CN1247560A - Dishwashing compositions containing organic diamines - Google Patents

Abstract

The present invention relates to detergent compositions containing low molecular weight organic diamines. More particularly, the present invention relates to detergent compositions for hand dishwashing which have improved grease removal and sudsing. The detergents of the invention also have improved low temperature stability and outstanding solvency.

Description

Dishwashing compositions containing organic diamines

Field of Invention

The present invention relates to detergent compositions containing low molecular weight organic diamines. More particularly, the present invention relates to detergent compositions for hand dishwashing having improved oil removal and sudsing. The detergents of the present invention also have improved low temperature stability and outstanding solvency as well as improved stubborn food stain removal and antibacterial properties. The detergent compositions of the present invention may be in any form including granules, pastes, gels or liquids, more preferred embodiments are in the form of liquids or gels.

Diamines are known in the dishwashing art to be more effective as surface active builders in place of calcium/magnesium ions used at low levels when formulating hand dishwashing detergents at a pH above about 8.0. The diamines simultaneously provide the benefits of greasy cleansing, lather, dissolution and low temperature stability without the disadvantages associated with calcium/magnesium.

Background of the Invention

Typical industrial hand dishwashing compositions incorporate divalent ions (magnesium, calcium) to ensure adequate oil removal performance in soft water. However, the presence of divalent ions in formulations containing anionic, nonionic, or additional surfactants (e.g., alkyldimethylamine oxides, alkylethoxylates, alkanoylglucamides, alkylbetaines) leads to Slow mixing rate of product with water (and thus poor foaming), poor rinsing and poor low temperature stability. Furthermore, it is very difficult to prepare stable calcium/magnesium containing dishwashing detergents due to the precipitation associated with calcium and magnesium as the pH increases.

US4556509 discloses diacid salts of diamines, under these conditions we have found that these materials are limiting, moreover the effect is limited to hardness < 70ppm. US4556509 also discloses the use of C2 spacers, such as ethylenediamine diacids and ethoxylated diamines, which severely limit performance in existing developments.

We have also now determined, as detailed below, that the use of certain magnesium or calcium in dishwashing compositions at a pH of about 8.0-12 (measured as a 10% solution) compared to the use of magnesium or calcium in conventional detergent compositions These organic diamines with surfactants lead to improved cleaning of stubborn food stains and removal of grease/oil. Unexpectedly, the organic diamine also improves foam stability in the presence of soils, especially soils containing fatty acids and proteins.

Furthermore, the strong degreasing properties of the diamines discussed herein allow for the reduction/elimination of magnesium/calcium ions from the formulation while maintaining the benefits in terms of greasiness performance. Removal of magnesium/calcium additionally results in improved solvency, rinsing and low temperature product stability effects.

The combination of diamines and surfactants of the present invention also provides sensory benefits. We have found that the presence of the composition of the present invention produces a "smooth" feel of the mother liquor and a "soft" feel to the skin. Diamines have also been found to exert an antimicrobial effect on detergent mother liquors, however, the particular composition presented herein has a relatively high pH, detergent surfactants, and selective enzymes, specifically designed for dishwashing, all of which are important in contact lens cleaning It is not desirable in the agent.

We have now found that these effects can be achieved by using low molecular weight organic diamines over a broad hardness range (8 -> 1000 ppm) in higher pH formulations (about 8-12).

Background technique

US4556509 discloses the use of low molecular weight organic diamine diacids in detergents in the pH range of about 6-8.

JP63131124-A88/06/03 describes contact lens cleaners containing diamines which react with halogen compounds such as 1,2-dichloroethane.

Summary of Invention

The detergent compositions of the present invention comprise a diamine and a surfactant. More specifically, the detergent of the present invention contains:

a) an effective amount of a low molecular weight (less than about 400 amu, preferably less than about 200 amu, more preferably less than or equal to about 150 amu) organic diamine, wherein the diamine has a pK1 and pK2 of about 8.0 to about 11.5; and

b) a detergent effective amount of surfactant;

wherein the detergent composition (measured as a 10% aqueous solution) has a pH of from about 8.0 to about 12, preferably from about 8.2 to about 12, more preferably from about 8.5 to about 11, most preferably from about 8.5 to about 10.2.

The preferred weight ratio of surfactant to organic diamine is from about 40:1 to about 2:1, more preferably from about 10:1 to about 5:1.

The detergent compositions also optionally contain reduced magnesium/calcium ions compared to known conventional detergent compositions. In other words, the compositions of the present invention preferably utilize no more than about 1.5%, more preferably no more than about 0.6%, of available divalent ions, preferably selected from calcium and magnesium. The detergent compositions of the present invention are most preferably substantially free (ie, less than about 0.1%) of additional divalent ions.

The surfactants of the present invention are selected from anionic or nonionic surfactants or mixtures thereof. Preferred anionic surfactants for use herein include linear alkylbenzene sulfonates, alpha olefin sulfonates, paraffin sulfonates, methyl ester sulfonates, alkyl sulfates, alkyl alkoxy sulfates, Alkyl Sulfonates, Alkyl Alkoxylate Sulfates, Sarcosinates, Alkyl Alkoxy Carboxylates and Taurates. Preferred nonionic surfactants for use herein are selected from the group consisting of alkyl dialkyl amine oxides, alkyl ethoxylates, alkanoyl glucamides, alkyl polyglycosides, alkyl betaines and mixtures thereof. In a more preferred embodiment, the anionic surfactant is selected from the group consisting of alkyl sulfates, alkyl alkoxy sulfates and mixtures thereof. In another more preferred embodiment, the nonionic surfactant is selected from the group consisting of amine oxides, alkyl betaines, alkanoyl glucamides and mixtures thereof. If a mixture of anionic and nonionic surfactants is used, the anionic:nonionic weight ratio is preferably from about 50:1 to about 1;50, more preferably from about 50:1 to about 3:1. Likewise, when mixtures of anionic and nonionic surfactants are present, the hand dishwashing detergent compositions of the present invention preferably also contain proteases, amylases or mixtures thereof. In addition, these hand dishwashing detergent embodiments preferably also contain solubilizing agents. Preferred solubilizers include sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluenesulfonic acid, naphthalenesulfonic acid, cumenesulfonic acid, xylenesulfonic acid.

The detergent also preferably contains one or more detergent builders selected from the group consisting of soil release polymers, dispersants, polysaccharides, abrasives, bactericides, tarnish inhibitors, builders, enzymes, dyes, buffers, anti- Fungus or mildew control agents, insect repellants, fragrances, solubilizers, thickeners, processing aids, foam boosters, brighteners, preservatives, stabilizers antioxidants and chelating agents. Although cationic surfactants may optionally be present in the detergent compositions of the present invention, preferred embodiments are substantially free of cationic surfactants. In addition, the compositions of the present invention are substantially free of halide ions (chlorine, fluorine, bromide or iodide ions) and substantially free of urea. Substantially free means less than about 1%, preferably less than about 0.1%, more preferably 0% by weight of the composition of each component.

Furthermore, the hand dishwashing detergent compositions of the present invention may also contain enzymes, preferably selected from proteases, lipases, amylases, cellulases and mixtures thereof, more preferably enzymes selected from proteases and amylases.

Furthermore, the diamines used in the present invention are preferably substantially free of impurities. That is, "substantially free" means that the diamine is more than 95% pure, ie preferably 97%, more preferably 99%, most preferably 99.5% free of impurities. Examples of impurities that may be present in commercially available diamines include 2-methyl-1,3-diaminobutane and alkylhydropyrimidines. Furthermore, it is believed that the diamine should be free of oxidizing reactants to avoid diamine degradation and ammonia formation. Additionally, if amine oxides and/or other surfactants are present, the amine oxides or surfactants should be free of hydrogen peroxide. The preferred level of hydrogen peroxide in the amine oxide or surfactant slurry of amine oxide is 0-40 ppm, more preferably 0-15 ppm. In amine oxides and betaines, if present, the amine impurity should be reduced to the above hydrogen peroxide level.

It is important that the composition be free of hydrogen peroxide when the composition contains enzymes. Peroxides will react with the enzymes, destroying any performance effect the enzymes impart on the composition. Even small amounts of hydrogen peroxide can cause problems in formulations containing enzymes. However, the diamine reacts with any peroxide present, acts as an enzyme stabilizer and prevents hydrogen peroxide from reacting with the enzyme. The only disadvantage of this method of stabilizing enzymes with diamines is the generation of nitrogen compounds which are believed to contribute to the off-flavor of diamine-containing compositions. The use of diamines as enzyme stabilizers also prevents the diamines from providing the composition with the benefits they were originally proposed to achieve, namely greasy cleansing, foaming, solvency and low temperature stability. Although diamines can be used as enzyme stabilizers, it is preferred to use components substantially free of hydrogen peroxide and/or The amount of hydrogen peroxide present as an impurity in the compositions of the present invention is minimized by the use of non-diamine antioxidants.

It is also preferred that the compositions of the present invention are "off-odor". That is, the headspace does not produce unpleasant odors perceived by consumers. This can be accomplished in a number of ways including the use of fragrances to mask any undesirable odors, the use of stabilizers such as antioxidants, chelating agents, etc. and/or the use of diamines which are substantially free of impurities. While not intending to be bound by theory, it is believed that impurities present in the diamine contribute to the primary malodor of the compositions of the present invention. These impurities may arise during the preparation and storage of the diamine, and they may also arise during the preparation and storage of the composition of the invention. The use of stabilizers, such as antioxidants and chelating agents, inhibits and/or avoids the formation of these impurities in the composition from the time of manufacture to end use by the consumer and beyond. Therefore, it is most preferred to remove, suppress and/or avoid the formation of these malodors by adding fragrances, stabilizers and/or using diamines which are substantially free of impurities.

In addition, the hand dishwashing detergent compositions of the present invention may also contain baking soda, especially if formulated below a pH of about 9. If present, baking soda will comprise from about 0.5% to about 5%, preferably from about 1% to about 3%, by weight of the total composition.

All parts, percentages and ratios used herein are expressed as percent by weight unless otherwise indicated. All documents listed in relevant sections are incorporated by reference herein.

Detailed description of the invention

Definitions - The detergent compositions of the present invention contain an "effective amount" or "grease removal improving amount" of each ingredient as defined herein. An "effective amount" of diamines and adjunct ingredients herein means an amount sufficient, within 90% confidence, to directionally or appreciably improve the performance of the cleaning composition on at least some of the targeted soils and stains. Thus, in compositions whose targets include certain greasy stains, the formulator will use sufficient diamine to at least directionally improve the cleaning performance on that stain. Importantly, in fully formulated detergents, as can be seen from the examples hereinafter, the diamines can be used in amounts that provide a directional improvement in at least one detergency performance on a wide variety of soils and stains.

Likewise, diamines are used in detergent compositions in combination with detersive surfactants at levels effective to obtain at least one directional improvement in detergency performance. In hand dishwashing compositions, the "use level" can vary according to the type and severity of soils and stains, and also according to the wash water temperature, the volume of the wash water and the length of time the dishes are in contact with the wash water.

Due to the obvious differences in the habits and practices of users of detergent compositions, it is desirable to include about 0.25% to about 15% by weight in the composition, preferably about 0.5% to about 10%, more preferably about 0.5% by weight. % to about 6% diamine.

In one of its several aspects, the present invention provides improved removal of greasy/oily soils by combining the specific diamines of the present invention and surfactants. Greasy/oily "everyday" soils are a mixture of triglycerides, liposomes, complex polysaccharides, fatty acids, inorganic salts and proteinaceous matter.

While not intending to be bound by theory, it is believed that the strong degreasing performance achieved by organic diamines over a broad hardness range (up to about 1000 ppm expressed as calcium carbonate) reduces the need for increased degreasing performance in soft water in hand dishwashing detergents. The need for divalent ions. Importantly, the removal of divalent ions from conventional hand dishwashing formulations results in an effect on the rate at which the product mixes with water (termed "solvability"), rapid foaming, rinsing, and low temperature stability.

Depending on consumer preference, the compositions of the present invention may be formulated at viscosities in excess of about 50, preferably in excess of about 100 centistokes, more preferably from about 100 to about 400 centistokes. For European formulations, the composition can be formulated to a viscosity of up to about 800 centistokes.

Furthermore, the excellent dissolution rate achieved by divalent ion reduction even allows formulators to prepare hand dishwashing detergents, especially compact formulations, at significantly higher viscosities (e.g., 1000 centistokes or higher) than conventional formulations, while maintaining excellent The solvency and washability of this product have obvious potential advantages for preparing compact products with higher viscosity while maintaining acceptable solvency. "Compact" or "ultrafine" refers to detergent formulations that contain a reduced water content compared to conventional liquid detergents. The water content is below 50%, preferably below 30% by weight of the detergent composition. The concentrated product offers the consumer the advantage of being able to use the product in smaller quantities and the producer the advantage of having lower shipping costs.

Excellent greasy cleaning and solvency performance is obtained if the pH of the detergent is maintained in the range of about 8.0 to about 12. This pH range is chosen to maximize the practical content of non-protonated diamine (on one of the nitrogen atoms).

This differs from the worse case that exists at pH below 8 (see US4556509, Colgate), where the diamine is highly protonated, has little or no buffering capacity, or differs from when using pre-formed amine salts or quaternary ammonium Worse case when compounding derivatives.

Diamines - Preferred organic diamines are those in which the pK1 and pK2 range from about 8.0 to about 11.5, preferably from about 8.4 to about 11, more preferably from about 8.6 to about 10.75. Preferred substances for performance and source considerations are 1,3 propanediamine (pK1=10.5; pK2=8.8), 1,6 hexanediamine (pK1=11; pK2=10), 1,5 pentanediamine (Dytek EP) (pK1 = 10.5; pK2 = 8.9); 2-methyl 1,5-pentanediamine (Dytek A) (pK1 = 11.2; pK2 = 10.0). Other preferred materials are primary/primary diamines with C4-C8 alkylene spacers. Primary diamines are generally considered to be preferred over secondary and tertiary diamines.

Definitions of pK1 and pK2 - "pKal" and "pKa2" as used herein are quantities known to those of skill in the art as "pKa". pKa is used in the present invention in the same manner generally known to those skilled in the chemical arts. Values cited herein are available from the literature, for example, in "Critical Stability Constants: Volume 2, Amines" by Smith and Martel, Plenum Press, NY and London, 1975. Additional information on pKa can be obtained from relevant company literature, such as that provided by Dupont, a supplier of diamines.

As a working definition herein, the pKa of a diamine is specified in full aqueous solution at 25°C and for an ionic strength at 0.1-0.5M. pKa is an equilibrium constant that can vary with temperature and ionic strength; therefore values reported in the literature sometimes do not agree according to measurement methods and conditions. To avoid confusion, the pKa used in the present invention is the relevant condition and/or reference is as defined herein or in "Critical Stability Constants: Volume 2, Amines". A typical method of measurement is potentiometric acid titration with sodium hydroxide to determine pKa by a suitable method described and referenced in "Chemist's Ready Reference Handbook", Shugar and Dean, McGraw Hill, NY, 1990.

It has been determined that substituents and structural modifications that lower pK1 and pK2 below about 8.0 are undesirable, resulting in a loss of performance. This can include diamines resulting in ethoxylated diamines, hydroxyethyl substituted diamines, diamines with oxygen in the beta position (and lower, i.e. gamma position) of the nitrogen atom in the spacer group (e.g. Jeffamine EDR 148) Substitution of diamines. Furthermore, substances based on ethylenediamine are unsuitable.

其中R_1-4分别选自H、甲基、-CH₃CH₂和环氧乙烷；C_x和C_y分别选自亚甲基或支链烷基，其中x+y是约3-约6；和A是选择性地存在的，选自给电子或吸电子基团以调节二胺的pKa至所需范围。如果A存在，由x和y必须均是1或更大。The diamines used in the present invention are defined by the following structures:

Wherein R _1-4 are respectively selected from H, methyl, -CH ₃ CH ₂ and oxirane; C _x and C _y are respectively selected from methylene or branched chain alkyl, wherein x+y is about 3-about 6; and A is optionally present, selected from electron donating or electron withdrawing groups to adjust the pKa of the diamine to the desired range. If A is present, x and y must both be 1 or greater.

1，6-己烷二胺：

1，3丙烷二胺：2-甲基1，5戊烷二胺-1，3-戊烷二胺，由商品名Dytek EP得到：

1-甲基-二氨基丙烷-                         

Jeffamine EDR 148-

异佛尔酮二胺-

1，3-双(甲基胺)-环己烷

和它们的混合物。Examples of preferred diamines include the following: Dimethylaminopropylamine:

1,6-Hexanediamine:

1,3 Propanediamine: 2-methyl-1,5-pentanediamine- 1,3-Pentanediamine, available under the tradename Dytek EP:

1-Methyl-diaminopropane-

Jeffamine EDR 148-

Isophoronediamine-

1,3-bis(methylamine)-cyclohexane

and their mixtures.

When tested with approximately equimolar replacements for calcium/magnesium in the near neutral pH range (7-8), the organic diamines only provided greasy cleaning performance equivalent to calcium/magnesium. This cannot be achieved by using calcium/magnesium or by using organic diamines below pH 8 or by using organic diamine diacids below pH 8.

Anionic Surfactants - The anionic surfactants used in the present invention are preferably selected from the group consisting of linear alkylbenzene sulfonates, alpha olefin sulfonates, paraffin sulfonates, methyl ester sulfonates, alkyl sulfates, alkanes alkyl alkoxy sulfates, alkyl sulfonates, alkyl alkoxy carboxylates, alkyl alkoxylated sulfates, sarcosinates, taurates and mixtures thereof. Effective amounts, generally from about 0.5% to about 90%, preferably from about 5% to 50%, more preferably from about 10% to about 30%, by weight, of anionic detersive surfactants can be used herein.

One type of anionic surfactant that can be used includes alkyl ester sulfonates, which are desirable because they can be prepared from renewable, non-petroleum resources. The preparation of the alkyl ester sulfonate surfactant component can be carried out according to known methods disclosed in the technical literature. For example, linear esters of _C8 - _C20 carboxylic acids are sulfonated with gaseous sulfur trioxide according to the method in "Journal of the American Petrochemical Society", 52 (1975), pp. 323-329. Suitable materials would include natural fatty materials derived from tallow, palm and coconut oils, and the like.

Preferred alkyl ester sulfonate surfactants, especially for laundry applications, include alkyl ester sulfonate surfactants of the formula:

R ³ -CH(SO ₃ M)-C(O)OR ⁴ wherein R ³ is C ₈ -C ₂₀ hydrocarbon group, preferably alkyl or their mixture, R ⁴ is C ₁ -C ₆ hydrocarbon group, preferably alkyl or their mixture, M is a cation that forms a water-soluble salt. Suitable salts include metal salts such as sodium, potassium and lithium salts, and substituted or unsubstituted ammonium salts such as methyl, dimethyl, trimethyl and quaternized ammonium cations such as tetramethylammonium and dimethylammonium piperidinium and cations derived from alkanolamines such as monoethanolamine, diethanolamine and triethanolamine. Preferably R ³ is C ₁₀ -C ₁₆ alkyl, and R ⁴ is methyl, ethyl or isopropyl. Especially preferred are methyl ester sulfonates wherein R ³ is C ₁₀ -C ₁₆ alkyl.

Alkyl sulfate surfactants are another type of anionic surfactant of interest for use herein. When used in combination with polyhydroxy fatty acid amides (see below) in addition to providing outstanding overall detergency, including good greasy/oily detergency over a wide range of temperatures, wash concentrations and wash times, the alkyl sulphate Solubility, and improved formulatability in liquid detergent formulations is a water-soluble salt or acid of formula ROSO ₃ M, wherein R is preferably a C ₁₀ -C ₂₄ hydrocarbyl, preferably an alkane containing a C ₁₀ -C ₂₀ alkyl moiety or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is H or a cation, which may be an alkali or alkaline earth (Group IA or Group IIA) metal cation (e.g. sodium, potassium, lithium, magnesium , calcium), or substituted or unsubstituted ammonium, such as methyl-, dimethyl- and trimethyl-ammonium cations and quaternary ammonium cations, such as tetramethylammonium and dimethylpiperidinium cations and Alcoholamines such as ethanolamine, diethanolamine, triethanolamine, cations derived from mixtures thereof, and the like. _C12 - _C16 alkyl chains are generally preferred for low wash temperatures (eg _{, below about 50°C) and C16-18 alkyl} chains are preferred for higher wash temperatures (eg, above about 50°C).

Alkyl alkoxy sulfate surfactants are another class of anionic surfactants. These surfactants are water soluble salts or acids of the formula RO(A) _m SO ₃ M, wherein R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl containing a C ₁₀ -C ₂₄ alkyl moiety, preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, usually from about 0.5 to about 6, more preferably From about 0.5 to about 3, M is H or a cation, which may be a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation. The present invention contemplates alkyl ethoxy sulfates and alkyl propoxy sulfates. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-ammonium cations, and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and those derived from alkanolamines such as mono Cations derived from ethanolamine, diethanolamine, triethanolamine, mixtures thereof. Exemplary surfactants are C ₁₂ -C ₁₈ alkyl polyethoxylated (1.0) sulfates, C ₁₂ -C ₁₈ alkyl polyethoxylated (2.25) sulfates, C ₁₂ -C ₁₈ alkyl Polyethoxylated (3.0) sulfates and _C12 - _C18 alkyl polyethoxylated (4.0) sulfates, where M is typically selected from sodium and potassium. Surfactants for use herein can be prepared from natural or synthetic alcohol feedstocks, and the chain length represents the average hydrocarbon distribution, including branching.

Other Anionic Surfactants - Other anionic surfactants suitable for detersive use may also be included in the compositions of the present invention. They may include soap salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts), C ₉ -C ₂₀ linear alkylbenzene sulfonates, C ₈ -C ₂₂ Primary or secondary alkane sulfonates, _C8 - _C24 olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonating the cleavage products of alkaline earth metal citrates, alkylglycerols as described, for example, in British Patent Specification 1082179 Sulfonates, fatty acylglycerolsulfonates, fatty oleoacylglycerolsulfates, alkylphenol oxirane ether sulfates, paraffinsulfonates, alkylphosphates, isethionates, e.g., acyl hydroxy Ethylates, N-acyl taurates, fatty acid amides of methyl taurine, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated _C12 -C ₁₈ monoesters) and sulfosuccinate diesters (especially saturated and unsaturated C ₆ -C ₁₄ diesters), N-acyl sarcosinates, sulfates of alkyl polysaccharides such as alkyl polyglucose Glycoside sulfates (nonionic _unsulfated compounds described below), branched primary alkyl sulfates ^and alkyl polyethoxy carboxylates, such as the formula RO( _CH2CH2O ) _k - _CH2COO- M ⁺ , wherein, R is a C ₈ -C ₂₂ alkyl group, k is an integer from 0 to 10, and M is a water-soluble salt-forming cation, a fatty acid esterified with isethionate and neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Volumes I and II, Schwartz, Perry and Berch). A variety of such surfactants are also generally described in US Patent 3,929,678, Laughlin et al., issued December 30, 1975 at column 23, line 58 through column 29, line 23.

Secondary Surfactant - The secondary detersive surfactant may be selected from nonionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants and mixtures thereof. By selection of the type and amount of detersive surfactants, together with other adjunct ingredients discussed herein, the detergent compositions of the present invention can be formulated for laundry or other various detersive applications, including especially the dishwashing range. The particular surfactant employed may thus vary widely depending upon the particular end use involved, suitable secondary surfactants being described hereinafter.

Nonionic Detergent Surfactants - Suitable nonionic detergent surfactants are generally described in US Pat. References for this article. Non-limiting examples of useful nonionic surfactants include: alkyl dialkyl amine oxides, alkyl ethoxylates, alkanoyl glucamides, alkyl betaines, and mixtures thereof.

Other nonionic surfactants useful in the present invention include:

Polyoxyethylene, polyoxypropylene and polyoxybutylene condensates of alkylphenols, polyoxyethylene condensates are generally preferred. These compounds include the condensation products of alkylphenols with alkylene oxides having an alkyl group having from about 6 to about 12 carbon atoms in a linear or branched configuration. In a preferred embodiment, ethylene oxide is present in an amount equal to about 5 to about 25 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepal ^™ CO-630 sold by the GAF company, Triton ^™ X-45, X-114, X-100 and X-102 sold by the Rohm & Haas company . These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

Condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Especially preferred are the condensation products of alcohols having alkyl groups containing from about 10 to about 20 carbon atoms with from about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol® 15-S-9 (condensation product of C ₁₁ -C ₁₅ linear secondary alcohols with 9 moles of ethylene oxide), Tergitol® 24- L-6 NMW (condensation product of a C ₁₂ -C ₁₄ primary alcohol with a narrow molecular weight distribution and 6 moles of ethylene oxide), both sold by Union Carbide; Neodol® 45-9 (C ₁₄ -C ₁₅ linear alcohol Condensation product with 9 moles of ethylene oxide), Neodol® 23-6.5 (condensation product of C ₁₂ -C ₁₃ linear alcohol with 6.5 moles of ethylene oxide), Neodol® 45-7 (C ₁₄ -C ₁₅ straight chain alcohol Condensation product of chain alcohol with 7 moles of ethylene oxide) and Neodol® 45-5 (condensation product of C ₁₄ -C ₁₅ linear alcohol with 5 moles of ethylene oxide), both sold by Shell Chemical Company; Kyro® EOB (Condensation product of C ₁₃ -C ₁₅ alcohols with 9 moles of ethylene oxide), sold by P&G. Other commercially available nonionic surfactants include Dobanol 91-8® sold by Shell Chemical Company and Genapol UD-080 sold by Hoechst, such nonionic surfactants are commonly referred to as "alkyl ethoxylates" .

Condensation product of ethylene oxide with hydrophobic groups formed by condensation of propylene oxide with propylene glycol. The hydrophobic groups of these compounds preferably have a molecular weight of from about 1500 to about 1800 and exhibit water insolubility. The addition of polyoxyethylene groups to this hydrophobic group will increase the overall water solubility of the molecule and the liquid character of the product will be maintained up to a polyoxyethylene content of about 50% of the total weight of the condensation product, which corresponds to a condensation of up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available Pluronic(R) surfactants, sold by BASF.

The condensation product of ethylene oxide with the product obtained by the reaction of propylene oxide and ethylenediamine. The hydrophobic groups of these products consist of the reaction product of ethylenediamine and excess propylene oxide and generally have a molecular weight of from about 2500 to about 3000. The hydrophobic group is condensed with ethylene oxide to such an extent that the condensation product contains from about 40% to about 80% by weight polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of nonionic surfactants of this type include certain of the commercially available Tetronic(R) compounds, sold by BASF.

Semi-polar nonionic surfactants are a special class of nonionic surfactants comprising one alkyl group containing from about 10 to about 18 carbon atoms and two selected from the group consisting of alkyl groups containing from about 1 to about 3 carbon atoms Water-soluble amine oxides of groups containing from about 10 to about 18 carbon atoms and two groups selected from the group consisting of alkyl and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms and water-soluble sulfoxides containing an alkyl group of about 10 to about 18 carbon atoms and a group selected from the group consisting of alkyl and hydroxyalkyl groups of about 1 to about 3 carbon atoms.

Semi-polar nonionic detergent surfactants include amine oxide surfactants having the formula: Wherein ^R is alkyl, hydroxyalkyl or alkylphenyl containing about 8 to about 22 carbon atoms; ^R is alkylene or hydroxyalkylene or their derivatives containing about 2 to about 3 carbon atoms Mixture; x is 0 to about 3; each ^R is an alkyl or hydroxyalkyl group containing about 1 to about 3 carbon atoms or a polyoxyethylene group containing about 1 to about 3 oxirane groups . The R ⁵ groups may be linked to each other, for example via an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants include C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxides, among others.

Alkyl polysaccharides disclosed in US4565647 of Llenado issued on January 21, 1986, which contain hydrophobic groups of about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms and about 1.3 to about 10 , preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7 saccharide units of polysaccharides, such as polyglycosides, hydrophilic groups. Any reducing sugar containing 5 or 6 carbon atoms can be used, eg glucose, galactose and galactosyl can be used in place of glucosyl. (Hydrophobic groups are selectively attached at 2-, 3-, 4-, etc. positions, resulting in glucose or galactose relative to glucoside or galactoside). An internal sugar bond may be, for example, between one position of the added sugar unit and the 2-, 3-, 4- and/or 6-position of the previous sugar unit.

Optionally, but less desirably, there may be a polyoxyalkylene chain linking the hydrophobic portion and the polysaccharide portion. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include saturated or unsaturated, branched or unbranched alkyl groups containing from about 8 to about 18, preferably from about 10 to about 16 carbon atoms, preferably straight chain saturated alkyl groups. The alkyl group may contain up to about 3 hydroxyl groups and/or the polyoxyalkylene chain may contain up to about 10, preferably less than 5, alkylene oxide moieties. Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and Octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucose, fructosides, fructose, and/or galactose. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyl tetra-, penta-, and hexaglucosides.

Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O) _t (glycosyl) _x wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl group contains about 10- About 18, preferably about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is 0 to about 10, preferably 0, x is about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 - about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxylated alcohol is first formed and subsequently reacted with glucose or a source of glucose to form the glucoside (attached at the 1-position). Further glycosyl groups may subsequently be attached between their 1-position and the 2-, 3-, 4- and/or 6-position of the preceding saccharide unit, preferably predominantly in the 2-position.

Fatty acid amide surfactants have the formula:

R ⁶ -C(O)-N(R ⁷ ) ₂ wherein R ⁶ is an alkyl group containing about 7 to about 21 (preferably about 9 to about 17) carbon atoms and each R ⁷ is selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, and -(C ₂ H ₄ O) _x H, wherein x is about 1 to about 3.

Preferred amides are C ₈ -C ₂₀ aminoamides, monoethanolamides, diethanolamides and isopropanolamides.

Cationic Surfactants - Cationic detersive surfactants can also be included in the detergent compositions of the present invention. Cationic surfactants include ammonium surfactants, such as alkyldimethylammonium halides, and surfactants having the formula:

[R ² (OR ³ ) _y ][R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X ^- wherein R ² is an alkyl or alkyl benzyl having from about 8 to about 18 carbon atoms in the alkyl chain Each R ³ is selected from the group consisting of -CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )-, -CH ₂ CH(CH ₂ OH)-, -CH ₂ CH ₂ CH ₂ - and mixtures thereof; Each R ⁴ is selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl, a ring structure formed by connecting two R ⁴ groups, -CH ₂ CHOHCHHOHCOR ⁶ CHOHCH ₂ OH, wherein R ⁶ is any hexose or hexose polymer having a molecular weight of less than about 1000, and when y is not 0, is hydrogen; ^R5 is the same as ^R4 or an alkyl chain, wherein the total number of carbon atoms of ^R2 plus ^R5 is not exceeds about 18; each y is from 0 to about 10, the sum of the y values is from 0 to about 15; and X is any compatible anion.

Other cationic surfactants useful in the present invention are also described in US Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.

Other Surfactants - Amphoteric surfactants can also be incorporated into the detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic group may be straight or branched. One of the aliphatic substituents contains at least about 8 carbon atoms, usually from about 8 to about 18 carbon atoms and at least one of the aliphatic substituents contains an anionic water solubilizing group, eg, carboxy, sulfonate, sulfate. See US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 19, lines 18-35, for examples of amphoteric surfactants. Preferred amphoteric surfactants include C ₁₂ -C ₁₈ alkyl ethoxylates ("AE"), including the so-called narrow peak alkyl ethoxylates and C ₆ -C ₁₂ alkylphenol alkoxylates (especially are ethoxylates and mixed ethoxylates/propoxylates), C ₁₂ -C ₁₈ betaines and sultaines, C ₁₀ -C ₁₈ ammonium oxides and mixtures thereof.

Zwitterionic surfactants can also be incorporated into the detergent compositions of the present invention. These surfactants can be broadly described as derivatives of secondary or tertiary amines or derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See US Patent 3,929,678, Laughlin et al., issued December 30, 1975, column 19, line 38 - column 22, line 48, for zwitterionic surfactants. Amphoteric and zwitterionic surfactants are often used in combination with one or more anionic and/or nonionic surfactants.

Polyhydroxy Fatty Acid Amide Surfactant - The detergent compositions of the present invention may contain an effective amount of a polyhydroxy fatty acid amide surfactant. "Effective amount"means the amount of polyhydroxy fatty acid amide that the formulator of the composition may choose to add to the composition to improve the cleaning performance of the detergent composition. Typically, at conventional levels, the addition of about 1% by weight of polyhydroxy fatty acid amide will improve detergency.

The detergent compositions herein will contain from about 1% by weight of the polyhydroxy fatty acid amide surfactant, preferably from about 3% to about 30% of the polyhydroxy fatty acid amide. The polyhydroxy fatty acid amide surfactant component comprises the compound of following structural formula:

R ² -C(O)-N(R ¹ )-Z wherein, R ¹ is hydrogen, C ₁ -C ₄ hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C ₁ - C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (i.e. methyl); R ² is C ₅ -C ₃₁ hydrocarbon, preferably straight chain C ₇ -C ₁₉ alkyl or alkenyl , more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ -C ₁₅ alkyl or alkenyl or a mixture thereof; Z is a poly having at least three hydroxyl groups directly attached to the linear hydrocarbon chain Hydroxyhydrocarbyl or alkoxylated (preferably ethoxylated or propoxylated) derivatives thereof. Z is preferably derived from a reducing sugar in a reductive amination reaction, more preferably Z is a glycosyl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup can be used as well as the individual sugars listed above. From these corn syrups a mixture of sugar components Z can be obtained. It should be appreciated that it is not intended to exclude other suitable starting materials. Z _{is preferably selected from -CH2(CHOH)n-CH2OH, -CH(CH2OH)(CHOH)n-1-CH2OH, -CH2-(CHOH)2 ( CHOR ' ) ( CHOH )} - CH ₂ OH, and its alkoxylated derivatives, wherein n is an integer from 3 to 5 inclusive, and R' is H or a cyclic or aliphatic monosaccharide. In the most preferred glycityls, n is 4, especially _-CH2- (CHOH) ₄ - _CH2OH .

R ¹ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R ² -CO-N< can be, for example, cocamide, stearylamide, oleamide, laurylamide, myristamide, capricamide, palmitamide, tallowamide, and the like.

Z can be 1-deoxyglucosyl, 2-deoxyfructosyl, 1-deoxymaltose, 1-deoxylactosyl, 1-deoxygalactosyl, 1-deoxymannosyl, 1-deoxyxylosyl wait.

Methods of preparing polyhydroxy fatty acid amides are known in the art. Typically they are obtained by reacting an alkylamine with a reducing sugar in a reductive amination reaction to form the corresponding N-alkylpolyhydroxylamine, followed by reacting the N-alkylpolyhydroxylamine with a fatty aliphatic polyhydroxylamine in a condensation/amidation step. Prepared by reacting esters or triglycerides to form N-alkyl, N-polyhydroxy fatty acid amide products. The method for preparing compositions containing polyhydroxy fatty acid amides is disclosed in for example Thomas Hedley & Co. on February 18, 1959, GB809060 of Ltd, US2965576 of E.R.Wilson issued on December 20, 1960, March 8, 1955 Disclosed in US 2,703,798, Anthony. M. Schwarrcher; US 1,985,424, Piggott, issued Dec. 26, 1934, each of which is incorporated herein by reference.

Builders - The compositions of the present invention may also contain a builder system. Any conventional builder system is suitable for use herein, including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphine acid salts, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Although less preferred for obvious environmental reasons, phosphate builders can also be used herein.

Suitable polycarboxylates for use in the present invention include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH), wherein R is a C10-20 alkyl or alkenyl Group, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo, sulfoxide or sulfone substituents. Specific examples include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.

Other suitable polycarboxylates are oxydisuccinates and mixtures of tartrate monosuccinates and tartrate disuccinates, as described in US 4,663,071.

Especially in the case of the liquids of the present invention, suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids and the corresponding soaps. The preferred saturated material contains 12-16 carbon atoms in the alkyl chain, and the preferred unsaturated fatty acid is oleic acid. Other preferred builder systems for liquid compositions are dodecenylsuccinic acid and citric acid.

Detergency builder salts will generally be present at 3% to 50%, preferably 5% to 30%, and most commonly 5% to 25% by weight of the composition.

Optional detergent ingredients: - The detergent compositions of the present invention also contain one or more enzymes which provide a cleaning performance benefit. Said enzyme comprises cellulase, hemicellulase, peroxidase, protease, glucoamylase, amylase, lipase, cutinase, pectinase, xylanase, reductase, oxidase, Enzymes of phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malic enzyme, beta-glucanase, arabinosidase or mixtures thereof. Preferred combinations are detergent compositions containing commonly used enzymes such as proteases, amylases, lipases, cutinases and/or cellulases in combination.

Cellulases - Cellulases useful in the present invention include bacterial or fungal cellulases. Suitable cellulases are disclosed in Barbesgoard et al. US 4,435,307 which discloses fungal cellulases produced by Humicola insilons. Suitable cellulases are also disclosed in GB-A-2075028, GB-A-2095275 and DE-OS-2247832.

An example of such a cellulase is a cellulase produced by a strain of Humicola insilons (Humicola grisea var. thermoidea), especially the strain DSM 1800. Other suitable cellulases are cellulases derived from Humicola insilons having a molecular weight of about 50 KDa, an isoelectric point of 5.5 and containing 415 amino acids. Particularly suitable cellulases are cellulases having a color care effect. Examples of such cellulases are the cellulases described in EP patent application No. 91202879.2 (Novo) filed on 06.11.1991.

Peroxidases are used in combination with an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are used for "solution bleaching", ie to avoid the transfer of dyes or pigments removed from a substrate during washing operations to other substrates in the wash solution. Peroxidases are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases, such as chloro- and bromo-peroxidases. Detergent compositions containing peroxidases are disclosed, for example, in PCT International Application WO89/099813 and European Patent Application EP91202882.6 filed November 6,1991.

The cellulases and/or peroxidases are typically incorporated into detergent compositions at levels of 0.0001% to 2% active enzyme by weight of the composition.

Protease - The protease may be of animal, vegetable or microbial (preferred) origin. Proteases useful in the detergent compositions of the present invention include, but are not limited to, trypsin, subtilisin, chymotrypsin and elastase. Preferred for use in the present invention are subtilisins. Especially preferred are bacterial serine proteases derived from Bacillus subtilis and Bacillus licheniformis.

Suitable proteases include Novo Industries A/S Alcalase® (preferred), Esperase®, Savinase® (Copenhagen, Denmark), Maxatase®, Maxacal® and Maxapem 15® from Gist-Brocades (Savinase® from Protein Engineering) (Delft, Netherlands) and Bacillus subtilis BPN and BPN' (preferred), which are commercially available. Preferred proteases are also modified bacterial serine proteases, such as those prepared by Genencor International, Inc. (San Francisco, California), which are described in EP251446B, issued December 28, 1994 (particularly pages 17, 24 and 98) , which is referred to herein as "Protease B". US5030378, Venegas, issued Jul. 9, 1991, relates to a modified bacterial serine proteolytic enzyme (Genencor International), which is referred to herein as "Protease A" (same as BPN'). See especially US5030378, columns 2 and 3 for a complete description of the compound, including the amino sequence, and its variants. Other proteases are sold under the tradenames Primase(R), Durazym(R), Opticlean(R) and Optimase(R). Preferred proteases are selected from the group consisting of Alcalase® (Novo Industries A/S), BPN', Protease A and Protease B (Genencor) and mixtures thereof, with Protease B being most preferred.

Proteases of particular interest for use in the present invention are described in US5470733.

Proteases described in our co-pending application USSN 08/136797 may also be included in the detergent compositions of the present invention.

Another preferred protease known as "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase via a In the position, it is also preferred to be selected from +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and/or +274 (according to the At one or more amino acid residue positions in the position in the counting method), various amino acid residues are replaced with different amino acids, which is disclosed in Genencor International WO 95/10615 published on April 20, 1995 (A.Baeck et al. , entitled "Protease-Containing Detergent Compositions", described in US Patent Application No. 08/322676 filed on October 13, 1994).

Useful proteases are also described in the following PCT publications: WO95/30010 published November 9, 1995 by Procter & Gamble Company; WO95/30011 published November 9, 1995 by Procter & Gamble Company; WO95 published November 9, 1995 by Procter & Gamble Company /29979.

Proteases are incorporated into the detergent compositions of the present invention at levels of 0.0001% to 2% active enzyme by weight of the composition.

Lipases - Suitable lipases include microorganisms of the genus Pseudomonas, such as the lipases mentioned in Pseudomonas stutzeri ATCC 19.154 disclosed in GB1372034. Suitable lipases include those produced by the microorganism Pseudomonas fluorescens IAM 1057 which show positive immunological cross-reactivity with lipase antibodies. This lipase is commercially available from Amano Pharmaceutical Co. Ltd. Nagoya, Japan under the tradename Lipase P "Amano", hereinafter referred to as "Amano-P". Other suitable lipases are lipases such as M1 ^Lipase® and ^Lipomax® (Gist-Broxades). Other suitable commercial lipases include Amano-CES, lipase from Chromobacter viscosus, such as Chromobacter viscosus var NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; from USBiochemical Corp., USA and Disoynth lipase from Chromobacter viscosus; and a lipase from Pseudomonas hyperichoria. The LIPOLASE(R) enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EP341947) is a preferred lipase for use in the present invention. Peroxidase-stable lipase and amylase variants are described in WO9414951A to Novo. See also WO9205249 and RD94359044.

A highly preferred lipase is the D96L lipolytic enzyme variant of the natural lipase produced by Humicola lanuginosa as described in US Serial No. 08/341826. (See also patent application WO92/05249, wherein the aspartic acid (D) residue at position 96 of the natural lipase obtained from Humicola lanuginosa was changed to leucine (L). According to the nomenclature, the above The substitution process of aspartic acid and leucine at position 96 is indicated as D96L). Preferably the Humicola lanuginosa strain DSM 4106 is used.

Despite numerous publications on lipases, so far only lipases produced by Humicola lanuginosa and Aspergillus oryzae as hosts have been found to be widely used as additives to fabric washing products. It is available under the trade names Lipolase ^(R) and Lipolase Ultra( ^R ) from Novo Nordisk as described above. To optimize the stain removal performance of Lipolase, Novo Nordisk has prepared various variants. As described in WO92/05249, the D96L variant of the native Humicola lanuginosa lipase was 4.4% more effective at removing lard stains than the wild-type lipase (enzymes compared in the range of 0.075-2.5 mg protein per liter). times. Research Disclosure No. 35944 (Novo Nordisk), published March 10, 1994, discloses that the lipase variant (D96L) can be added in an amount corresponding to 0.001-100 mg per liter of wash liquor (5-500000 LU/l).

Also suitable are cutinases [EC 3.1.1.50], which are considered a special class of lipases, i.e. lipases that do not require interfacial activation. The incorporation of cutinases in detergent compositions is described eg in WO-A-88/09367 (Genencor).

Lipase and/or cutinase are typically incorporated into detergent compositions at levels of 0.0001% to 2% active enzyme by weight of the detergent composition.

Amylases - Amylases (alpha and/or beta) may be involved in the removal of sugar hydrate based stains. Suitable amylases are ^Termamyl® (Novo Nordisk), ^Fungamyl® and ^BAN® (Novo Nordisk). Enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Amylases are typically added to the wash at levels of 0.0001% to 2%, preferably 0.0001% to about 0.5%, more preferably about 0.005% to about 0.1%, most preferably about 0.001% to about 0.05% active enzyme by weight of the detergent composition agent composition.

Amylases also include those described in WO/95/26397 and Novo Nordisk's concurrent application PCT/DK96/00056. Other specific amylases useful in the detergent compositions of the present invention include:

(a) an α-amylase characterized in that it has a higher specific activity than Termamyl® in the temperature range of 25°C-55°C and at a pH of 8-10, as determined by the Phadebas® α-amylase activity test A specific activity of at least 25%, the Phadebas(R) alpha-amylase activity test described in WO 95/26397 pages 9-10.

(b) The α-amylase according to (a), which contains the amino sequence shown in the SEQ ID table in the above-listed documents or an α-amylase that is at least 80% homologous to the amino sequence shown in the SEQ ID table.

(c) α-amylase according to (a), obtained from the genus Alkalinophilus, which contains the following amino sequence at the N-terminus: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln -Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp.

A polypeptide is said to be X% homologous to the parent amylase if comparison of the respective amino acid sequences, completed by a rule system, eg as described by Lipman and Pearsin in Science 227, 1985, p. 1435, demonstrates X% identity.

(d) α-amylases according to (a-c), wherein the α-amylases are obtained from the genus Alkalinophilus, especially from any of the strains NCIB 12289, NCIB 12512, NCIB 12513 and DSM 935.

In the context of the present invention, the term "obtainable from" refers not only to the amylase produced by a Bacillus, but also to an amylase encoded by a DNA sequence isolated from that Bacillus and produced in a host organism transformed with that DNA sequence Amylase.

(e) α-amylases showing positive immunological cross-reactivity to antibodies raised by α-amylases having amino acid sequences corresponding to those in (a-d), respectively.

(f) variants of the parent alpha-amylase which (i) each have one of the amino acid sequences shown in (a-e), or (ii) show at least 80% homology to one or more of said amino acid sequences , and/or show positive immunological cross-reactivity to antibodies produced by an α-amylase having one of the amino acid sequences described above, and/or are encoded by a DNA sequence that is identical to the α-amylase encoding one of the amino acid sequences The same probe hybridizes to the DNA sequence of the enzyme; where variants:

1. At least one amino acid residue of the parent alpha-amylase is omitted; and/or

2. At least one amino acid residue of the parent alpha-amylase is replaced by a different amino acid residue; and/or

3. Insertion of at least one amino acid residue relative to said parent alpha-amylase;

The variant has alpha-amylase activity exhibiting at least one of the following properties relative to the parent alpha-amylase: increased thermostability, increased oxidative stability, decreased calcium ion dependence, neutral to relatively Increased stability and/or α-amylase activity at high pH values, increased α-amylase activity at higher temperatures and increased or decreased isoelectric point (pI) so that the pi of the α-amylase variant The value is better adapted to the pH of the medium.

Said variants are described in application PCT/DK96/00056.

Other amylases suitable for the present invention include, for example, the alpha-amylases described in Novo's GB 1296839: RAPIDASE(R) from International Bio-Synthetic, Inc and TERMAMYL(R) from Novo, FUNGAMYL(R) from Novo is particularly useful. Methods for improving the stability of enzymes, such as oxidative stability, are known. See, eg, J. Biological Chem, No. Vol. 260, Jun. 11, 1985, pp. 6518-6521. Certain preferred embodiments of the present invention may be used in detergents, such as automatic dishwashing types, having improved stability, especially improved oxidative stability relative to a reference point measured since 1993 on commercially used TERMAMYL® of amylase. These preferred amylases of the invention are characterized as "stability-increased" amylases characterized at least by oxidative stability, such as hydrogen peroxide/tetraacetylethylenediamine in a buffered solution at pH = 9-10 Oxidative stability; thermal stability as measured at normal wash temperatures such as about 60°C; or alkaline stability as measured against the aforementioned reference point amylase at a pH of about 8-11. Stability may be measured using any known art assay, see for example that disclosed in WO9402597. Amylases with increased stability are available from Novo or Genencor International. A more preferred amylase of the present invention has the following in common: it is derived from one or more bacillus amylases, especially from bacillus α-amylases by site-directed mutagenesis, and is combined with one, two or more It is irrelevant whether the species amylase is the immediate precursor or not. Preference is given to using amylases with increased oxidative stability relative to the reference enzymes mentioned above, especially for bleaching, more preferably oxygen bleaching as opposed to chlorine bleaching. Such preferred amylases include (a) amylases according to the above-mentioned Novo WO 9402597, which can be further illustrated by a mutant wherein alanine or threonine is used, preferably threonine Acid substitution at position 197 of a methionine residue in a Bacillus licheniformis known as TERMANYL®, or a homologous positional variant of a similar proamylase such as Bacillus amyloanaerobacillus, Bacillus subtilis, or stereogenic thermophiles; (b) Genencor International Stability-increased amylases described in a paper entitled "Antioxidant Alpha-Amylases", presented by C. Mitchinson to the 207th Annual Meeting of the American Chemical Society, March 13-17, 1994. Bleach inactivation of alpha-amylases in automatic dishwashing detergents is mentioned, but Genencor has produced amylases with improved oxidative stability from Bacillus licheniformis NCIB8061. Methionine (Met) proved to be the most easily modifiable residue. Met is simultaneously substituted at positions 8, 15, 197, 256, 304, 366, and 438 to obtain specific mutations, especially M197L and M197T, among which the M197T variant is the most stable variant. Stability was measured in CASCADE® and SUNLIGHT®; (c) particularly preferred amylases of the invention include amylase variants with additional modifications in the immediate parent as described in WO9510603A, available from Novo under the trade name DURAMYL® . Other particularly preferred amylases with increased oxidative stability include those described in WO9418314 to Genencor International and WO9402597 to Novo. Any other amylase with increased oxidative stability may be used, for example derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parents of available amylases. Other preferred enzymatic modifications can be made, see WO9509909A to Novo.

Various carbohydrases that impart antibacterial activity may also be included in the present invention. Such enzymes include endoglucanases, type II endoglucanases and glucanases disclosed in US5041236, 5395541, 5238843 and 5356803, which are incorporated herein by reference. Accordingly, other enzymes containing antimicrobial activity may be used, including peroxidases, oxidases, and various other enzymes.

Enzyme Stabilizing System - Enzyme-containing compositions of the present invention can optionally contain from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. The enzyme stabilization system can be any stabilization system compatible with the wash enzyme. Such systems may themselves be provided by other formulation active ingredients, or added separately, for example by the formulator or manufacturer of enzyme-containing detergents. Such stabilizing systems can, for example, include calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acids, and mixtures thereof, and are used to address stabilization problems of varying nature depending on the type and physical form of the detergent composition.

One way to create stabilization is to use water-soluble sources of calcium and/or magnesium ions in the final composition that provide the enzyme with its ions. Calcium ions are generally more effective than magnesium ions, so it is preferred if only one cation is used. Typical detergent compositions, especially liquids, contain from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of final detergent composition, although according to the Factors including the type, type and amount of enzyme added may vary. Water-soluble calcium or magnesium salts are preferably used, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or all The corresponding magnesium salts of the calcium salts are listed. It may of course be useful to further increase the calcium and/or magnesium content, for example to increase the degreasing effect of certain types of surfactants.

Another way of producing stabilization is the use of borate species, see US4537706 to Severson. Borate stabilizers can be used at levels up to 10% or more of the composition, but boric acid or other borate compounds such as borax or orthoborate are generally suitable for use in liquid detergents at levels up to about 3 weight%. Substituted boric acids, such as phenylboronic acid, butyric acid, p-bromophenylboronic acid, etc., can be used instead of boric acid, and despite the use of such substituted boron derivatives, it is still possible to reduce the total boron content of detergent compositions .

Stabilizing systems for certain detergent compositions, such as automatic dishwashing detergent compositions, may further contain from 0 to about 10%, preferably from about 0.01% to about 6%, by weight of a chlorine bleach scavenger, which may be added to prevent the presence of Chlorine bleach species in many water sources attack and inactivate enzymes, especially under alkaline conditions. Although the chlorine content in water can be very little, generally in the range of about 0.5 ppm to about 1.75 ppm, the amount of chlorine in all water accessible to enzymes can be considerable, for example during the washing of dishes or fabrics; In some cases, the stability of the enzyme is sometimes problematic. Since perborates or percarbonates capable of reacting with chlorine bleaching substances are present in some of the present compositions in amounts metered separately from the stabilizing system, the use of other chlorine stabilizers may generally not be necessary, Although their use may increase the effect. Suitable chlorine scavenger anions are well known and readily available and, if used, may be sulfites, bisulfites, thiosulfites, thiosulfates, iodides, etc. containing ammonium cations. Additionally, antioxidants such as carbamates, ascorbic acid, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or its alkali metal salts, monoethanolamine (MEA) and mixtures thereof may be used. In addition, a special enzyme inhibition system can be added so that different enzymes have the greatest compatibility. Other conventional scavengers such as bisulphates, nitrates, chlorides, hydrogen peroxide sources such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphates, condensation Phosphates, acetates, benzoates, citrates, formates, lactates, malates, tartrates, salicylates, etc., and mixtures thereof. In general, since ingredients listed individually on the basis of their perceived superior function (such as a source of hydrogen peroxide) can perform the function of a chlorine scavenger, it is not necessary to require the addition of a different chlorine scavenger unless that function is performed to the extent indicated. Compounds to the required extent are not present in the enzyme-containing embodiments of the invention, and even then the scavenger is only added for optimum effect. Also, the formulator can use ordinary skill as a chemist in order to avoid the use of any enzyme traps or stabilizers that are substantially incompatible when formulated with other active ingredients, if used. For the use of ammonium salts, such salts can simply be premixed with the detergent composition, but tend to absorb water and/or release ammonia during storage. Therefore, it is desirable to protect such material, if present, within the particles, as described in Baginski et al. US 4,652,392.

Perfumes - Perfumes and perfume components useful in the compositions and methods of the present invention include a variety of natural and synthetic chemical components including, but not limited to, aldehydes, ketones, esters, and the like. Also included are various natural extracts and fragrances which can contain complex mixtures of components such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic essence, sandalwood oil, pine oil, cedarwood, etc. . The final perfume can contain extremely complex mixtures of these components. The detergent compositions of the present invention typically contain from about 0.01% to about 2% by weight of the final perfume. Individual perfume components can account for about 2% of the final perfume composition. 0.0001% - about 90%.

Non-limiting examples of perfume ingredients useful in the present invention include: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylbenzene , Methyl citronone, γ-methyl citronone, methyl cedronone, 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-dimethyldi Indane, p-hydroxyphenylbutanone, benzophenone, methyl β-naphthyl ketone, 6-acetyl-1,1,2,3,3,5-hexamethylindane, 5-acetyl Base-3-isopropyl-1,1,2,6-tetramethylindane, 1-dodecanal, 4-(4-hydroxy-4-methylphenyl)-3-cyclohexene- 1-Aldehyde, 7-Hydroxy-3,7-Dimethyloctylal, 10-Undecen-1-Aldehyde, Isohexenylcyclohexylcarbaldehyde, Formyltricyclodecane, Hydroxycitronellal, and Methylamine Condensation products of anisyl ester, condensation products of hydroxycitronellal and indole, condensation products of phenylacetaldehyde and indole, 2-methyl-3-(p-tert-butylphenyl) propionaldehyde, ethyl aromatic Lantin, heliotrope, hexyl cinnamaldehyde, amyl cinnamaldehyde, 2-methyl-2-(p-isopropylphenyl) propionaldehyde, coumarin, γ-decalone, cyclopentadecanol anhydride , 16-hydroxy-9-hexadecenolactone, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2 -benzopyran, β-naphthyl alcohol methyl ether, ambroxane, dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan, cedrol, 5- (2,2,3-Trimethylcyclopent-3-enyl)-3-methylpentan-2-ol, 2-ethyl-4-(2,2,3-trimethyl-3-cyclo Penten-1-yl)-2-buten-1-ol, Caryophyllol, Tricyclodecenyl Propionate, Tricyclodecenyl Acetate, Benzyl Salicylate, Cedar Acetate and p-(tert-butyl)cyclohexyl acetate.

Especially preferred perfume materials are those which provide the greatest odor improvement in the final product composition containing cellulase. These fragrances include, but are not limited to, hexylcinnamaldehyde, 2-methyl-3-(p-isopropylphenyl)propanal, 7-acetyl-1,2,3,4,5,6,7 , 8-octahydro-1,1,6,7-tetramethylnaphthalene, benzyl salicylate, 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene, p-tert-butylcyclohexyl acetate, methyl dihydrojasmonate, β-naphthyl alcohol methyl ether, methyl β-naphthyl ketone, 2-methyl-2-(p-isopropylphenyl)propane Aldehydes, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran, dodecahydro-3a, 6,6,9a-Tetramethylnaphtho[2,1-b]furan, anisaldehyde, coumarin, cedrol, vanillin, cyclopentadecanyl anhydride, tricyclodecenyl acetate and tricyclodecenyl acetate Cyclodecenyl Propionate.

Other fragrance materials include essential oils, balsams, and resins obtained from various sources including, but not limited to, Peru balsam, frankincense, styrax, cistus resin, nutmeg, cinnamon oil, benzoin resin, coriander oil and Lavender. Other fragrance compounds include phenylethyl alcohol, terpene alcohol, linalool, linalyl acetate, geraniol, nerol, 2-(1,1-dimethylethyl)cyclohexanol esters, benzyl acetate and eugenol. Carriers such as diethylphthalate may be used in the final fragrance composition.

Polymeric Dispersants - Polymeric dispersants may advantageously be used in the compositions of the present invention at levels of from about 0.1% to about 7% by weight. While not wishing to be bound by theory, it is believed that the overall performance of the detergent builder can be enhanced when the polymeric dispersant acts through crystal growth inhibition, especially peptization of soil release and anti-redeposition.

The polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in the acid form. Unsaturated monomeric acids which can be polymerized to produce suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and Methylenemalonic acid. In the polymeric polycarboxylates of the present invention, monomeric moieties containing monomeric moieties not having carboxylate groups such as vinylmethyl ether, styrene, ethylene, etc. are suitable as long as they do not exceed Count about 40%.

Especially suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers useful in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably from about 2,000 to 10,000, more preferably from about 4,000 to 7,000, most preferably from about 4,000 to 5,000. Examples of water-soluble salts of such acrylic acid polymers include alkali metal salts, ammonium salts and substituted ammonium salts. Such soluble polymers are known. The use of such polymeric acrylates in detergent compositions is disclosed in US Patent 3,308,067, Diehl, issued March 7, 1967.

Acrylic/maleic acid based copolymers can also be used as a preferred component of the dispersing/anti-deposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is preferably from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylic acid moieties to maleic acid moieties in such copolymers is generally from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Such water-soluble acrylic acid/maleate copolymers are known materials and are disclosed in EP66915, published December 15, 1982, and in EP193360, published September 3, 1986, which also describes Such polymers based on acrylates. Other useful dispersants include terpolymers of maleic acid/acrylic acid/vinyl alcohol, which are also disclosed in EP193360, including for example the 45/45/10 terpolymer of maleic acid/acrylic acid/vinyl alcohol.

Another class of polymers that can be included is polypropylene glycol (PPG), propylene glycol (PG) and polyethylene glycol (PEG). PEG can exhibit dispersant properties as well as act as a clay soil removal/anti-redeposition agent. The average molecular weight of polyethylene glycol for this use is generally from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyaspartate and polyglutamate dispersants can also be used, especially in combination with zeolite builders. Dispersants, such as polyaspartate, preferably have a molecular weight (average) of about 10,000.

In addition, polymeric soil release agents, hereinafter "SRA", can optionally be used in the detergent compositions of the present invention. If used, SRA will typically range from 0.01% to 10.0%, typically 0.1% to 5%, preferably 0.2% to 3.0%, by weight of the composition.

SRA preferably contains a hydrophilic segment to hydrophilize the surface of hydrophobic fibers such as polyester and nylon; SRA also contains a hydrophobic segment to deposit on the surface of the hydrophobic fiber and remain attached to the fiber surface throughout the washing and rinsing cycle. The hydrophilic part plays a fixing role. This makes it easier to remove stains after SRA treatment in subsequent washes.

SRAs may comprise various charged, eg anionic or even cationic species (see US4956447) as well as uncharged monomeric units, which may be linear, branched or star-shaped in structure. They may include capping groups which are especially effective in controlling molecular weight or modifying physical or surface active properties. The structure and charge distribution can be varied for application to different fiber or textile types and different detergent or detergent additive products.

Preferred SRAs include oligomeric terephthalates, typically prepared by at least one transesterification/oligomerization process, typically using a metal catalyst such as titanium(IV) alkoxide. The esters may be prepared using additional monomers capable of incorporating the ester structure through one, two, three, four or more positions without forming a tightly crosslinked overall structure.

合适的SRA包括在如下专利文献中描述的产物：US4968451、US4711730、US4721580、US4702857、US4877896、US3959230、US3893929、US4000093、EP0219048、US5415807、US4201824、US4240918、US4525524、US4201824、US4579681、EP279134A、EP457205、DE2335044、US4240918 , US4787989, US4525524, US4877896, US4968451, US4702857 and US application 08/545351 and US application 08/355938. Commercially available examples include SOKALAN HP-22 from BASF, Germany; ZELCON 5126 from Dupont and MILEASE T from ICI.

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are useful herein to provide additional grease removal performance. This material is described in WO91/08281 and PCT90/01815, page 4 onwards, incorporated herein by reference. These substances chemically contain polyacrylates with one ethoxy side chain for every 7-8 acrylate units. The side chain has the formula -(CH ₂ CH ₂ O) _m (CH ₂ ) _n CH ₃ , where m is 2-3 and n is 6-12. The side chains are ester linked to the polyacrylate "backbone" to provide a "comb" polymer structure. Molecular weight can vary, but generally ranges from about 2,000 to about 50,000, and the alkoxylated polycarboxylates can comprise from about 0.05% to about 10% by weight of the composition.

Another polymeric dispersant useful in the present invention includes polyethoxylated polyamine polymers (PPP). Preferred polyethoxylated polyamines for use in the present invention are generally polyalkyleneamines (PAA), polyalkyleneimines (PAI), preferably polyethyleneamine (PEA), polyethyleneimine (PEI). Typically the polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA is usually obtained by reaction of ammonia with dichloroethane followed by fractional distillation. Commonly available PEAs are triethylenetetramine (TETA) and tetraethylenepentamine (TEPA). Beyond the pentamines, ie hexamines, heptamines, octaamines and possibly nonamines, the resulting mixtures generally show no separation by distillation and may include other substances such as cyclic amines and especially piperazines. Cyclic amines with side chains containing nitrogen atoms may also be present. See US 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA.

Polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of catalysts such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, and the like. The specific method for preparing these polyamine skeletons is in US2182306 issued by Urich et al on December 5, 1939, US3033746 issued by Mayle et al on May 8, 1962, US2208095 issued by Esselmann et al on July 16, 1940, 1957 US 2,806,839, issued September 17, to Crowther, and US 2,553,696, issued May 21, 1951, to Wilson, are incorporated herein by reference.

其中R选自直链或支链C₂-C₁₂亚烷基、C₃-C₁₂羟基亚烷基、C₄-C₁₂二羟基亚烷基、C₈-C₁₂二烷基亚芳基、[(CH₂CH₂O)_qCH₂CH₂]-、-CH₂CH(OH)CH₂O-、[(CH₂CH₂O)_qCH(OH)CH₂]-，其中q是约1-约100。如果存在，每个R₁分别选自C₁-C₄烷基、C₇-C₁₂烷芳基或A。在某些氮原子上可以不存在R₁，但必须至少三个氮原子被季铵化。In addition, certain alkoxylated (especially ethoxylated) quaternized polyamine dispersants are useful in the present invention as dispersants. Alkoxylated quaternized polyamine dispersants useful in the present invention have the formula:

Wherein R is selected from linear or branched C ₂ -C ₁₂ alkylene, C ₃ -C ₁₂ hydroxyalkylene, C ₄ -C ₁₂ dihydroxyalkylene, C ₈ -C ₁₂ dialkylarylene , [(CH ₂ CH ₂ O) _q CH ₂ CH ₂ ]-, -CH ₂ CH(OH)CH ₂ O-, [(CH ₂ CH ₂ O) _q CH(OH)CH ₂ ]-, where q is About 1 to about 100. If present, each R ₁ is independently selected from C ₁ -C ₄ alkyl, C ₇ -C ₁₂ alkaryl or A. _R1 may be absent on some nitrogen atoms, but at least three nitrogen atoms must be quaternized.

其中R₃选自H或C₁-C₃烷基，n是约5-约100，和B选自H、C₁-C₄烷基、乙酰基或苯甲酰基；m是约0-约4，X是水溶性阴离子。A has the formula:

Wherein R is selected from H or C ₁ -C ₃ alkyl, n is about 5 to _about 100, and B is selected from H, C ₁ -C ₄ alkyl, acetyl or benzoyl; m is about 0 to about 4, X is a water-soluble anion.

其中R₃选自H或甲基，n是约10-约50；和m是1。In a preferred embodiment, R is selected from C ₄ -C ₈ alkylene, R ₁ is selected from C ₁ -C ₂ alkyl or C ₂ -C ₃ hydroxyalkyl, and A is:

wherein R _is selected from H or methyl, n is from about 10 to about 50; and m is 1.

In another preferred embodiment, R is straight or branched C ₆ , R ₁ is methyl, R ₃ is H, and n is from about 20 to about 50, and m is 1.

These dispersants are used at levels of from about 0.1% to about 10%, usually from about 0.4% to about 5%, by weight. These dispersants can be synthesized according to the methods described in US4664848 or other methods known to those skilled in the art.

Brighteners - Any optical brighteners or other brighteners known in the art can generally be incorporated into the detergent compositions herein at a level of from about 0.01% to about 1.2% by weight. Commercially available optical brighteners that can be used in the present invention can be divided into the following groups including, but not necessarily limited to, stilbenes, pyrazolines, coumarins, carboxylic acids, methinecyanines, dibenzothiophenes - 5,5-dioxides, pyrroles, derivatives of 5- and 6-membered heterocycles, and other heterochromants. Examples of these brighteners are disclosed in "Preparation and Use of Optical Brighteners", M. Zahradnik, published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners useful in the compositions of the present invention are the same as disclosed in US Patent 4,790,856, Wixon, issued December 13,1988. These brighteners include Verona's PHOR WHITE range of brighteners. Other brighteners disclosed in this reference include: Ciba-Geigy's Tinopal UNPA, Tinopal CBS and Tinopal 5BM; ArcticWhite CC and Artic White CWD; 2-(4-styrylphenyl)-2H-naphtho[ 1,2-d]triazole; 4,4'-bis(1,2,3-triazol-2-yl)stilbene; 4,4'-bistyrylbiphenyl and aminocoumarin. Specific examples of these brighteners include: 4-methyl-7-diethylaminocoumarin; 1,2-bis(benzimidazol-2-yl)ethylene; 1,3-diphenylpyrazoline ; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphtho[1,2-d]oxazole and 2-(stilbene-4-yl)-2H-naphtho [1,2-d]triazole. See US3646015, Hamilton, issued February 29,1972.

Chelating Agents - The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, as defined below. While not wishing to be bound by any theory, it is believed that these substances are effective in part because they remove iron and manganese ions from the wash liquor through the formation of water-soluble chelates.

Aminocarboxylates useful as selective 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 suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions and include ethylenediamine tetrakis (methylene phosphonates) such as DEQUEST . These amino phosphonates preferably do not contain alkyl or alkylene groups of more than about 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents are also suitable for use in the compositions of the present invention. See US3812044, Connor et al., issued May 21,1974. Preferred compounds of this type in the acid form are dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use in the present invention is ethylenediamine disuccinate ("EDDS"), especially as described in US4704233, Hartman and Perkins, issued November 3, 1987 [S, S] isomer.

The compositions of the present invention may also contain water-soluble methylglycine diacetic acid (MGDA) salt (or acid form) as a chelating agent or co-builder. Likewise, so-called "weak" builders, such as citrates, can also be used as chelating agents.

If utilized, these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. Even more preferably, if used, such chelating agents comprise from about 0.1% to about 3% by weight of the composition.

Composition pH

The dishwashing compositions of the present invention are subject to acid stress from food soils during use, ie after dilution and application to soiled dishes. It is more effective if the pH of the composition is greater than 7, and preferably should contain a compound that provides a more alkaline pH, usually in the composition and in diluted solution, i.e. about 0.1% to 0.4% by weight of the composition in water. buffer. The pKa of the buffer should be about 0.5-1.0 pH units below the desired pH of the composition (measured as described above). Preferably the pKa of the buffer should be from about 7 to about 10. Under these conditions, the buffer is the most effective in controlling the pH, although the least amount is used.

The buffering agent can function as an active detergent by itself, or it can be a low molecular weight, organic or inorganic material used in the composition solely to maintain an alkaline pH. Preferred buffering agents for use in compositions of the invention are nitrogenous substances, some examples being amino acids such as lysine or lower alcohol amines such as mono-, di- and triethanolamine. Other preferred nitrogen-containing buffers are tris(hydroxymethyl)aminomethane (HOCH ₂ ) ₃ CNH ₃ (TRIS), 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl Propanol, 2-amino-2-methyl-1,3-propanol, disodium glutamate, N-methyldiethanolamide, 1,3-diamino-propanol, N,N'-tetramethyl -1,3-diamino-2-propanol, N,N-bis(2-hydroxyethyl)glycine (diglycine) and N-tris(hydroxymethyl)methylglycine (triglycine). Mixtures of any of the foregoing are acceptable. Useful inorganic buffers/alkalinity sources include alkali metal carbonates and alkali metal phosphates, eg sodium carbonate, sodium polyphosphate. For other buffers, see McCutcheon's EMULSIFIERS ANDDETERGENTS, North American Edition, 1977, McCutcheon Division, MC Publishing Company Kirk and WO 95/07971, both incorporated herein by reference.

If used, buffering agents are present in the compositions of the present invention at a level of from about 0.1% to 15%, preferably from about 1% to 10%, most preferably from about 2% to 8%, by weight of the composition.

Other Components - Other components useful in various detergent compositions may also be included in the compositions of the present invention, including other active ingredients, carriers, solubilizers, antioxidants, processing aids, dyes or pigments, Solvent for liquid formulations, solid filler for block compositions. If high foam is required, a foam booster such as C ₁₀ -C ₁₆ alkanolamide can be added to the composition, generally at a content of 1%-10%. C ₁₀ -C ₁₄ monoethanols and diethanolamides are typical examples of this class of suds boosters. It is also advantageous to use such suds boosters with high sudsing co-surfactants, such as the amine oxides, betaines, sultaines mentioned above.

Antioxidants can optionally be incorporated into the detergent compositions of the present invention. It can be any conventional antioxidant used in detergent compositions, such as 2,6-di-tert-butyl-4-methylphenol (BHT), carbamates, ascorbates, thiosulfates , monoethanolamine (MEA), diethanolamine, triethanolamine, etc. When present, antioxidants are preferably present in the composition at 0.001% to about 5% by weight.

The various detergent ingredients used in the compositions of the present invention can optionally be further stabilized by absorbing the ingredients onto a porous hydrophobic substrate and then coating the substrate with a hydrophobic coating agent. . Preferably the detergent component is mixed with the surfactant prior to adsorption with the porous substrate. During use, the detergent components are released from the substrate into the aqueous wash solution to accomplish their intended detergency.

To illustrate the technique in more detail, a proteolytic enzyme containing porous hydrophobic silica (trademark SIPERNATD10, DeGussa) with a nonionic surfactant containing 3%-5% _C13-15 ethoxylated alcohol (EO7) The solution is mixed. The amount of the enzyme/surfactant solution is typically 2.5 times the weight of silica. The obtained powder is stirred and dispersed in polysiloxane oil (various polysiloxane oils with a viscosity of 500-12500 can be used). The resulting silicone oil dispersion is emulsified or incorporated into the final detergent base. By this method, the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactive agents, dyes, optical brighteners, fabric conditioners and hydrolyzable surfactants can be used in "protected form" in Detergents, including liquid laundry detergent compositions.

Liquid detergent compositions may contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol and isopropanol are suitable. For solubilizing surfactants, monohydric alcohols are preferred, but polyols, such as those containing 2 to about 6 carbon atoms and 2 to about 6 hydroxyl groups (e.g., 1,3-propanediol, ethylene glycol, glycol, glycerol and 1,2-propanediol). The compositions may contain from 5% to 90%, usually from 10% to 50%, of such carriers.

An example of a method for preparing detergent composition granules is as follows: linear alkylbenzene sulfonate, sodium tripolyphosphate, sodium silicate, sodium sulfate, perfume, diamine and water are added with a blender, heated and mixed, and The resulting slurry was spray dried to granulate form.

An example of the method of preparing the liquid detergent composition of the present invention is as follows: citrate and magnesium chloride are added and dissolved in free water, and amine oxide, betaine, ethanol, solubilizer and nonionic surfactant are added to the solution. If free water is not available, magnesium chloride and citrate can be added to the above mixture and stirred until dissolved. In addition, acids are added to neutralize the formulation, preferably organic acids are chosen, such as maleic acid and citric acid, however, inorganic acids can also be used. In a preferred embodiment, these acids are added to the formulation after the addition of the diamine and AExS is added last, in the same way as in formulations without Mg ⁺⁺ .

            Non-aqueous liquid detergent

The preparation of the liquid detergent composition containing non-aqueous carrier can be carried out according to the following documents: US4753570, 4767558, 4772413, 4889652, 4892673, GB-A-2158838, GB-A-2195125, GB-A-2195649, U.S.4988462, U5266233 , 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), listed as references herein. The compositions may contain various particulate detergent ingredients (such as the above-mentioned bleaching agents) stably suspended therein. The non-aqueous composition thus contains a liquid phase and optionally, but preferably a solid phase, which are described in detail hereinafter and in the references cited.

The compositions of the present invention are useful in forming aqueous washing solutions for hand dishwashing, typically by adding an effective amount of the composition to water to form an aqueous washing or soaking solution. The resulting aqueous solution is then brought into contact with dishes, cutlery, cooking utensils.

Add water to form the effective amount detergent composition of aqueous wash solution and can comprise enough to form the quantity of about 500-20000ppm composition in aqueous solution, more preferably detergent composition of the present invention provides about 800-5000ppm in aqueous wash mother liquor Detergent composition.

The following examples serve to illustrate the invention, but not to limit or otherwise define its scope. All used parts, percentages and ratios are expressed as percent by weight unless otherwise indicated.

In the following examples all contents are expressed in % by weight of the composition.

Example I

Prepare the following liquid detergent compositions: A B C pH10% 9 10 10 AS 0 28 25 AES 30 0 0 Amine oxide 5 3 7 betaine 3 0 1 Polyhydroxy fatty acid amides (C14) 0 1.5 0 AE Nonionic Surfactant 2 0 4 diamine 1 5 7 Mg++ (as magnesium chloride) 0.25 0 0 Citric acid (cit2K3) 0.25 0 0 Total (fragrance, dye, water, alcohol, etc.) to 100% D. E. f pH10% 9.3 8.5 11 AES 0 15 10 paraffin sulfonate 20 0 0 linear alkylbenzene sulfonate 5 15 12 Betaine 3 1 0 Polyhydroxy fatty acid amides (C12) 3 0 1 AE Nonionic Surfactant 0 0 20 DTPA 0 0.2 0 Citrate (as cit2K3) 0.7 0 0 diamine 1 5 7 Mg++ (as magnesium chloride) 1 0 0 Ca++ (as CaXS)2) 0 0.5 0 protease 0.01 0 0.05 Amylase 0 0.05 0.05 Solubilizers 2 1.5 3 Total (fragrance, dye, water, alcohol, etc.) to 100%

The degree of ethoxylation in AES is from 0.6 to about 3.

The diamine is selected from dimethylaminopropylamine, 1,6-hexanediamine, 1,3 propanediamine, 2-methyl 1,5-pentanediamine, 1,3-pentanediamine, 1- Methyl-diaminopropane.

Amylases are selected from the group consisting of: Termamyl®, Fungamyl®, Duramyl®, BAN® and the amylases described in WO 95/26397 and Novo Nordisk PCT/DK/96/00056 co-pending applications.

The lipase is selected from: Amano-P, M1 Lipase®, Lipomax®, Lipolase®, D96L lipolytic enzyme variant of the natural lipase produced by the fungus Humicola lanuginosa described in US Serial No. 08/341826 and Humicola sp. Lanuginosa strain DSM 4106.

The protease is selected from the group consisting of Savinase®, Maxatase®, Maxacal®, Maxapem 15®, Bacillus subtilis BPN and BPN', Protease B, Protease A, Protease D, Primase®, Durazym®, Opticlean® and Optimase® and Alcalase®.

The solubilizing agent is selected from sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluenesulfonic acid, naphthalenesulfonic acid, cumenesulfonic acid and xylenesulfonic acid.

DTPA is a diethylenetriaminepentaacetic acid chelating agent.

Example II A B C D. pH10% 8.5 9 9.0 9.0 AE0.6S 0 0 0 0 AE1S 0 30 0 0 AE1.4S 30 0 27 0 AE2.2S 0 0 0 15 Amine oxide 5 5 5 3 betaine 3 3 0 0 AE Nonionic Surfactant 2 2 2 2 diamine 1 2 4 2 Mg++ (as magnesium chloride) 0.25 0.25 0 0 Ca++ (as CaXS)2) 0 0.4 0 0 Total (fragrance, dye, water, alcohol, etc.) to 100% E. f G h I J pH10% 9.3 8.5 11 10 9 9.2 AES 0 0 0 0 27 0 AES 0 15 10 27 0 20 paraffin sulfonate 20 0 0 0 0 0 linear alkylbenzene sulfonate 5 15 12 0 0 0 betaine 3 1 0 2 2 0 Amine oxide 0 0 0 2 5 7 Polyhydroxy fatty acid amides (C12) 3 0 1 2 0 0 AE Nonionic Surfactant 0 0 20 1 0 2 Solubilizers 0 0 0 0 0 5 diamine 1 5 7 4 2 5 Mg++ (as magnesium chloride) 1 0 0 0 0 0 Ca++ (as CaXS)2) 0 0.5 0 0 0.1 0.1 protease 0.1 0 0 0 0.06 0.1 Amylase 0 0.02 0 0.005 0 0.05 Lipase 0 0 0.025 0 0.05 0 DTPA 0 0.3 0 0 0.1 0.1 Citrate (as cit2K3) 0.65 0 0 0.3 0 0 Total (fragrance, dye, water, alcohol, etc.) to 100%

The diamine is selected from dimethylaminopropylamine, 1,6-hexanediamine, 1,3 propanediamine, 2-methyl 1,5-pentanediamine, 1,3-pentanediamine, 1- Methyl-diaminopropane.

Amylases are selected from the group consisting of: Termamyl®, Fungamyl®, Duramyl®, BAN® and the amylases described in WO 95/26397 and Novo Nordisk PCT/DK/96/00056 co-pending applications.

The lipase is selected from: Amano-P, M1 Lipase®, Lipomax®, Lipolase®, D96L lipolytic enzyme variant of the natural lipase produced by the fungus Humicola lanuginosa described in US Serial No. 08/341826 and Humicola sp. Lanuginosa strain DSM 4106.

The protease is selected from the group consisting of Savinase®, Maxatase®, Maxacal®, Maxapem 15®, Bacillus subtilis BPN and BPN', Protease B, Protease A, Protease D, Primase®, Durazym®, Opticlean® and Optimase® and Alcalase®.

The solubilizing agent is selected from sodium, potassium, ammonium or water-soluble substituted ammonium salts of toluenesulfonic acid, naphthalenesulfonic acid, cumenesulfonic acid and xylenesulfonic acid.

DTPA is a diethylenetriaminepentaacetic acid chelating agent.

Claims (10)

1. detergent composition that is applicable to manual dishwashing, it contains:

A) the low-molecular-weight organic diamine of significant quantity with pK1 and pK2, the pK1 and the pK2 of wherein said diamines are 8.0-11.5; With

B) tensio-active agent of washing significant quantity;

Wherein pH (aqueous solution as 10% is measured) is 8.0-12.

2. detergent composition that is applicable to manual dishwashing, it contains:

A) the low-molecular-weight organic diamine of significant quantity with pK1 and pK2, the pK2 of wherein said diamines for greater than 9.2 to 11 and the pK1 of described diamines be 8.0-11.5; With

B) tensio-active agent of washing significant quantity;

Wherein pH (aqueous solution as 10% is measured) is 8.0-12.

3. detergent composition that is applicable to manual dishwashing, it contains:

A) the low-molecular-weight organic diamine with pK1 and pK2 of significant quantity, the pK2 of wherein said diamines are that the pK1 of 8-9.2 and described diamines is 8.0-11.5; With

B) tensio-active agent of washing significant quantity;

Wherein pH (aqueous solution as 10% is measured) is 8.0-12.

4. one of any detergent for washing dishware with hand composition of claim 1-3, wherein said tensio-active agent is selected from anion surfactant, nonionogenic tenside and their mixture.

5. one of any detergent for washing dishware with hand composition of claim 1-4, wherein said diamines is selected from:

R wherein _1-4Be selected from H, methyl, ethyl and oxyethane respectively; C _xAnd C _yBe selected from methylene radical or branched-chain alkyl respectively, wherein x+y is 3-6; Optionally exist with A, be selected to electronics or electron-withdrawing group with the pKa that regulates diamines to required scope; If A exists, and must all be 2 or bigger by x and y.

6. one of any detergent for washing dishware with hand composition of claim 1-5, wherein said diamines is selected from:

Dimethylaminopropyl amine:

1,6-hexane diamines:

1,3 propanediamine: 2-methyl 1,5 pentane diamine-

1, the 3-pentane diamine-

1-methyl-diaminopropanes-

Jeffamine EDR 148-

Isophorone diamine-

1, two (the methylamine)-hexanaphthenes of 3-

With their mixture.

7. one of any detergent for washing dishware with hand composition of claim 1-6, it also contains the enzyme that is selected from proteolytic enzyme, lipase, amylase, cellulase and their mixture.

8. the liquid detergent composition of claim 7, wherein said amylase is α-Dian Fenmei, by the test determination of Phadebas  alpha-amylase activity, have under its pH in 25 ℃-55 ℃ temperature range and at 8-10 than the ratio of Termamyl  high at least 25% ratio alive and live.

9. the liquid detergent composition of claim 8, wherein said α-Dian Fenmei is obtained by close alkali bacillus genus, and it contains the following amino sequence at the N end: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp.

10. the method for a wash dining set, described method comprise that the aqueous solution with one of any detergent composition of the dirty tableware of needs washing and claim 1-9 contacts.