N in the NO group can be with any of the above The groups are attached to or form part of the above groups; the amine oxide units of the polyamine N-oxides have a pKa<10, more preferably a pKa<7, most preferably a pKa<6.

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

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

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers are also preferably used (classified as PVPVI). Usually the average molecular weight of PVPVI is 5,000～1,000,000, preferred range is 5,000～200,000, preferably 10,000～20,000 (the scope of average molecular weight is determined by light scattering method, as people such as Barth in " chemical analysis " (Chemical Analysis), Vol .113, described in "Modern Methods of Polymer Characterization" (Modern Methods of Polymer Characterization), the disclosure of which is incorporated herein by reference. In PVPVI, the molar ratio of N-vinylimidazole to N-vinylpyrrolidone is usually from 1:1 to 0.2:1, the preferred range is from 0.8:1 to 0.3:1, the optimum range is from 0.6:1 to 0.4:1, these copolymers may be linear or branched.

The composition of the present invention may also contain polyvinylpyrrolidine (PVP) having an average molecular weight of 5,000-400,000, preferably 5,000-200,000, most preferably 5,000-50,000. PVP is well known to those skilled in the detergent art. See, for example, EP-A-262897 and EP-A-256696 (see references herein). Compositions containing PVP may also contain polyethylene glycol (PEG), with an average molecular weight of PEG ranging 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 usually from 2:1 to 50:1, preferably from 3:1 to 10:1.

The present detergent compositions may also optionally contain 0.005% to 5% by weight of certain types of hydrophilic optical brighteners which also inhibit dye transfer. When used, it is preferably in the range of 0.01% to 1% by weight of the composition.

The hydrophilic fluorescent whitening agent that the present invention can use has following structural formula:

Wherein R ₁ is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R ₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- Methylamino, morpholino, chlorine, amino; M is a salt-forming cation, such as Na ⁺ or K ⁺ .

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

When R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino, M is a cation such as Na ⁺ , then the whitening agent is 4,4'-bis[(4-anilino- 6-(N-2-Hydroxyethyl-N-methylamino)-1,3,5-triazin-2-yl)amino]2,2′-stilbene disulphonic acid disodium salt, this whitening agent Also sold by Ciba-Geigy under the tradename Tinapol 5BM-GX.

When R ₁ is anilino, R ₂ is morpholino, M is a cation such as Na ⁺ , then the brightener is 4,4'-bis[(4-anilino-6-morpholino-1,3,5 -Triazin-2-yl)amino]2,2'-stilbene disulfonic acid disodium salt, this brightener is also sold by Ciba-Geigy under the trade name Tinapol AMX-GX.

The special fluorescent whitening agent selected in the present invention, when used in combination with the selected polymeric dye transfer inhibitor as mentioned above, can produce a very effective effect of inhibiting dye transfer. The combination of selected polymers (such as PVNO and/or PVPVI) and selected optical brighteners (such as Tinapol-UNPA-GX, Tinapol 5BM-GX and Tinapol AMX-GX) in the aqueous wash solution is more effective than any of them One exerts better dye transfer inhibition effect when used alone. Without wishing to be bound by theory, it is believed that such brighteners act in this manner due to their high affinity for fabrics in the wash liquor and thus relatively rapid attachment to these fabrics. The degree to which the brightener adheres to the fabric in the wash solution can be determined by the "exhaustion coefficient". The exhaustion factor is usually the ratio of a) the brightener attached to the fabric to b) the original concentration of brightener in the wash liquor. Brighteners with relatively high exhaustion coefficients are most suitable for inhibiting dye transfer in the present invention.

Of course, it should be appreciated that other classes of conventional optical brightener compounds may optionally be used in the compositions of the present invention to provide a general fabric "brightening" effect rather than a true dye transfer inhibiting effect. Such usage is customary and known in detergent formulations.

Chelating agent

The present detergents may also optionally contain one or more iron and/or manganese chelating agents. These chelating agents may be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all of which will be explained in detail hereinafter. Without intending to be bound by theory, it is believed that the advantages of these materials are due in part to their special ability to remove iron and manganese ions from the wash solution by forming soluble chelates.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, Triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate and ethanol diglycine, their alkali metal, ammonium and substituted ammonium salts and mixtures thereof.

Amino phosphonates are also useful as chelating agents in the compositions of the invention when at least low levels of total phosphorus are tolerated in detergent compositions, including ethylenediaminetetrakis (methylene phosphonates), such as DEQUEST. These amino phosphonates preferably do not contain alkyl or alkenyl groups having more than 6 carbon atoms.

Multifunctional substituted aromatic chelating agents are also useful in the compositions of this patent, see U.S. 3,812,044, issued May 21, 1974, to Connor et al. 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"), especially described in U.S. 4,704,233, December 3, 1987 by Hartman and Perkin et al [S ,S] isomer.

The compositions of this patent may also contain water-soluble methylglycine diacetic acid (MGDA) salts (or in acid form) as chelating agents or in combination with other insoluble auxiliary builders such as zeolites and layered silicates.

If used, such chelating agents generally comprise from 0.1% to 15% by weight of the detergent compositions, more preferably from 0.1% to 3.0% by weight.

Foam inhibitor

Compounds that reduce or inhibit the formation of suds can be added to the compositions of the present invention. Sud suppression is of great importance in the so-called "high density cleaning process" and front-loading European washing machines described in U.S. Patent Nos. 4,489,455 and 4,489,574.

A wide variety of substances can be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, eg, Kirk Othmer's Encyclopedia of Chemical Engineering, Third Edition, Vol. 7, pp. 430-447 (John Wiley & Son Co., 1979). A very important class of suds suppressors comprises monocarboxylic fatty acids and their soluble salts. See U.S. Patent 2,954,347 issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof useful as suds suppressors generally contain hydrocarbon chains of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium, lithium and ammonium and alkanolammonium salts.

Non-surfactant suds suppressors can also be included in the detergent compositions. Including, for example: high molecular weight hydrocarbons such as paraffin hydrocarbons, fatty acid esters (eg fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic ketones having 18 to 40 carbon atoms (eg sterone) and the like. Other suds suppressors include N-alkylated aminotriazines, such as three to hexaalkylmelamine or di to tetraalkyldiamine chlorotriazines, which are composed of cyanuric chloride and 2 or 3 moles containing 1 to 24 Primary or secondary amines of carbon atoms, propylene oxide and monostearyl phosphates such as monostearyl phosphate and monostearyl di-alkali metal (such as K, Na and Li) phosphates and phosphates . Hydrocarbons, such as paraffins and haloparaffins, can be utilized in liquid form. Liquid hydrocarbons are liquid at room temperature and one atmospheric pressure, the solidification point is in the range of -40°C to 50°C, and the minimum boiling point is not lower than 110°C (one atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferably having a melting point below 100°C. Hydrocarbons constitute a preferred class of suds suppressors in detergent compositions. Hydrocarbon foam suppressants have been described, for example, in US Patent No. 4,265,779, Gandolfo et al., issued May 5, 1981. Also hydrocarbons include aliphatic, cycloaliphatic, aromatic and heterocyclic saturated or unsaturated hydrocarbons containing 12 to 70 carbon atoms. In discussions of suds suppressors, the term "paraffins" is used to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred class of non-surfactant suds suppressors includes silicone suds suppressors. Such foam suppressors include the use of polyorganosiloxanes such as polydimethylsiloxane, suspensions or emulsions of polyorganosiloxane oils or resins, polyorganosiloxanes chemisorbed or fused to silica A mixture of polyorganosiloxane and silica particles formed above. Silicone suds suppressors are well known in the art, see, for example, U.S. Patent 4,265,779, Gandolfo, May 5, 1981, and European Patent Application No. 89307851.9, Starch M.S., February 7, 1990.

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

Mixtures of polysiloxanes and silanized silicas are also described, see, for example, German Patent Application DOS 2,124,526. Silicone antifoam and suds control agents in granular detergent compositions are disclosed in US Patent 3,933,672 to Bartolotta et al. and US Patent 4,652,392, Baginski et al., issued March 24,1987.

A typical polysiloxane suds suppressor used here is a class of suds control agents that suppress suds at a dosage, and basically consists of:

(i) Polydimethylsiloxane fluids with viscosities from 20cs to 1,500cs at 25°C

(ii) From about 5 to about 50 parts by weight per 100 parts of (i) a polysiloxane resin consisting of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, (CH ₃ ) ₃ SiO _1/ The ratio of ₂ units to SiO ₂ units is from about 0.6:1 to 1.2:1; and

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

In preferred suds suppressors herein, the solvent of the continuous phase consists of certain polyethylene glycols or polyethylene glycol-polypropylene glycol copolymers or mixtures thereof (preferred) or polypropylene glycol. The main polysiloxane suds suppressors are branched/crosslinked, preferably non-linear.

To further illustrate this point of view, a typical liquid laundry detergent capable of controlling foam may optionally contain the above-mentioned polysiloxane suds suppressor at a weight percentage of about 0.001% to about 1%, preferably in the range of about 0.01% to About 0.7%, preferably 0.05% to about 0.5%. These polysiloxanes comprise (1) a non-aqueous emulsion of a primary antifoam agent which is a mixture of (a), (b), (c) and (d) as follows: (a) polyorganosiloxane , (b) resinous siloxanes or polysiloxane compounds that yield polysiloxane resins, (c) finely ground fillers and (d) to facilitate the reaction of mixtures of (a) (b) and (c) A silanolate-forming catalyst; (2) at least one nonionic polysiloxane surfactant and (3) polyethylene glycol or a polyethylene glycol-polypropylene glycol copolymer having a solubility in water at room temperature of about 2%, and no polypropylene glycol. Similar contents can be used in granular composition gels, etc., also see U.S. Patent 4,978,471 issued by Starch on December 18, 1990 and U.S. Patent 4,983,316 issued by Starch on January 8, 1991, Huber et al. in February, 1994 U.S. 5,288,431 of the 22nd and Aizawa et al. in U.S. Patents 4,639,489 and 4,749,740, column 1, line 46 to column 4, line 35.

The silicone suds suppressors herein preferably comprise polyethylene glycol and polyethylene glycol/polypropylene glycol copolymers, both having an average molecular weight of less than about 1,000, more preferably between 100 and 800. The polyethylene glycol and polyethylene glycol/polypropylene glycol copolymers herein have a solubility in water at room temperature of 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, most preferably between 200 and 400; and polyethylene glycol/polypropylene glycol copolymers, most preferably PPG 200/PEG 300. The weight ratio of polyethylene glycol to polyethylene glycol/polypropylene glycol copolymer is preferably about 1:1 to 1:10, most preferably 1:3 to 1:6.

The silicone suds suppressors preferably used herein do not contain polypropylene glycol, especially polypropylene glycol having a molecular weight of 4,000. It is also best not to contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101.

Other useful suds suppressors for use in the present invention include secondary alcohols such as 2-alkyl alkanols and mixtures of these alcohols with silicone oils, such as the silicones disclosed in US Pat. Alcohols include _C6 - _C16 alkanols having a _C1 - _C16 chain. Preferred is 2-butyloctanol, available from Condea under the trademark ISOFOL 12. Secondary alcohol mixtures are available from Enichem under the trademark ISALCHEM 123. The suds suppressor mixture typically contains alcohol and silicone in a weight ratio of 1:5 to 5:1.

As with all washing compositions for use in automatic washing machines or dishwashers, suds formation should not exceed a level that would overflow the washing machine or adversely affect the washing mechanism of the dishwasher. When used, the suds suppressor is preferably present in a "suds suppressing amount". "Amount of suds suppressing" means that the composition formulator selects an amount of such suds suppressing agent which provides sufficient suds control. The result is a low sudsing laundry or dish detergent that can be used in automatic washing machines or dishwashers.

Typically 0% to 10% suds suppressor is present in the compositions. When used as suds suppressors, monocarboxylic fatty acids and salts thereof are generally used at levels up to 5% by weight of the detergent composition, preferably from 0.5% to 3% of fatty monocarboxylate suds suppressors. Silicone suds suppressors are typically used at levels up to 2.0% by weight of the detergent composition, although higher concentrations can also be used. Since the primary consideration is to keep costs to a minimum and maintain low dosage and high efficiency to effectively control foaming, in practice, this upper limit depends on the actual situation. The preferred level of use of silicone suds suppressors is from 0.01% to 1%, most preferably from 0.25% to 0.5%. As used herein, these weight percent values include all silicas that may be used in combination with the polyorganosiloxane, as well as any alternative materials. Monostearyl phosphate foam inhibitor is generally used in an amount of 0.1%-2% by weight of the composition. Hydrocarbon suds suppressors are typically used in amounts of 0.01% to 5%, although higher concentrations can also be used. Alcohol suds suppressors generally comprise from 0.2% to 3% by weight of the finished composition.

Alkoxylated Polycarboxylates

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are useful in the present invention to provide additional degreasing capability. These materials are described on pages 4 et seq. of WO 91/08281 and PCT90/01815, incorporated herein by reference.

Chemically, these materials consist of polyacrylates with one ethoxy branch per 7-8 acrylate units. The molecular formula of the side chain is -(CH ₂ CH ₂ O) _m (CH ₂ ) _n CH ₃ , m is equal to 2-3, and n is equal to 6-12. The side chains are ester-linked to the polyacrylate backbone, resulting in a "comb" polymer structure. Molecular weight can vary, but is usually between 2,000-50,000. The compositions may contain from 0.05% to 10% by weight of such alkoxylated polycarboxylates.

fabric softener

Various fabric softeners that have been through the laundering process, especially the finely divided montmorillonite clays of U.S. Patent 4,062,647 issued December 13, 1977 by Storm and Nirsclal, and other softener clays known in the art, can be optionally Optionally used, levels generally from 0.5% to 10% by weight in the compositions of the present invention can function as a fabric softener while also cleaning fabrics. Clay softeners can be used with amine and cationic softeners which have been disclosed, for example, by Crisp et al., U.S. Patent 4,375,416, March 1, 1983, and by Harris et al., September 22, 1981 Published U.S. 4,291,071.

spices

Perfume and fragrance components 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, impatiens essence, sandalwood oil, Pine oil and cedar. Finished perfumes generally comprise from 0.01% to 2% by weight of the present detergent compositions, and the scented components may comprise from 0.0001% to 90% of the finished perfume compositions.

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-tetramethyl Naphthalene; methyl ionone, γ-methyl ionone, methyl cedryl ketone, methyl dihydrojasmonate, methyl 1,6,10-trimethyl-2,5,9-cyclododecane En-1-yl ketone; 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene; 4-acetyl-6-tert-butyl-1,1-dimethylindene p-Hydroxy-phenyl-butanone; Benzophenone; Methyl-β-naphthalenone; 6-Acetyl-1,1,2,3,3,5-hexamethylindan; 5-Acetyl 4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-1 -Formaldehyde; 7-Hydroxy-3,7-dimethyloctanal; 10-undecene-1-al; Isohexenylcyclohexylcarbaldehyde; Formyltricyclodecane; Condensate of anisate, condensate of hydroxycoumarin and indole, condensate of phenylacetaldehyde and indole; 2-methyl-3-(p-tert-butylphenyl)-propionaldehyde; ethyl Vanillin; Piperonal; Hexylcinnamaldehyde; Amylcinnamaldehyde; 2-Methyl-2-(p-isopropylphenyl)-propionaldehyde; Coumarin; Gamma-decalactone; Cyclopentadecane Alcohol anhydride; 16-Hydroxy-9-hexadecanolactone; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopentane- γ-2-benzopyran; β-naphthyl methyl ether; ambroxane; dodecahydro-3a,6,6,9a-tetramethylnaphtho[1,2d]furan; cedrol; 5-(2,2 ,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol; 2-ethyl-4-(2,2,3-trimethyl-3-cyclopentene-1 -yl)-2-buten-1-ol; caryophyllenol; tricyclodecenyl propionate; tricyclodecenyl acetate; benzyl salicylate; Butyl) cyclohexyl acetate.

The most suitable fragrances should be able to improve the odor of the finished cellulase-containing composition to the greatest extent, and these fragrances include (but are not limited to): hexyl cinnamaldehyde; 2-methyl-3-(p-tert-butylphenyl) -propionaldehyde; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene; benzyl salicylate; 7-acetyl -1,1,3,4,4,6-hexamethyltetralin; p-tert-butyl cyclohexyl acetate; methyl dihydrojasmonate; β-naphthyl methyl ether; methyl-β- Naphthalenone; 2-Methyl-2-(p-isopropylphenyl)-propionaldehyde; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8- Hexamethyl-cyclopentane-γ-2-benzopyran; Dodecahydro-3a,6,6,9a-tetramethylnaphtho[1,2d]furan; Anisaldehyde; Coumarin; Cedrol ; vanillin; cyclopentadecanyl anhydride; tricyclodecenyl acetate and tricyclodecenyl propionate.

Other fragrances include aromatic oils, balsams and resins of various origins. These include (but are not limited to): Peru balsam, frankincense resin, benzoin, cistus resin, nutmeg, cinnamon oil, benzoin resin, coriander oil, and hybrid lavender. Some other fragrance compounds include phenylethyl alcohol, terpineol, linalool, picalyl acetate, geraniol, nerol, 2-(1,1-dimethylethyl)-cyclohexyl alcohol esters, benzyl acetate and eugenol. Carriers 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, stick compositions Required solid fillings and more. If high suds is desired, the composition typically incorporates from 1% to 10% of a suds booster, such as an alkanolamide containing 10-16 carbon atoms. The monoethanol and diethanol amides of 10-14 carbon atoms are typical of these suds boosters. Combine these suds boosters with high sudsing optional surfactants such as the aforementioned amine oxides, betaines and sulfonates It is also beneficial to use with betaine. If necessary, water-soluble magnesium and/or calcium salts, such as MgCl ₂ , MgSO ₄ , CaCl ₂ , CaSO ₄ , can also be added, usually at a level of 0.1% to 2%, to generate more foam and enhance the ability to remove grease .

Various optional washing ingredients in the composition can be adsorbed into the porous hydrophobic substance, and then the above-mentioned hydrophobic substance is coated with a hydrophobic coating to further stabilize it. The detersive ingredients are preferably mixed with a surfactant prior to adsorption onto the porous substrate. During use, the detergent ingredients are released from the substrate into the water wash to perform the washing function.

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

Liquid detergent compositions can 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. Monohydric alcohols are best used to dissolve surfactants, but polyols such as those containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups (eg, 1,3-propanediol, ethylene glycol, glycerol, and 1 , 2-propanediol). The content of these carriers can range from 5% to 90%, typically 10% to 50%.

The present cleaning compositions are preferably formulated to have a wash water pH of 6.5 to 11, more preferably 7.5 to 10.5, and liquid dishwashing formulations preferably have a pH of 6.8 to 9.0 when used in aqueous cleaning operations. Laundry detergents are usually at pH 9-11. Methods of controlling the pH at the recommended value include the use of buffers, bases, acids, etc., which are well known to those skilled in the art.

pellet production

The bis-alkoxylated cations of the present invention are added to the blender mixture followed by conventional spray drying to help remove any residual odorous short chain amine contamination that may be present. In this case, the formulator would like to prepare a mixed granule containing the alkoxylated cationic surfactant for use in, for example, high density granular detergents, preferably the granule composition is not strongly alkaline. The high density (greater than 650 g/L) pellet preparation process is described in detail in US Patent No. 5,366,652. These particles are formed at pH 9 or below, which can effectively avoid the odor of impure amines. This can be achieved by adding a small amount of an acidic substance such as boric acid, citric acid or the like or a suitable pH buffer to the granules. In another approach, perfume components can also be used as described herein to mask the potential problem of amine off-flavors.

Example

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

LAS Alkylbenzenesulfonate anion surface with an average chain length of 11.5 carbon atoms

Active agent, preferably sodium salt

AS primary alkyl sulfate anion with an average chain length of 14-15 carbon atoms

   Surfactant, preferably sodium salt

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

  Alcohol (Nonionic Surfactant)

SKS-6 Multilayer silicate, such as Hoechst

Copolymer Sodium salt of copolymer of acrylic acid and maleic acid

Zeolite 1-10μm Zeolite A

PEG4000 polyethylene glycol; the average molecular weight is 4000

NOBS nonanoyloxybenzenesulfonate bleach activator

PB-1 Sodium perborate monohydrate

Proteases Detergent enzymes that break down proteins, as described above; includes BIOSAM 3.0

Amylase Detergent enzyme that hydrolyzes starch

SRA-1 soil release agent; methyl cellulose; molecular weight about 13000, take

Generation degree 1.8-1.9

Soil release agent in SRA-2 US 5415807

Brightener X Tinopal CBS_X; Distyrene biphenyl disulfonates;

Ciba-Geigy

Brightener Y Tinopal UNPA-GX; Cynauric Chlorine/Diaminostilbenes;

Ciba-Geigy

Foam Control Agents Silica/Polysiloxane Foam Inhibitors

The following examples are illustrative of the invention, not intended to limit or define its scope. All parts, percentages and ratios are expressed as percentages by weight unless otherwise specified.

Granular detergents are as in Example A and Example B below.

Example A

Components % by weight (%) ppm

Surfactant

LAS 21.47 143.20

AS 6.55 43.69

NI 3.30 22.01

CocoMeEO2 ^* 0.47 3.13 Alkaline builder

SKS-6 3.29 21.94

Copolymer 7.10 47.36

Zeolite 8.40 56.03

PEG4000 0.19 1.27

Sodium carbonate 17.84 118.99

Silicate (2.0R) 11.40 76.04

Whitening agent

NOBS 4.05 27.01

PB-1 3.92 26.15

enzyme

Protease 0.85 5.67

Amylase 1.20 8.00 Others

SRA-1 0.26 1.73

SRA-2 0.26 1.73

Brightener X 0.21 1.40

Brightener Y 0.10 0.67

Hydrophobic silica 0.30 2.00

Foam inhibitor 0.17 1.13

Sodium sulfate 5.14 34.28

Spices 0.25 1.67

Moisture and Miscellaneous 3.28 21.88 Total 100 667.00 Dosage-20g/30L* The surfactant AQA-1 (CocoMeEO2) in the embodiment can be used with the same amount of AQA-2

- Any one of AQA-22 or other AQA surfactant substitutions herein.

                                                                            % by weight (%) ppm surfactant

LAS 21.47 143.20

AS 6.55 43.69

NI 3.30 22.01

CocoMeEO2 ^* 0.47 3.13 Alkaline builder

SKS-6 3.29 21.94

Copolymer 7.10 47.36

Zeolite 8.40 56.03

PEG4000 0.19 1.27

Sodium carbonate 19.04 127.00

Silicate (2.0R) 11.40 76.04

brightener

NOBS 4.05 27.01

PB-1 3.92 26.15

enzyme

Protease 0.85 5.67

other

SRA-1 0.26 1.73

SRA-2 0.26 1.73

Brightener X 0.21 1.40

Brightener Y 0.10 0.67

Hydrophobic silica 0.30 2.00

Foam inhibitor 0.17 1.13

Sodium sulfate 5.14 34.28

Spices 0.25 1.67

Moisture and miscellaneous 3.28 21.88

Total 100 667.00

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

The following exemplifies the use of compositions within the scope of the present invention to carry out laboratory operations and test results on various soils and stains. It will be seen from the data that the cleaning power of a wide variety of soils and stains on various fabrics is improved. up.

The process of performance testing

sample preparation

Sample preparation basically includes the following steps:

1. Preparation of premixed LAS+AS.

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

3. Preparation of bulk nonionic (AE) surfactants.

4. Preparation of builder solution

5. Preparation of Particulate Matter.

Surfactant:

Surfactant Weight ^* gms Active % Wash Concentration (ppm)

LAS 78.85 44.50 143.20

AS 34.55 31.00 43.70

Cationic surfactant 01.90 40.00 3.10

AE 19.44 100.00 22.00

*Actual weight varies from active percentage

Preparation steps of products for performance testing:

Step I:

Each surfactant is weighed and mixed according to the following steps

1. Weighs 78.85gm LAS.

2. Weigh another 34.55gm AS into the same beaker.

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

4. Premix LAS and AS until completely dissolved, heat at 40°C for about 30 minutes until completely dissolved.

Step II:

1. Weigh 01.90 gm of the cationic surfactant of the present invention into the same beaker containing the premixed LAS and AS liquids.

2. The total volume of the solution at this point is 500 ml.

The 500ml surfactant mixture was effective for 5 washes, using 100ml of this batch for each wash. When adding 49 liters of tap water in this 100ml solution, it is the corresponding washing concentration of each surfactant.

Step Ⅲ:

1. Weighs 19.44gm AE alone.

2. Add 900ml of distilled water to AE.

3. This 900ml solution is effective for 18 washes.

4. Use 50ml of this solution for each wash.

Step IV:

Silicate: 148.32gm per 900ml of distilled water; use 50ml of this solution for each wash.

Copolymer: 92.88gm per 900ml of distilled water; use 50ml of this solution for each wash.

Particulate matter: Weigh out each particulate component into the same beaker.

Sequence of adding to washing machine:

Components are added with stirring in the following order:

1. Silicate (2.0R).

2. Copolymer (as above).

3. particulate matter.

Stop stirring at this point (to avoid foaming when adding surfactant).

4. LAS+AS+cationic surfactant solution.

5. AE solution.

Stir for 15 seconds.

Hardness: No added hardness below tap water hardness.

Load: usually use the washing load with a composition of less than 2.4Kg.

Cotton Uniform Shirts (1)

Old T-shirts (from reviewer) (3)

Big T-shirt(11)

DKPE T-shirt(1)

P/C Shorts(2)

cotton shorts(1)

DKPE is polyester double knit.

DMO is Dirty Motor Oil.

Test results I are as follows, showing the performance of the composition using coconut MeEO2 plus LAS, AS mixture according to the present invention. Test results II show the performance of coconut MeEO10 plus LAS/AS compared to coconut MeEO2/LAS. Performance in the tests is measured on various soils, namely body soils, builder sensitive soils, bleach sensitive soils, surfactant sensitive soils and socks. The term "bis", "EO10" herein indicates two polyethylene oxide chains having a total average of 10 ethylene oxide units in the molecule, usually (but not limited to) about 5 per chain.

  Test Result Ⅰ

  Using LAS and AS (total anion system) with

  Coconut MeO2 Cationic Surfactant Pre-Mixed

Dirt Detection Ⅰ Detection Ⅱ Average

Old collar -0.02 -0.27 -0.15

Collar 0.77S 0.73S 0.75

Cuffs -0.17 0.33 0.08

Dirty -0.1 0.17S 0.04

Body contamination (average) 0.12 0.24 0.18

Clay C/D 1.03S 0.7S 0.87

Clay DKPE 0.7S -0.02 0.34

sensitive to builders

dirt (average) 0.87 0.34 0.61

Spinach 0.33 0.56 0.45

Coffee 0.21 0.42S 0.32

sensitive to bleach

dirt (average) 0.27 0.49 0.38

Meat Sauce 0.84S 1.08S 0.96

Curry 1.14S 1.11S 1.13

Bacon oil 0.1 0.16 0.13

DMO 0.44 -0.34 0.05

sensitive to surfactants

Feeling of dirt (average) 0.63 0.5 0.57

Average (including socks) 0.39 0.38 0.39

Socks (Front) 0.32 0.35A 0.34

Socks (back) 0.08 0.64A 0.36

Socks (δ) -0.24 0.28 0.02

       Test Result Ⅰ

Coconut MEEO2 ion surfactant and LAS alone mixing dirt detection Ⅰ Test II average old collar 0.27 -0.73 -0.23 collar-0.04 0.06 cuffs-0.35 -0.25 -0.30 Fillets 0.13 0.32 body filth (average) 0.00 0.00 -0.08 -0.04 clay C/D 0.59 0.79S 0.69 clay DKPE 0.04 0.66 0.35 Sensitive dirt (average) 0.32 0.73 0.53 spinach 0.07 0.33 coffee 0.24 0.24 0.24 0.24 0.24 0.16 0.41 0.299 Meat sauce -0.1 -0.08 -0.09 Curry 0.1 0.54 0.32 meat oil-0.53 -02 -0.28dmo -0.22 0.05 -0.09 Sensitive dirt (average) -0.19 0.12 -0.04 average (including socks) 0.04 0.19 0.12 socks (front) 0.33 -0.07 0.13 socks (rear) 0.7S -0.05 0.33 socks (δ) 0.36 0.02 0.19

  Test Result Ⅱ

Coconut MEEO2 ion surface active agent and LAS+AS hybrid dirt detection Ⅰ Test Ⅱ average old collar 0.48 -0.02 0.23 collar 0.02 0.06 0.04 cuffs 0.33 0.25 0.29 Fillet-0.28 0.11 -0.09 body dirt 0.14 0.10 0.12 clay C/D 0.75S 0.44 0.60 Clane DKPE 0.27 -0.47 -0.10 Sensitive dirt (average) 0.51 -0.02 0.25 spinach 0.00 0.33 0.38 0.82s 0.60 sensitive dirt (average) 0.19 0.58 0.39 meat Sauce 0.05 0.96s 0.51 curry 0.42 0.91S 0.67 Mental oil 0.23 -0.07 0.08dmo 0.31 -0.13 0.09 Sensitive dirt (average) 0.25 0.42 0.34 average (including socks) 0.26 0.23 short socks (front) 0.14 0.23 0.19 socks (back) -0.19 0.48S 0.15 socks (δ) -0.32 0.25 -0.04

Test results Ⅱ Coconut MEE10 cation surface active agent and LAS alone pre-pre-dirt 0.17 inlaid-0.52 cuffs 0.19 Dirty-0.17 Personal dirt (average) -0.08 clay C/D -0.34 clay dkpe 0.09

Builder sensitive soil (average) -0.13

Spinach 0.06

Coffee 0.08

Bleach Sensitive Dirt (average) 0.07

Meat sauce -0.20

Curry -0.38

Bacon Grease -0.33

DMO -0.33

Surfactant sensitive dirt (average) -0.31

Average (including socks) -0.11

Socks (Front) 0.42S

Socks (Back) 0.64S

Socks (δ) 0.22

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

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

LAS Linear C ₁₂ Alkylbenzene Sulfonate Sodium

TAS Sodium Tallow Alkyl Sulfate

C45AS C _14-15 Linear Alkyl Sulfate Sodium

Condensation of CxyEzS C _1x -C _1y Branched Alkyl Sodium Sulfate with z Moles of Ethylene Oxide

C45E7 C _14-15 is mainly a linear primary alcohol with an average of 7 moles of ethylene oxide

Condensation

C25E3 C _12-15 branched primary alcohols condensed with an average of 3 moles of ethylene oxide

C25E5 _C12-15 branched primary alcohol is condensed with an average of 5 moles of ethylene oxide

Coconut EO2 R ₁ N ⁺ (CH ₃ )(C ₂ H ₄ OH) ₂ where R ₁ is C _12-14

Soap Linear Alkyl Carboxyl from 80/20 Butter Coconut Oil Blend

Sodium Sodium Acid

TFAA C _16-18 Alkyl N-Methyl Glucamide

TPKFA C _12-14 Total Cut Fatty Acid Top Fraction

STPP Sodium Tripolyphosphate Anhydrous

Zeolite A Hydrated Sodium Aluminosilicate Molecular Formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ 27H ₂ O,

The size of the basic particles is 0.1-10μm

NaSKS-6 crystalline layered silicate δ-Na ₂ Si ₂ O ₅

Citric Acid Anhydrous Citric Acid

Carbonate Anhydrous sodium carbonate, particle size 200-900μm

Bicarbonate Anhydrous sodium bicarbonate, particle size 400-1200μm

Silicate Amorphous sodium silicate (SiO ₂ :Na ₂ O=2.0)

Sodium Sulfate Anhydrous Sodium Sulfate

Citrate Trisodium citrate dihydrate, activity 86.4%, particle distribution

          425-850 μm

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

CMC Sodium Carboxymethyl Cellulose

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

For sale by NOVO Industries A/S

Alcalase proteolytic enzyme, activity 3AU/g, NOVO Industries A/S

for sale

Cellulase Hydrolyzing cellulase, activity 1000 CEVU/g,

Trade name Carezyme, sold by NOVO Industries A/S

Amylase Hydrolytic amylase, activity 60 KNU/g, trade name Termamy

                                                             

Lipase Hydrolyzed lipase, activity 100 KLU/g, trade name Lipolase,

For sale by NOVO Industries A/S

Endoenzyme Endoglucose, activity 3000 EVU/g, NOVO Industries

For sale by A/S

PB4 Sodium perborate tetrahydrate, general formula NaBO ₂ .3H ₂ OH ₂ O ₂

PB1 Anhydrous sodium perborate bleach, general formula NaBO ₂ .H ₂ O ₂

Percarbonate Sodium percarbonate, general formula 2NaCO ₃ .3H ₂ O ₂

NOBS Sodium nonanoyloxybenzenesulfonate

TAED Tetraacetylethylenediamine

NACA-OBS (6 nonanoylaminocaproyl) oxybenzenesulfonate

DTPMP Diethylenetriaminepenta(methylene phosphonate)

Cobalt Catalyst Cobalt(Ⅲ) Pentaamine Acetate

Manganese catalyst Mn ^Ⅳ ₂ (mo) ₃ (1,4,7-trimethyl-1,4,7-triazacyclic

Nonane) ₂ -(PF ₆ ) ₂ such as US Patent Nos. 5,246,621 and 5,244,594

as stated

Photosensitizer Sulfonated zinc phthalocyanine, encapsulated in bleached dextrin soluble polymer

Brightener 1 4,4′-bis(2-sulfostyrene)biphenyl disodium

Brightener 2 4,4'-bis(4-anilino-6-morpholino-1,3,5-

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

Sodium

HEDP 1,1-Hydroxyethyldiphosphonic acid

PVNO Polyvinylpyridine N-oxide

PVPVI Copolymer of polyvinylpyrrolidone and vinylimidazole

SRA1 Sulfobenzoyl-terminated with oxyethyleneoxy and p-phenylene

Ester of diacyl backbone

SRA2 Diethoxylated poly(1,2-propylene terephthalate) short insert

Segment Polymer

Polysiloxane defoamers Polydimethylsiloxane foam control agents and silicon as dispersants

                                                                         

from 10:1 to 100:1

In the following examples, all contents are represented by weight percent (%) of the composition

Example 1

Detergent formulations were prepared in accordance with the present invention wherein A and C are phosphorus-containing detergent compositions and B is a zeolite-containing detergent composition.

A B 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 7.0 3.0 3.0

CMC 1.0 1.0 0.5

Brightener 2 0.2 0.2 0.2

Soap 1.0 1.0 1.0

Spray DTPMP 0.4 0.4 0.2 on it

C45E7 2.5 2.5 2.0

C25E3 2.5 2.5 2.0

Polysiloxane defoamer 0.3 0.3 0.3

Spices 0.3 0.3 0.3 dry additives

Carbonate 6.0 13.0 15.0

PB4 18.0 18.0 10.0

PB1 4.0 4.0 0

TAED 3.0 3.0 1.0

Photosensitive bleach 0.02 0.02 0.02

Protease 1.0 1.0 1.0

Lipase 0.4 0.4 0.4

Amylase 0.25 0.30 0.15 Sodium Sulfate Dry Mix 3.0 3.0 5.0

Equilibrium (moisture & miscellaneous) 100.0 100.0 100.0 Concentration (g/L) 630 670 670* The surfactant AQA-1 (coconut MeEO2) in this embodiment can be any one of double AQA-2-double AQA-22 of equal amount or other dual AQA surfactants herein.

The bleach-free detergent composition below Example II is especially useful for washing colored clothes

D E F blown powder

Zeolite A 15.0 15.0 2.5

Sodium sulfate 0.0 5.0 1.0

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 4.0 4.0 - Agglomerates

C45AS - - - 9.0

LAS 6.0 5.0 2.0

TAS 3.0 2.0 -

Silicate 4.0 4.0 -

Zeolite A 10.0 15.0 13.0

CMC - - - 0.5

MA/AA - - - - 2.0

Carbonate 9.0 7.0 7.0 sprayed on it

Spices 0.3 0.3 0.5

C45E7 4.0 4.0 4.0

C25E3 2.0 2.0 2.0 dry additive

MA/AA - - - - 3.0

NaSKS-6 - - - 12.0

Citrate 10.0 - 8.0

Bicarbonate 7.0 3.0 5.0

Carbonate 8.0 5.0 7.0

PVPVI/PVNO 0.5 0.5 0.5

Alcalase 0.5 0.3 0.9

Lipase 0.4 0.4 0.4

Amylase 0.6 0.6 0.6

Cellulase 0.6 0.6 0.6

Polysiloxane defoamer 5.0 5.0 5.0 dry additive

Sodium Sulfate 0.0 9.0 0.0 Equilibrium (Moisture & Miscellaneous) 100.0 100.0 100.0 Concentration (g/L) 700 700 850 * In this example, the surfactant double AQA-1 (coconut MeE double O2) can be used in an equivalent amount of 2 Any of AQA-22 or other dual AQA surfactants herein substituted.

Example Ⅲ

The following are detergent formulations prepared according to the invention.

G G H H I Blown Powder

Zeolite A 30.0 22.0 6.0

Sodium sulfate 19.0 5.0 7.0

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 - 1.0 5.0

Soap - - - 2.0

Brightener 1 0.2 0.2 0.2

Carbonate 8.0 16.0 20.0

DTPMP - 0.4 0.4 sprayed on it

C45E7 1.0 1.0 1.0

dry additive

PVPVI/PVNO 0.5 0.5 0.5

Protease 1.0 1.0 1.0

Lipase 0.4 0.4 0.4

Amylase 0.1 0.1 0.1

Cellulase 0.1 0.1 0.1

NOBS - 6.1 4.5

PB1 1.0 5.0 6.0

Sodium Sulfate - 6.0 -Balance (Moisture & Miscellaneous) 100.0 100.0 100.0*The surfactant bis-AQA-1 (coconut MeEO2) in this example can be any one of bis-AQA-2-bis-AQA-22 or this Replace with other double AQA surfactants.

               Example Ⅳ The following is a high-density and bleach-containing detergent formulation prepared according to this patent

J K K L Blown powder

Zeolite A 15.0 15.0 15.0

Sodium sulfate 0.0 5.0 0.0

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 4.0 2.0 2.0 agglomerates

LAS 5.0 5.0 5.0

TAS 2.0 2.0 1.0

Silicate 3.0 3.0 4.0

Zeolite A 8.0 8.0 8.0

Carbonate 8.0 8.0 4.0 sprayed on it

Spices 0.3 0.3 0.3

C45E7 2.0 2.0 2.0

C25E3 2.0 - - Dry additive

Citrate 5.0 - 2.0

Bicarbonate - 3.0 -

Carbonate 8.0 15.0 10.0

TAED 6.0 2.0 5.0

PB1 13.0 7.0 10.0

Molecular weight 5,000,000

polyethylene oxide - - - 0.2

Bentonite clay - - - 10.0

Protease 1.0 1.0 1.0

Lipase 0.4 0.4 0.4

Amylase 0.6 0.6 0.6

Cellulase 0.6 0.6 0.6

Polysiloxane defoamer 5.0 5.0 5.0 dry additive

Sodium Sulfate 0.0 3.0 0.0 Equilibrium (Moisture & Miscellaneous) to 100.0 100.0 100.0 Concentration (g/L) 850 850 850 * In this example an equivalent amount of Surfactant Bis-AQA-1 (Coconut MeEO2A) can be used Any of AQA-22 or other AQA surfactants herein substituted.

Example V The following is a high-density cleaning composition prepared according to the present invention:

M N blown powder

Zeolite A 2.5 2.5

Sodium sulfate 1.0 1.0

Coconut MeEO2 ^* 1.5 1.5 Agglomerates

C45AS 11.0 14.0

Zeolite A 15.0 6.0

Carbonate 4.0 8.0

MA/AA 4.0 2.0

CMC 0.5 0.5

DTPMP 0.4 0.4 sprayed on it

C25E3 5.0 5.0

Spices 0.5 0.5 dry additives

HEDP 0.5 0.3

SKS-6 13.0 10.0

Citrate 3.0 1.0

TAED 5.0 7.0

Percarbonate 15.0 15.0

SRA1 0.3 0.3

Protease 1.4 1.4

Lipase 0.4 0.4

Cellulase 0.6 0.6

Amylase 0.6 0.6

Polysiloxane defoamer 5.0 5.0

Brightener 1 0.2 0.2

Brightener 2 0.2 -Balance (Moisture & Miscellaneous) to 100.0 100.0 Concentration (g/L) 850 850*The surfactant Bis AQA-1 (coconut MeEO2) in this example can be used with an equivalent amount of Bis AQA-2-bis Any of AQA-22 or other dual AQA surfactants herein substituted.

    Example Ⅵ Following is the liquid detergent composition prepared according to the present invention

O P Q R SLAS 10.0 13.0 9.0 2.0 15.0C25AS 4.0 10.0 2.0 8.0 10.0C25E3S 1.0 -3.0 -C25E7 5.0 11.0 2.0 -TFAA -3.5 -Coconut MEEO2 ^* 0.5 1.0 1.5 3.0TPKFA 2.0 -13.0 -rapeseed fatty acids - 5.0 - Citric Acid 2.0 3.0 1.0 1.5 1.0 Dodecene/Tetradecenyl Succinic Acid 12.0 10.0 - - 15.0 Oleic Acid 4.0 2.0 1.0 - 1.0 Ethanol 4.0 4.0 7.0 2.0 7.0 1,2-Propanediol 4.0 4.0 2.0 7.0 6.0 Monoethanolamine - - - 5.0 -Triethanolamine - - 8 - -NaOH adjusted to pH 8.0 8.0 7.6 7.7 8.0Ethoxylated tetraethylenepentamine 0.5 - 0.5 0.2 -DTPMP 1.0 1.0 0.5 1.0 2.0SRA2 0.3 - 0.2 0.1 -PVNO - - 0.1 - - Protease 0.5 0.5 0.4 0.25 -Alcalase - - - - 15 Lipase - 0.10 - 0.01 - Amylase 0.25 0.25 0.6 0.5 0.25 Cellulase - - - 0.05 - Endoenzyme - - - 0.10 - Boronic acid 0.1 0.2 - 2.0 1.0 Sodium Formate - - 1.0 - - Calcium Chloride - 0.015 - 0.01 - Bentonite Clay - - - - 4.0 Suspended Clay SD3 - - - - 0.6 Equilibrium (Moisture & Misc) to 100 100 100 100 100

*The surfactant bis-AQA-1 (coconut MeEO2) in this example can be replaced with an equivalent amount of any 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 tableting methods.

Heavy duty liquid detergent compositions, especially heavy duty liquid detergents for laundry, comprise a non-aqueous carrier base. The manner in which they are produced will be described in detail below. This non-aqueous composition can also be prepared in another way disclosed in the following patents: US4753570; 4767558; 4772413; 4889652; 4892673; US5266233; EP-A-225654 (6/16/87); EP-A-510762 (10/28/92); EP-A-540089 (5/5/93); EP-A-540090 (5/5 /93); US4615820; EP-A-565017 (10/13/93); EP-A-030096 (6/10/81), the above patents are incorporated by reference. Such a composition can contain various granular detergent ingredients (such as: the aforementioned brightener) that can be stably suspended therein. Therefore, this non-aqueous composition just includes a liquid phase, and the solid phase is optional, but It's better to have. All of this is also described in detail in the cited literature and below. For the production of other laundry detergent compositions, the AQA surfactant is added to the composition at the above-mentioned level and in the manner of addition. liquid phase

The liquid phase usually accounts for 35%-99% of the weight of the detergent composition, the preferred range is 50-95%, and the best when the content is 45-75%. The liquid phase of the present detergent compositions essentially contains a relatively high concentration of an anionic surfactant in combination with a non-aqueous liquid diluent.

(A) Necessary anionic surfactant

Anionic surfactants mainly used as essential components of the non-aqueous liquid phase are selected from alkali metal salts of alkylbenzenesulfonic acids, wherein the alkyl group contains 10-16 carbon atoms and is present in a linear or branched configuration ( See US Patents US2220099 and US2477383, incorporated by reference). A particularly preferred anionic surfactant is the sodium or potassium linear alkylbenzene sulfonate (LAS), wherein the alkyl group has an average of 11-14 carbon atoms. The sodium salt of LAS containing 11-14 carbon atoms is most preferred.

The non-aqueous liquid diluent forms the second essential component of the non-aqueous phase in which the alkylbenzene sulfonate anionic surfactant is soluble. In order to form a structured liquid phase to meet the requirements of suitable phase stability and qualified rheology, the weight content of alkylbenzenesulfonate anionic surfactants in the liquid phase is generally 30%-65%, more preferably alkyl The benzenesulfonate anionic surfactant accounts for 35%-50% by weight of the non-aqueous liquid phase of the present invention. The use of anionic surfactants at these concentrations corresponds to an anionic surfactant concentration in the total composition of 15% to 60% by weight of the composition, preferably in the range of 20% to 40%.

(B) Non-aqueous liquid diluent To form the liquid phase of the detergent composition, the above-mentioned alkylbenzenesulfonate anionic surfactant is combined with a non-aqueous liquid diluent. This diluent contains two essential ingredients, a liquid alcohol alkoxylate and a non-aqueous, low-polarity organic solvent.

i) Alkoxylated Alcohols

The alkoxylated fatty alcohol is an essential ingredient in the liquid diluent used to form the present composition, which is itself a nonionic surfactant and corresponds to the general formula:

R ¹ (C _m H _2m O) _n OH wherein R ¹ is C ₈ -C ₁₆ alkyl; m is 2-4; n is 2-12. R ¹ is preferably primary or secondary alkyl, containing 9-15 carbon atoms, preferably 10-14 carbon atoms; alkoxylated fatty alcohols are preferably ethoxylates, containing 2- 12 ethylene oxide units, preferably 3-10 ethylene oxide units per molecule.

The alkoxylated fatty alcohol component of the liquid diluent generally has a hydrophilic-hydrophobic balance (HLB) in the range of 3-17, preferably 6-15, most preferably 8-15.

Examples of alkoxylated fatty alcohols useful as one of the main components of the non-aqueous liquid diluent of the compositions of the present invention include those made from alcohols having 12 to 15 carbon atoms and containing 7 moles of ethylene oxide Alkoxylated fatty alcohols such as those sold by Shell under the tradenames Neodol 25-7 and Neodol 23-6.5. Other useful Neodols include Neodol 1-5, which is an ethoxylated fatty alcohol with an average alkyl chain of 11 carbon atoms and 5 moles of ethylene oxide; Neodol 23-9, which is an ethoxylated fatty alcohol with 9 moles of ethylene oxide; Alkanes and primary ethoxylated alcohols of 12-13 carbon atoms; Neodol 91-10, which is an ethoxylated primary alcohol containing 10 moles of ethylene oxide and 9-11 carbon atoms, this type of ethylene oxide Oxylated alcohols are also sold by Shell Chemical Company under the tradename Dobanol. 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 - Ethoxylated fatty alcohols of 15 carbon atoms.

Examples of other suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol 115-S-9, both of which are straight chain ethoxylated secondary alcohols sold by the Union Carbide Company. The former is a mixed ethoxylated product of straight-chain ethoxylated secondary alcohols with 11-15 carbon atoms and 7 moles of ethylene oxide. The latter is similar to the former, except that there are 9 moles of ethylene oxide Alkanes participate in the reaction.

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 condensation polymer of similar higher aliphatic alcohols. Fatty alcohols containing 14-15 carbon atoms and 11 moles of ethylene oxide groups per mole have also been marketed by Shell Chemical Company.

In this non-aqueous composition, the alkoxylated alcohol as an essential component of the liquid diluent usually accounts for 1%-60% of the liquid phase components, wherein 5%-40% is the preferred range, and 5-30% is the most good. These concentrations of the alkoxylated alcohols in the liquid phase correspond to concentrations in the total composition in the range of 1% to 60% by weight, with 2% to 40% being the preferred range and 5% to 25% being the optimum range. ii) Non-aqueous low-polarity organic solvents

A second essential ingredient in the liquid diluent which forms part of the liquid phase of the detergent composition consists of a non-aqueous, low polarity organic solvent. "Solvent" here includes the non-surface active carrier or diluent part of the liquid phase. While certain essential and/or optional ingredients of the composition are actually soluble in the "solvent"-containing liquid phase, other components will be dispersed in the form of particulate matter in the "solvent"-containing liquid phase. Thus, "solvent" does not imply that the solvent is capable of dissolving virtually all of the components of the cleaning composition added thereto.

The non-aqueous organic substances used here as solvents refer to liquids with low polarity. For the purposes of the present invention, a "low polarity" liquid means that it has little, if any, low solvency for one of the preferred particulate materials used in the present compositions. The so-called preferred particulate matter refers to peroxygen brightener, sodium perborate or sodium percarbonate. Therefore, relatively polar solvents such as ethanol cannot be used. Suitable solvents of low polarity for use in non-aqueous liquid detergent compositions include alkylene glycols other than 4-8 carbon atoms, lower alkyl ethers of alkylene glycols, low molecular weight polyethylene glycols, Low molecular weight methyl esters and amides.

A preferred type of non-aqueous low polarity solvent for use in the composition consists of non-linked 4-8 carbon atom branched or linear chain alkylene glycols. 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 class of non-aqueous low polarity solvents for use in the present invention include mono-, di-, tri-, or tetra- _C2-3 alkylene glycol mono _C2-6 alkyl ethers. Specific examples include 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 already commercially available under the tradenames Dowanol, Carbitol and Cellosolve.

Another preferred class of nonaqueous low polarity solvents for use in the present invention includes low molecular weight polyethylene glycols (PEGs), such materials having a molecular weight of at least 150, preferably 200-600.

Still another preferred non-polar non-aqueous solvent includes lower molecular weight methyl esters of the general formula R ¹ -C(O)-OCH ₃ , where R ¹ is from 1-18. Examples of suitable low molecular weight methyl esters are methyl acetate, methyl propionate, methyl octanoate and methyl dodecanoate.

Of course, the non-aqueous low-polarity organic solvent employed should be compatible with and non-reactive with other components, such as bleach and/or activators used in liquid detergent compositions. Such a solvent component is usually used in an amount in the range of 1% to 70% by weight of the liquid phase, preferably in the range of 10% to 60%, most preferably in the range of 20% to 50%. These concentrations of organic solvent used in the liquid phase correspond to a concentration of 1% to 50% in the total composition, with 5% to 40% being the preferred range, most preferably from 10% to 30%. iii) Ratio of alkylated alcohol to solvent

The weight ratio of alkoxylated alcohol to organic solvent in the liquid diluent can be used to modify the rheology of the final detergent composition. Usually, this ratio ranges from 50:1 to 1:50, preferably from 3:1 to 1:3. iv) Liquid diluent concentration

With regard to the concentration of the alkylbenzenesulfonate anionic surfactant mixture, the total amount of liquid diluent in the non-aqueous liquid phase of the present invention is determined by the type and amount of the other components of the composition and the desired properties of the composition. Usually, the liquid diluent accounts for 35%-70% of the non-aqueous liquid phase of the composition, preferably in the range of 50%-65%, which corresponds to a concentration of the non-aqueous liquid diluent in the total composition of 15%-70%, The preferred range is 20%-50%. Solid Phase

The non-aqueous detergent composition also needs to include 1%-65% by weight of solid particles, preferably 5%-50%, which are dispersed and suspended in the liquid phase. Usually the size of such particles is between 0.1-1500 μm, preferably 5-200 μm.

The particulate material used herein can contain one or more particulate detergent ingredients which are substantially insoluble in the non-aqueous liquid phase of the detergent composition. The types of particulate material which can be utilized are described in detail below:

Preparation and use of detergent compositions

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

In the first step of this typical preparation process, the composition is formed by mixing and heating the two essential ingredients of an alkylbenzenesulfonate anionic surfactant and a non-aqueous diluent at 30°C to 100°C.

In the second step, the heated mixture formed above is maintained at 40° C. to 100° C. for 2 minutes to 20 hours under certain shear stirring. Optionally, a vacuum can be applied to the mixture at this point. The second step is to completely dissolve the anionic surfactant in the non-aqueous liquid phase.

In the third step, the liquid phase mixture is cooled to 0°C-35°C. This cooling step is to form a structured, surfactant-containing liquid base, so that the particulate matter in the detergent composition can be added. and disperse it.

In the fourth step, the particulate material is added to the liquid base while maintaining the liquid base under shear stirring conditions, so that the particulate material is mixed with the liquid base. When adding more than one particulate material, it is best to follow a certain order of addition. For example, substantially all solid particles of the optional surfactant ranging in size from 0.2 to 1000 microns can be added while shear agitation is maintained. After adding all optional surfactant particles, substantially all organic builder particles such as citrate and/or fatty acid and/or alkali source such as sodium carbonate can be added while continuing to keep the mixture under shear agitation, At this point, other solid phase optional ingredients can be added to the mixture. Stirring of the mixture is continued and increased if necessary to form a uniform dispersion of the insoluble solid phase particles in the liquid phase.

The highly preferred particulate peroxygen bleach can be added to the composition after some or all of the solid material previously added to the stirred mixture while maintaining the mixture under stirring. The desired stabilization of the peroxygen bleach can be obtained by adding the peroxygen bleach last or after all or most of the other ingredients, especially after the alkali source particles. If enzyme particles are to be added, it is best to add them last to the non-aqueous liquid matrix.

In the final step, after all of the particulate material has been added, the mixture is continued to be agitated long enough to form a composition with the desired viscosity and phase stability characteristics. Often this involves stirring for periods of 1 to 30 minutes.

As a variation of the composition preparation procedure described above, one or more solid components may be premixed with a small amount of one or more liquid components and added in the form of a mixed slurry to the stirred composition, whereby a small amount of alkane The oxygenated 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 can be separately preformed and added as a slurry to the agitated mixture. These premixed slurries are added prior to the addition of peroxygen bleach and/or enzyme granules, which may themselves form part of a mixed slurry formed in a similar manner.

Compositions of the present invention, prepared as described above, can be used to form aqueous wash solutions for washing or bleaching fabrics. Typically, such aqueous wash/bleach solutions are formed by adding an effective amount of such compositions to water, preferably into a conventional fabric washing automatic washing machine. The wash/bleach solution thus formed is preferably contacted with agitation to the fabrics to be cleaned or bleached.

An effective amount of liquid detergent added to water to form an aqueous-based wash/bleach solution comprises an amount sufficient to form from 500 to 7,000 ppm of the composition in aqueous solution. Detergent compositions are preferably added at from 800 to 3,000 ppm to the wash/bleach solution.

Example VII

Prepare a non-aqueous liquid laundry detergent containing bleach, which has the composition listed in Table I, although not limited to this example.

Table 1 Component Weight percent (%) Weight percent range (%) Liquid phase C ₁₂ Sodium linear alkylbenzene sulfonate (LAS) 25.3 18-35C _12-14 , 5 ethylene oxide units 13.6 10-20 Ethoxylated Alcohol

Hexylene glycol 27.3 20-30

Spices 0.4 0-1.0

Dual-AQA-1 ^* 2.0 1-3.0

Solid Phase

Protease 0.4 0-1.0

Trisodium citrate anhydrous 4.3 3-6

Sodium perborate 3.4 2-7

Sodium nonanoyloxybenzenesulfonate (NOBS) 8.0 2-12

Sodium carbonate 13.9 5-20

Diethyltriaminepentaacetic acid (DTPA) 0.9 0-1.5

Brightener 0.4 0-0.6

Foam inhibitor 0.1 0-0.3

Minor Components Balance -

*Coconut MeEO2. Bis-AQA-1 can be replaced by Bis-AQA Surfactant 2-22 or other Bis-AQA Surfactants.

This composition was prepared by first mixing - AQA and LAS, then adding hexanediol and ethoxylated alcohol and holding together at 54°C (130°F) for 1/2 hour. The mixture was cooled to 29°C (85°F), at which point the other ingredients were added. The resulting composition was maintained at 29°C (85°F) with stirring for 1/2 hour.

The resulting composition is a stable anhydrous heavy duty liquid laundry detergent capable of producing very high soil removal in normal laundry operations.

The following Examples A and B further illustrate the invention with respect to a laundry soap bar.

Example Ⅷ

Composition Weight Content (%) Range (%)

A B B

C ₁₂ -C ₁₈ Sulfate 15.75 13.50 0-25

LAS 6.75 - 0-25

_{Na2CO3 15.00} 3.00 1-20

^DTPP1 0.70 0.70 0.2-1.0

Bentonite clay - 10.0 0-20

Sokolan CP-5 ² 0.40 1.00 0-2.5

Dual-AQA-1 ³ 2.0 0.5 0.15-3.0

TSPP 5.00 0 0-10

STPP 5.00 15.00 0-25

Zeolite 1.25 1.25 0-15

Sodium Laurate - 9.00 0-15

SRA-1 0.30 0.30 0-1.0

Protease - 0.12 0-0.6

Amylase 0.12 - 0-0.6

Lipase - 0.10 0-0.6

Cellulase - 0.15 0-0.3

---- Balance ⁴ ----

1. Sodium diethylenetriaminepenta(phosphonate)

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

3. -AQA-1 can be replaced by an equivalent amount of 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.

Embodiment IX

The following handwash detergent compositions according to the present invention are prepared by mixing the ingredients in the weight percents of the ingredients 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 0.4 0.4 0.4 0.4DTPMP 1.0 1.6 1.6 1.6碳酸盐2.0 2.0 5.0 5.0 Bicarbonate - - 2.0 2.0 Silicate 7.0 7.0 7.0 7.0 Protease 1.0 - 1.0 1.0 Amylase 0.4 0.4 0.4 - Lipase 0.12 0.12 - 0.12 Photosensitive Bleach 0.3 0.3 0.3 0.3 Sulfate 2.2 2.2 2.1 4.2P 5.4 4.0 2.3 NOBS 2.6 3.1 2.5 1.7 SRA1 0.3 0.3 0.7 0.3 Brightener 1 0.15 0.15 0.15 0.15 Balance Misc/Water to 100 100.0 100.0 100.0 100.0 AQA-9 ^* : Can be replaced by any of the AQA surfactants described herein. Preferred AQA surfactants in this example are AQA containing 10-15 ethoxy groups; eg AQA-10, AQA-16.

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

Modern and efficient hand dishwashing detergents contain ingredients that impart specific in-use attributes to the product, such as degreasing power, high sudsing, mildness and a good hand feel. Such ingredients used with bis-AQA surfactants include, such as amine oxide surfactants, betaine and/or sultaine surfactants, alkyl sulfate and alkyl ethoxy sulfate surfactants agents, liquid carriers, especially water and water/propylene glycol mixtures, natural oils such as lemon oil. In addition, good liquid and/or gel dishwashing detergents for hand washing may also contain Ca ²⁺ , Mg ²⁺ , or a Ca ²⁺ /Mg ²⁺ mixture for greater detergency, especially in combination with Amine oxide, alkyl sulphate and alkyl ethoxy sulphate combined bis-AQA surfactant wash mixtures are used together. Ca ²⁺ , or Mg ²⁺ or mixed Ca ²⁺ /Mg ² sources will generally comprise from 0.01% to 4%, preferably from 0.02% to 2%, by weight of such compositions. Various sources of water-soluble ions include, for example, sulfates, chlorides, and acetates. Furthermore, these compositions may also contain nonionic surfactants, especially polyhydroxy fatty acid amides and alkyl polyglucosides, members of this class containing 12-14 carbon atoms (coconut alkyl) being preferred. A particularly preferred nonionic surfactant for water dishwashing liquids is C _12-14 N-methyl glucamide, preferred amine oxides include C _12-14 dimethyl amine oxide, alkyl sulfate Salt and Alkyl Ethoxy Sulfate are as described above, and this surfactant is typically used in dishwashing liquids at levels of 3-50% of the finished product. The formulation of dishwashing liquid compositions has been described in detail in various patent publications, including US Patents US5378409, US5576310 and US5417893, which are incorporated by reference.

Modern automated dishwashing detergents may contain bleaching agents such as hypochlorous acid sources; perborate, percarbonate or persulfate bleaches; enzymes such as proteases, lipases and amylases or mixtures thereof; rinse aids , especially nonionic surfactants; builders, including zeolite and phosphate builders; low-foaming detersive surfactants, especially ethylene oxide/propylene oxide condensates, usually in the form of granules or Gum form exists. If used in gel form, 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

Composition Weight Content (%) Range (%)

Dual-AQA-1 ^* 2.0 0.15-3

C _12-13 Alkyl Ammonium Sulfate 7.0 2-35

C _12-14 ethoxylated (1) sulfate 20.5 5-35

Coconut amine oxide 2.6 2-5

Betaine/Tetronic 704 ^_ 0.87-0.10 0-2(mix)

Ethoxylated Alcohol C ₈ E ₁₁ 5.0 2-10

Ammonium xylenesulfonate 4.0 1-6

Ethanol 4.0 0-7

Ammonium citrate 0.06 0-1.0

Magnesium chloride 3.3 0-4.0

Calcium chloride 2.5 0-4.0

Ammonium sulfate 0.08 0-4.0

Hydrogen peroxide 200ppm 0-300ppm

Spices 0.18 0-0.5

^{Maxatase_Protease} 0.50 0-1.0

Water and Minor Components ----Balance----

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

^** Coconut Alkyl Betaine

The following Examples A and B further illustrate the present invention with respect to a phosphate-containing granular automatic dishwashing detergent.

Example Ⅺ

% by weight of active substance

Ingredients A B

STPP (anhydrous) ¹ 31 26

Sodium carbonate 22 32

Silicate (%SiO ₂ ) 9 7

Surfactant (non-ionic) 3 1.5

NaDCC Bleach ² 2 -

Dual-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

Sulphate 25 25

Fragrance/minor components to 100% to 100%

1 sodium tripolyphosphate

2 sodium dichlorocyanurate

^* Dual-AQA-1 can be replaced by Dual-AQA-2 to Dual-AQA-22

Example Ⅻ

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

% ingredients by weight of active substance A B C D E F G Citric Acid 16.5 16.5 16.5 16.5 16.5 10 10 Sodium Carbonate / Potassium Carbonate - - 25 25 25 15 15 Bis-AQA-1 ^* 0.5 0.7 0.5 0.5 0.4 0.6 0.7 Dispersant (480N) 4 4 4 4 4 4 4HEDP/SS-EDDS 2 2 0-2 2 2 1.5 1.5 Benzoyl Peroxide 8 8 8 8 8 1.5 1.5 Butylated Hydroxytoluene 0.05 0.05 0.05 0.05 0.05 0.05 0.05 (BHT) Surfactant 2.5 2.5 1.5 1.5 1.5 1.5 1.5 Boric acid - 4 4 4 4 4 4 Sorbitol - 6 6 6 6 6 Savinase 24L - - 0.2 0.53 - 0.53 - Suspended Savinase 16L - - - - 0.53 - 0.53Maxamyl/Termamy 0.54 - 0.31 0 - 1.0 1 - Suspended Temamyl - 0.54 - - - 0.31 0.31 Water ----Balance----

^* Bis-AQA-1 (coconut MeEO2) can be replaced by an equivalent amount of bis-AQA-2 to bis-AQA-22 or other bis-AQA surfactants.

Various gelling agents such as CMC and clays can be used in the composition to provide various viscosities and hardnesses according to the formulator's requirements.

Example ⅩⅢ

The following exemplifies mixtures of bis-AQA surfactants that can be substituted for the bis-AQA listed in any of the above examples. As noted above, the use of such mixtures can achieve various beneficial properties and/or provide cleaning compositions suitable for various conditions of use. In this mixture it is preferred that the bis-AQA surfactants differ by at least 1.5, preferably by 2.5-20 ethylene oxide units, in a weight ratio of from 10:1 to 1:10, examples not limited to the following table stated.

Components Proportion (weight)

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

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

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

Dual-AQA-1+Dual-AQA-5

+ Dual-AQA-20 1:1:1

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

Dual-AQA-5+Dual-AQA-15 1.5∶1

Dual-AQA-1+Dual-AQA-20 1∶3

Mixtures of bis-AQA surfactants with corresponding cationic surfactants containing only one ethoxylated chain can also be used here. Thus, for example, a mixture of ethoxylated cationic surfactants of the formula R ¹ N ⁺ CH ₃ [EO] _X [EO] _Y X ^- and R ¹ N ⁺ (CH ₃ ) ₂ [EO] _z X ^- can be used in In the present invention, wherein R ^and X are as described above, (x+y) or z of a cationic surfactant can be 1-5, preferably 1-2, and another (x+y) or z is from 3-100, better is from 10-20, the best is 14-16. Such compositions are capable of producing higher detergency over a wider range of water hardness conditions than the cationic surfactants of the invention alone (especially in laundered fabric conditions). Shorter ethylene oxide cationic surfactants (such as EO2) have been found to improve the detergency performance of anionic surfactants in soft water, while longer ethylene oxide cationic surfactants (such as EO15) can improve anionic surface The tolerance of the active agent to hardness, thereby improving the cleaning performance of anionic surfactants in hard water. Common knowledge in the detergency art indicates that builders optimize the "window" of performance of anionic surfactants. However, until now, it has not been possible to expand this "window" to encompass essentially all conditions of water hardness.

Example XIV

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

(%weight)

Fragrance Component A A B C

Hexylcinnamaldehyde 10.0 - 5.0

2-Methyl-3-(p-tert-butylphenyl)-propionaldehyde 5.0 5.0 -

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

Tetramethylnaphthalene 5.0 10.0 10.0

Benzyl salicylate 5.0 - -

7-Acetyl-1,1,3,4,4,6-hexamethyltetralin 10.0 5.0 10.0

p-(tert-butyl)cyclohexyl acetate 5.0 5.0 -

Methyl dihydrojasmonate - 5.0 -

β-naphthyl ether - 0.5 -

Methyl-β-naphthone - 0.5 -

2-Methyl-2-(p-iso-propylphenyl)-propionaldehyde - 2.0 -

1,3,4,6,7,8-Hexahydro-4,6,6,7,8,8-Hexamethyl

-cyclopenta-γ-2-benzopyran - 9.5 -

Dodecahydro-3a,6,6,9a-tetramethyl

Naphtho[1,2d]furan - - - 0.1

Anisaldehyde - - - 0.5

Coumarin - 5.0

Cedrol - 0.5

Vanillin - 5.0

Cyclopentalactone 3.0 - 10.0

Tricyclodecene acetate - - - 2.0

Labdanum Resin - - - 2.0

Tricyclodecanyl propionate - - - 2.0

Phenylalcohol 20.0 10.0 27.9

Terpineol 10.0 5.0 -

Linalool 10.0 10.0 5.0

Linalyl acetate 5.0 - 5.0

Geraniol 5.0 - -

Nerol - 5.0 -

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

Orange Oil, Cold Pressed - 5.0 -

Benzyl acetate 2.0 2.0 -

Orange Terpenes - 10.0 -

Eugenol - 1.0 -

Diethyl phthalate - 9.5 -

Lemon Oil, Cold Pressed - - - 10.0

Total 100.0 100.0 100.0

The above perfume composition (normally present in an amount up to about 2% by weight of the total detergent composition) is blended or sprayed in the various bis-AQA surfactant-containing cleaning (including bleaching) compositions disclosed herein, thereby Ensuring enhanced deposition and/or retention of fragrance or its single ingredients on the surface to be cleaned (bleached).

Claims (24)

1. A detergent composition comprising or being prepared by mixing the following components: an enzyme, a non-alkoxy quaternary ammonium surfactant and an effective amount of a dialkoxy quaternary ammonium of the following structural formula Cationic Surfactants:

In the formula, R ¹ is linear, branched, or substituted C ₈ -C ₁₈ alkyl, alkenyl, aryl, alkaryl, ether with glycosyl ether moiety; R ² is C ₁ -C ₃ alkyl; R ³ and R ⁴ vary independently and are selected from one of hydrogen, methyl, ethyl; X is an anion; A and A' vary independently and are each C ₁ -C ₄ alkoxy; p and q are independently variable and are integers between 1-30. 2. The composition according to claim 1, wherein the enzyme is selected from lipase. 3. The composition according to 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 according to 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 according to claim 1 or 7, further comprising an enzyme stabilizer. 9. The composition according to any one of claims 1 to 8, which is made by mixing non-alkoxy quaternary ammonium surfactant and 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. The composition according to any one of claims 1 to 10, wherein the ratio of the dialkoxy quaternary ammonium cationic surfactant to the non-alkoxy quaternary ammonium surfactant is 1:8 to 1:15. 12. ^The composition according to any one of claims 1 to 11, wherein R of the dialkoxy quaternary ammonium surfactant is a C ₈ -C ₁₈ alkyl group, R ² is a methyl group, and A and A' are respectively B Oxygen and propoxy, p and q are integers between 1-8. 13. The composition according to any one of claims 1 to 12, wherein R of the dialkoxy quaternary ammonium surfactant is a C ₈ -C ₁₈ alkyl group, ^{R 2 is} a methyl group, and A and A' are respectively B Oxygen and propoxy, p and q are integers between 1-4. 14. According to the composition described in any one of claims 1 to 13, p and q in the structural formula of the dialkoxy quaternary ammonium cationic surfactant are integers between 10-15. 15. A composition according to any one of claims 1 to 14 comprising two or more dialkoxyquaternary ammonium surfactants, or a dialkoxyquaternary ammonium surfactant and a monoethylenmonium A mixture of oxygenated cationic surfactants. 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 dialkoxylated quaternary ammonium surfactants. 17. A composition according to any one of claims 1 to 16 which is substantially free of bleach. 18. The composition according to any one of claims 1 to 17, which is in the form of granules, sticks, water-based liquids, non-aqueous-based liquids, or tablets. 19. A method of removing soils and stains by contacting said soils and stains with a detergent composition as claimed in any one of claims 1 to 18 or an aqueous phase containing said detergent composition. 20. A method according to claim 19 for removing enzyme sensitive soils, greasy/oily soils or surfactant sensitive soils from fabrics. twenty one. A method according to claim 19 or 20, carried out by hand. twenty two. A method according to any one of claims 19 to 21 carried out in a washing machine. twenty three. A method of enhancing the deposition and durability of a perfume or perfume component on a fabric or other surface comprising contacting said surface with a perfume or perfume component in the presence of a dialkoxyquaternary ammonium surfactant. twenty four. 23. A method according to claim 23, carried out using a detergent composition comprising a bisalkoxy quaternary ammonium surfactant in combination with a perfume or perfume component.