CN1239986A - Detergent composition containing isopeptidase - Google Patents

Abstract

The cleaning composition, preferably a laundry detergent composition, contains an isopeptidase capable of catalytically breaking down the isopeptide bond between glutamine γ-formamide and lysine ε-amino group.

Description

Detergent composition containing isopeptidase

                 

This application claims priority under Section 35, USC 119(e), of Provisional Application Serial No. 60/028496, filed October 15, 1996.

Field of Invention

The present invention relates to cleaning compositions, preferably laundry detergent compositions, comprising isopeptidases. Preferred laundry compositions are in granular form. More particularly, the present invention relates to detergents containing isopeptidases, detersive surfactants and builders (e.g. aluminosilicates, silicates), preferably in combination with detersive enzymes (e.g. proteases, lipases, amylases, cellulases) Combined detergent composition.

Background of the Invention

Most conventional detergent compositions contain a mixture of ingredients, typically including enzymes which have cleaning properties. Detergent enzymes commonly encountered commercially in laundry compositions include: proteases, amylases, cellulases and lipases. Additionally, the literature also contains numerous combinations of other types of enzymes that have been investigated for use in cleaning compositions. However, they rarely go beyond the initial evaluation stage for use in commercial compositions. Obvious technical problems encountered with the use of any enzyme in cleaning compositions include: compatibility with other conventional cleaning components (e.g. surfactants, builders, other enzymes), under typical storage and use pH conditions The stability and validity and usability of these are just a few to name a few.

One class of enzymes that has not previously been investigated for use in cleaning compositions is called isopeptidases. The first such enzyme has recently been identified after the discovery of a new enzymatic activity in the salivary gland secretion of the medicinal leech that cleaves between the γ-formamide of glutamine and the ε-amino group of lysine. After the inter-isopeptide bond [see, e.g., Fradkov et al., Enzyme from Hirudo medicinalis that specifically breaks down the endo-ε-(-γ-Glu-)-Lys isopeptide bond: cDNA clone and protein Primary Structure ("Enzyme from the medicinal leech (Hirudo medicinalis) that specifically splits endo-ε(-γ-Glu-)-Lys isopeptide bonds: cDNA cloning and protem primary structure"), FEBS Letters, 390(1996) 145-148 ]. This enzyme (termed "destabilase") inter alia breaks down the isopeptidase crosslinks in the stabilized fibrin chains, but leaves the polypeptide chains intact, thereby liquefying the stabilized fibrin in vitro. Based on this enzymatic activity, which reverses the last step in blood coagulation, isopeptidases are currently being investigated for possible use as thrombolytic agents.

It has now been determined that such activity is useful in cleaning processes where removal of certain body soils is desired. It includes the laundry process in an attempt to remove normally intractable body soil and stains. One such body soil or stain material sought to be removed is soil fragments that are partially resistant to detergent and protease removal due to chemically stable endo-ε(-γ-Glu-)-Lys isopeptide bonded cross-links, which found In the cornified shell of the stratum corneum (skin) cells, from which some or all of the body soil and stains on washed fabrics are derived. Such stubborn soils and stains, which may consist in part of endo-ε(-γ-Glu-)-Lys cross-linked proteins, are commonly found on the collars and cuffs of clothing and on underwear. Accordingly, it is an object of the present invention to provide cleaning compositions and methods using isopeptidases.

Background technique

Finot.P.-A., Mottu.F., Bujard, E. and Mauron, J. (1978) Adv.Exp.Med.Bio.105, 549-570, which describes the gamma-glutamyl-ε - Hydrolytic activity of lysine in mouse kidney extracts. Baskova, I.P., and Nikonov, G.I. (1985) Biokhimya 50(3), 424-431, which reports the leech destabilase mechanism of liquefied fibrin (hydrolysis of γ-glutamyl-ε-lysine) , including kinetics on the artificial substrate γ-glutamyl-pNA. [See also, Baskova, I.P. and Nikonov, G.I. (1991) Blood Coagulation and Fibrinolysis 2, 167-172, which contains the kinetics of additional substrates. ] Fradkov, A., Berezhnoy, S., Barsova, E., Zavalova, L, Lukyanov, S., Baskova, I. and Sverdlov, E.D. (1996) FEBS Letters 390, 145-148, which describe destabilizing enzymes cloning and sequencing. See also: Baskova, I.P., Nikonov, G.I., "Destabilase, an enzyme in the salivary gland secretion of the medicinal leech, hydrolyzes the isopeptide bonds in stable fibrin" ("Destabilase: An Enzyme in the Salivary GlandSecretion of Medicinal Leech-Hydrolyzes Isopetide Bonds in Stabilized Fibrin"), Biokhimiya, Vol50(3), 1985, pp.424-431; Baskova, I.P., Nikonov, G.I., Zavalova, L.L., and Larionova, "Destabilizing enzymes, a Kinetics of the Hydrolysis of L-γ-Glu-pNA by Destabilase, an Enzyme from the Leech Hirudo medicinalis, Biochimiya, Vol 55( 4), pp674-479 (1990).

Hoshino, E., Maruta, K., Wada, Y. and Kazuo, M. (1995) JAOCS72 (7), 785-791, which describe the observation by electron microscope from Bacillus KSM-K16 (it is said , K16 protease has been isolated and used in laundry detergent) for the interaction of highly purified alkaline protease with human skin keratinocytes contained in skin dirt. It is said that the protease first penetrates into keratinocytes, and then mainly adsorbs on the inner structure of the cells at the initial stage of hydrolysis, and directly hydrolyzes keratin fibers.

Invention Summary

According to the present invention there is provided a cleaning composition (preferably a laundry detergent composition, eg a composition for washing machine washing or pre-soaking) comprising an isopeptidase active amount.

Preferred are laundry detergent compositions comprising:

a) about 0.0001-5% (preferably about 0.001-2%) by weight isopeptidase; and

b) from about 95% to about 99.9999% by weight of detergent composition additive components.

The present invention also relates to laundry detergent compositions comprising:

a) about 0.1-80%, preferably about 1-50%, by weight of a detersive surfactant;

b) about 0.0001-5% (preferably about 0.001-2%) by weight isopeptidase; and

c) from about 0.1 to 99.8% by weight of detergent composition additive components, preferably including from about 0.1 to 80% of builders (eg, aluminosilicates, silicates, phosphates, phosphonates, etc.). Preferred compositions are in granular form.

The present invention also relates to detergent compositions comprising:

a) about 0.0001-2% by weight of active detergent enzymes (preferably selected from proteases, cellulases, lipases, amylases, peroxidases, and mixtures thereof);

b) about 0.0001-5% (preferably about 0.001-2%) by weight isopeptidase; and

c) From about 0.1 to 99.8% by weight of detergent composition additive components (preferably selected from detersive surfactants and/or builders).

Preferably, these detergent compositions comprise one or more detersive surfactants selected from the group consisting of anionic surfactants, preferably selected from alkyl alkoxylated sulphates, alkyl sulphates and/or linear Alkylbenzenesulfonate surfactants; cationic surfactants, preferably selected from quaternary ammonium surfactants; nonionic surfactants, preferably selected from alkyl ethoxylates, alkyl polyglucosides and/or amine oxides Surfactants; amphoteric surfactants, preferably selected from betaines and/or polycarboxylates (eg polyglycinates); and zwitterionic surfactants.

Preferred detergent compositions also include oxygen bleaches selected from perborates, percarbonates, and mixtures thereof, more preferably in combination with bleach activators such as nonanoyloxybenzenesulfonate (NOBS) and tetraacetyl ethylenediamine (TAED) activator combinations, and mixtures thereof. Premade percarboxylic acid bleach can also be used.

Preferred compositions of the present invention relate to granular detergent compositions comprising:

a) about 0.1-50% by weight of bleaching agent;

b) about 1-80% by weight of a builder selected from aluminosilicates, silicates and mixtures thereof;

c) about 0.0001-2% by weight of an active detergent enzyme selected from the group consisting of proteases, amylases, lipases, cellulases, and mixtures thereof;

d) about 0.0001-5% (preferably about 0.001-2%) by weight isopeptidase; and

e) From about 0.1% to about 99.8% by weight of detergent composition additive components.

The invention also relates to a method of laundering fabrics. It involves a machine washing process in which fabrics to be cleaned are contacted in a washing machine with an aqueous solution containing an isopeptidase active amount (and preferably also a detersive surfactant). Another laundering method is a hand laundering method which comprises soaking (preferably at least about 5 minutes, more preferably at least about 15 minutes) the fabric to be cleaned in an aqueous solution containing an isopeptidase active amount.

All percentages, ratios and proportions herein are by weight of the components to prepare the final composition, unless otherwise specified. All documents cited herein are, in relevant part, incorporated herein by reference.

                    Invention Details

The present invention provides detergent compositions by using an isopeptidase as described herein, preferably in combination with one or more bleaches, aluminosilicates, silicates, detersive surfactants and/or The detergent enzyme combination provides effective soil and stain cleaning, preferably in granular form.

Preferred compositions are formulated with one or more detersive surfactants to assist in the cleaning process using isopeptidases. Typical and preferred detersive surfactants are selected from: anionic surfactants, preferably selected from alkyl alkoxylated sulphate, alkyl sulphate and/or linear alkylbenzene sulphonate surfactants; cationic surfactants Active agents, preferably selected from quaternary ammonium surfactants; and nonionic surfactants, preferably alkyl ethoxylates, alkyl polyglucosides and/or amine oxide surfactants.

Percarbonate and perborate, which deliver peroxide bleach into the wash liquor, are the foundational technology for modern ultra-compact granular laundry detergent formulations. Peroxide bleach is very hydrophilic, although it cannot compare to the bleaching action provided by peracids (such as those formed by the interaction of peroxides with TAED), but in pigments (such as in particles or beverage stains) ) is effective in decolorizing and also aids in the removal of color from organic residues associated with body soiling.

The present invention also provides detergent compositions which provide soil and stain protection by use of bleach activators, including preformed peracids, preferably hydrophobic bleach activators, in combination with isopeptidases in the compositions and methods of the present invention. effective cleaning.

The present invention also provides compositions which provide effective cleaning of soils and stains through the use of bleach catalysts in the compositions and methods of the present invention. Bleach catalysts, characterized by the presence of at least one transition metal atom, interact with peroxides to form very effective hydrophilic bleaches. These bleaches provide strong results on pigmented hydrophilic stains and hydrophilic everyday soils (i.e. socks). Catalysts are generally used in cleaning products at very low levels. Products containing isopeptidases and bleaches and catalysts, as disclosed herein, provide excellent cleaning and/or whiteness performance. However, it should be recognized that the use of bleach catalysts has been difficult in the past because of the fabric damage involved (dimanganese catalysts are known to cause fabric damage) and this must be taken into account when formulating compositions of the invention containing bleach catalysts.

The present invention also provides such compositions by using in the compositions of the present invention, preferably in granular form, selected from the group consisting of aluminosilicates, silicates, phosphates, carbonates, and the like. The blend's builders provide effective cleaning of dirt and stains.

Additionally, the present invention provides compositions which provide effective cleaning of soils and stains through the use of additional detergent enzymes in the compositions and methods of the present invention.

Isopeptidase:

An essential component of the cleaning compositions of the present invention is an isopeptidase. The term "isopeptidase" as used herein refers to an enzyme having the ability to catalyze the breakdown of the isopeptide bond between glutamine γ-formamide and lysine ε-amino group. For the purposes of the present invention, the term "active amount of isopeptidase" as used herein refers to the amount of isopeptidase which has the requisite amount of catalytic activity effective to provide a cleaning benefit under normal use conditions. Preferably, the isopeptidase is added to the compositions of the present invention in an amount of about 0.0001-5%, preferably about 0.01-2%.

The catalytic activity of isopeptidases can generally vary, depending on the particular enzyme variant used. The catalytic activity of each isopeptidase can be determined by the method of Baskova, IP and Nikonov, GI (1991), Blood Coagulation and Fibrinolysis 2, 167-172, which is as follows: "According to the method described by Svendsen et al [Svendsen L., Blomback B, Blomback M. et al., Synthetic chromogenic substrate for determination of trypsin, thrombin and thrombin-like enzymes.Thromb Res 1972; 1:267-278], using the chromogenic substrate L-γ-Glu-pNA (Behringwerke, Austria) in Measure the amidolytic activity of test preparation at 405nm place.With (0.9-x)ml 0.05M Tris (trishydroxymethylaminomethane)-HCl buffer solution (pH8.0), 0.2ml substrate solution (0.45mg/ml , 1.58×10 ^-3 M, in 0.05M Tris-HCl buffer solution containing 0.01M CaCl ₂ , pH 8.0) and xml destabilizing enzyme solution are placed in the transparent small container of the spectrophotometer. Use Lineweaver and Kinetic data were determined by the Burk method."

"In a system containing 32nmol isopeptide, 11.9nmol enzyme, 2.5μl of H ₂ O and 80μl of 0.05M boric acid buffer solution, pH 7.4, the destabilizing enzyme effect on isopeptide ε-(γ- Glu)-Lys hydrolysis. The 0.1N HCl of 10 μl and the 0.2M citric acid buffer solution (pH2.2) of 100 μl are divided into the aliquots of 20 μl. Control sample contains saline instead of destabilizing enzyme. Will A sample of 50 μl was placed on an analytical column (400×32mm) of resin Biotronic BTC2710 of Biotronic LC500l for amino acid analysis only, 7-8mmk (400×32mm).” [on page 168]

Using these methods, it is reported (at page 169) that the isopeptidase "destabilase" has the following properties: "specific activity of 0.15 x 10 ^-9 mol/s.mg, K _m = 2.2 x 10 ^-4 M , k _kat =3.53×10 ^-3 s ^-1 (pH9.0, 37°C)."

The isopeptidases herein include naturally derived isopeptidases such as "destabilases" whose amino acid sequences are obtained from literature [Fradkov et al. "Enzyme from the medicinal leech (Hirudomedicalis) that specifically splits endo-ε-(γ-Glu)- Lys isopeptidebonds: cDNA cloning and protein primary structure", FEBS Letters, 390 (1996) 145-148; See SEQ ID Nos.2 and 7] are known, and can provide the purpose of the cleaning composition and method of the present invention Any variation of the amount of isopeptidase activity (eg SEQ ID Nos. 4 and 6). Such variants may be naturally occurring or genetically engineered. Preferred variants show positive immunological cross-reactivity with antibodies to naturally occurring isopeptidases.

Since the isopeptidase to be used in the compositions and methods of the invention should be as cheap as possible, the enzyme must be economically produced in large quantities and its expression is therefore preferably engineered in a transgenic expression system. These systems are known in the art of protein expression and may include, but are not limited to: expression in the following systems: Gram-negative bacteria such as E. pastoris, molds such as Aspergillus, mammalian or insect cell cultures, or crops such as tobacco, corn, soybeans or other plants whose genes can be altered to express and accumulate proteins. The cDNA nucleotides have been isolated and sequenced for the destabilase and its two variants (SEQ ID Nos 1, 3 and 5).

Any such variations may be specifically designed for optimum performance efficacy in the detergent compositions and methods of the present invention. For example, variants can be designed such that the enzyme has increased compatibility with commonly encountered cleaning composition components. Variants can also be designed such that the optimum pH, bleach stability, catalytic activity etc. of the enzyme is suitable for granular detergent applications.

additional detergent ingredients

The detergent compositions of the present invention may also contain additional detergent ingredients. The exact nature of these additional ingredients and the levels at which they are added will depend upon the physical form of the composition and the exact nature of the laundering operation with which the composition is to be used.

The compositions of the present invention preferably contain one or more additional detergent ingredients selected from the group consisting of: surfactants, bleaches, other enzymes, builders, alkaline systems, organic polymers, suds suppressors, soil Suspending and anti-redeposition agent, and corrosion inhibitor.

Detergent Surfactants:

The detergent compositions of the present invention preferably further comprise a surfactant, also referred to herein as a co-surfactant, which is preferably selected from the group consisting of: anionic surfactants, preferably selected from alkyl alkoxylated sulfates, alkyl Sulfate and/or linear alkylbenzene sulfonate surfactants; cationic surfactants, preferably selected from quaternary ammonium surfactants; nonionic surfactants, preferably alkyl ethoxylates, alkyl polyglucosides and/or amine oxide surfactants; amphoteric surfactants, preferably selected from betaines and/or polycarboxylates (eg polyglycinate); and zwitterionic surfactants. A wide variety of co-surfactants can be used in the detergent compositions of the present invention. A list and class of anionic, nonionic, amphoteric and zwitterionic classes of these co-surfactants is given in US Pat. No. 3,664,961, Norris, issued May 23,1972. Amphoteric surfactants are also described in detail in "Amphoteric Surfactants (Second Edition)" edited by E.G. Lomax, published by Marcel Dekker, Inc., 1996.

The laundry detergent compositions of the present invention will generally contain from about 0.1% to about 35%, preferably from about 0.5% to about 15%, by weight, of a co-surfactant. The selected surfactants are further described below:

(1) Anionic co-surfactant:

Non-limiting examples of anionic co-surfactants useful herein, typically at levels from about 0.1 to 50% by weight, include conventional C ₁₁ -C ₁₈ alkylbenzene sulfonates ("LAS") and primary, branched chain and random C ₁₀ -C ₂₀ alkyl sulfates (“AS”) of the formula CH ₃ (CH ₂ ) _x (CHOSO ₃ ^- M ⁺ )CH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ ^- M ⁺ ) C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfates of CH ₂ CH ₃ , wherein x and (y+1) are integers of at least about 7, preferably at least about 9, and M is a water-soluble cation, especially are sodium, unsaturated sulfates such as oleyl sulfate, C ₁₀ -C ₁₈ α-sulfonated fatty acid esters, C ₁₀ -C ₁₈ alkyl polyglucosides, C ₁₀ -C ₁₈ alkyl alkoxy sulfates (" AE _x S", especially EO1-7 ethoxysulfate), C ₁₀ -C ₁₈ alkyl alkoxy carboxylates (especially EO1-5 ethoxy carboxylates). _C12 - _C18 betaines and sultaines ("sultaines"), _C10 - _C18 amine oxides and the like may also be included in the overall composition. Conventional _C10 - _C20 soaps may also be used. If high sudsing is desired, branched _C10 - _C16 soaps can be used. Other conventionally useful anionic co-surfactants are listed in standard textbooks.

Alkyl alkoxylated sulfate surfactants useful herein are preferably 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 has C ₁₀ -C ₂₄ alkyl moiety of hydroxyalkyl, preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₅ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than 0, generally about 0.5-6, more preferably about 0.5-3, and M is H or a cation, which can be, for example, a metal cation (such as sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include: ethanol, triethanol, methyl, dimethyl, trimethylammonium cations and quaternary ammonium cations tetramethylammonium and dimethylpiperidinium cations and from alkylamines such as ethylamine, Diethylamine, triethylamine, those cations derived from mixtures thereof, and the like. Illustrative surfactants are: C ₁₂ -C ₁₅ alkyl polyethoxylate (1.0) sulfate (C ₁₂ -C ₁₅ E(1.0)M), C ₁₂ -C ₁₅ alkyl polyethoxylate (2.25) Sulfate (C ₁₂ -C ₁₅ E(2.25)M), C ₁₂ -C ₁₅ Alkyl Polyethoxylate (3.0) Sulfate (C ₁₂ -C ₁₅ E(3.0)M) and C ₁₂ -C ₁₅ alkyl polyethoxylate (4.0) sulfate (C ₁₂ -C ₁₅ E(4.0)M), wherein M is conveniently selected from sodium and potassium.

Alkyl sulfate surfactants useful herein are preferably water-soluble salts or acids of the formula ROSO ₃ M, wherein R is preferably a C ₁₀ -C ₂₄ hydrocarbyl, preferably an alkyl or hydroxyl group having a C ₁₀ -C ₁₈ alkyl moiety Alkyl, more preferably C ₁₂ -C ₁₅ alkyl or hydroxyalkyl, and M is H or a cation, such as an alkali metal cation (such as sodium, potassium, lithium), or ammonium or substituted ammonium (such as methyl, dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, etc.).

Other suitable anionic surfactants that can be used are alkyl ester sulfonate surfactants including sulfonation with gaseous SO according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. _323-329 Linear esters of C ₈ -C ₂₀ carboxylic acids (ie fatty acids). Suitable materials include natural fatty materials derived from tallow, palm oil, 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 a C ₈ -C ₂₀ hydrocarbon group, preferably an alkyl group, or a mixture thereof, R ⁴ is a C ₁ -C ₆ hydrocarbon group, preferably an alkyl group, or mixtures thereof, and M is a cation that forms a water-soluble salt with an alkyl ester sulfonate. Suitable salt-forming cations include metal cations such as sodium, potassium and lithium and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. Preferably, R ³ is C ₁₀ -C ₁₆ alkyl, and R ⁴ is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates, wherein R ⁵ is C ₁₀ -C ₁₆ alkyl.

Other anionic co-surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. They may include: salts of soaps (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di-, and triethanolamine salts), _C8 - _C22 primary or secondary alkane sulfonates, _C8 - _C24 alkenes Sulfonates, sulfonated polycarboxylic acids prepared by sulfonation of alkaline earth metal citrate pyrolysis products (as described, for example, in British Patent No. 1082179), C ₈ -C ₂₄ alkyl polyethylene glycols Ether sulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oil based glycerol sulfates, alkylphenol oxirane ether sulfates, paraffins Sulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinic acid (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and diesters of sulfosuccinic acid (especially saturated and unsaturated C ₆ -C ₁₂ diesters), sulfates of alkyl polysaccharides such as alkylpolyglucose Sulfates and alkyl polyethoxy carboxylates of glycosides (nonionic, non-sulfated compounds described below ₎ such as those of 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 cation that forms a soluble salt. 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. Other 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 disclosed in US Patent 3,929,678 (Laughlin et al., issued December 30, 1975) at column 23, line 58 to column 29, line 23 (which is incorporated herein by reference).

Preferred disulfates have the formula:

wherein R is _alkyl , substituted alkyl, _{alkenyl , aryl ,} alkaryl, ether _, ester, Amine or amide groups, or hydrogen; A and B are each independently selected from alkyl, substituted alkyl and chain lengths of C ₁ -C ₂₈ , preferably C ₁ -C ₅ , most preferably C ₁ or C ₂ alkenyl, or a covalent bond, and A and B together contain at least 2 atoms; A, B and R together contain 4 to about 31 carbon atoms; X and Y are anionic groups selected from sulfate and sulfonate, Provided that at least one of X or Y is sulfate; M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali metal or alkaline earth metal ion.

The most preferred disulfate surfactants have the above formula, wherein R is an alkyl chain length of C ₁₀ -C ₁₈ , A and B are each independently C ₁ or C ₂ , X and Y are both sulfate groups, M is a potassium, ammonium or sodium ion.

The disulfate surfactants are generally present at a level of about 0.1-50%, preferably about 0.1-35%, most preferably about 0.5-15%, by weight of the detergent compositions.

Preferred disulfate surfactants herein include:

(a) 1,3 disulfate compounds, preferably 1,3 C7-C23 (i.e. the total number of carbons in the molecule) linear or branched chain alkyl or alkenyl disulfates, more preferably have the following formula:

wherein R is a linear or branched alkyl or alkenyl group with a chain length of about _C4 - _C18 ;

(b) 1,4 disulfate compounds, preferably 1,4 C8-C22 linear or branched chain alkyl or alkenyl disulfates, more preferably having the following formula:

wherein R is a linear or branched chain alkyl or alkenyl group with a chain length of about C ₄ -C ₁₈ ; preferred R is selected from the group consisting of: octyl, nonyl, decyl, dodecyl, tetradecyl, Cetyl, octadecyl, and mixtures thereof; and

(c) 1,5 disulfate compounds, preferably 1,5 C9-C23 linear or branched chain alkyl or alkenyl disulfates, more preferably having the following formula:

wherein R is a straight or branched chain alkyl or alkenyl group with a chain length of about C ₄ -C ₁₈ .

Known syntheses of certain disulfate surfactants generally use alkyl or alkenyl succinic anhydrides as the primary starting material. It initially undergoes a reduction step from which diols are obtained. Next, the diol is subjected to a sulfation step to obtain a disulfated product. As an example, US-A-3634269 describes 2-alkyl or alkenyl-1,4-butanediol disulfates prepared by reducing alkenyl succinic anhydride with lithium aluminum hydride to prepare chain alkenyl or alkyl diol, and then sulfate the diol. In addition, US-A-3959334 and US-A-4000081 describe 2-hydrocarbyl-1,4-butanediol disulfate, which also uses lithium aluminum hydride to reduce alkenyl succinic anhydride to prepare alkenyl or Alkyl glycols are then prepared by sulphating them.

See also US-A-3832408 and US-A-3860625, which describe 2-alkyl or alkenyl-1,4-butanediol ethoxylate disulfate, which is the reduction of alkenes with lithium aluminum hydride Alkenyl or alkyl diols prepared from succinic anhydrides, which are then ethoxylated prior to sulfation.

These compounds may also be prepared by a process comprising the synthesis of disulfate surfactants from substituted cyclic anhydrides having one or more carbon chain substituents totaling at least 5 carbon atoms, including the following step:

(i) reducing said substituted cyclic anhydride to form a diol; and

(ii) sulfating the diol to form a disulfate

The reduction step described therein comprises a pressurized hydrogenation step in the presence of a transition metal-containing hydrogenation catalyst.

When included, the laundry detergent compositions of the present invention generally contain from about 0.1% to about 50%, preferably from about 1% to about 40%, by weight, of anionic surfactants.

(2) Nonionic co-surfactant:

Non-limiting examples of nonionic co-surfactants useful herein in amounts generally from about 0.1 to 50% by weight include: alkoxylated alcohols (AE) and alkylphenols, polyhydroxy fatty acid amides (PFAA) , Alkyl Polyglucoside (APG), C ₁₀ -C ₁₈ Glyceryl Ether, etc.

More specifically, condensates of primary and secondary aliphatic alcohols with about 1 to 25 moles of ethylene oxide (AE) are suitable for use as nonionic surfactants in the present invention. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally contains from about 8 to 22 carbon atoms. Preferred are alcohols having an alkyl group of about 8-20 carbon atoms, more preferably about 10-18 carbon atoms, and about 1-10 moles, preferably 2-7 moles, most preferably 2-5 moles of epoxy per mole of alcohol Condensation product of ethane. Particularly preferred nonionic surfactants of this type are _C9 - _C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, especially 5-10 moles of ethylene oxide per mole of alcohol C ₁₂ -C ₁₅ primary alcohols.

Examples of commercially available nonionic surfactants of this type include: Tergitol ^™ 15-S-9 (condensation product of _C11 - _C15 linear alcohols with 9 moles of ethylene oxide) sold by UnionCarbide Corporation and Tergitol ^™ 24-L-6 NMW (the condensation product of narrow molecular weight distribution C ₁₂ -C ₁₄ primary alcohols with 6 moles of ethylene oxide); and Neodol ^™ 45-9 (C ₁₄ -C ₁₅ Condensation product of linear alcohol with 9 moles of ethylene oxide), Neodol ^TM 23-3 (condensation product of C ₁₂ -C ₁₃ linear alcohol with 3.0 moles of ethylene oxide), Neodol ^TM 45-7 (C ₁₄ - Condensation product of C ₁₅ linear alcohol with 7 moles of ethylene oxide), Neodol ^™ 45-5 (condensation product of C ₁₄ -C ₁₅ linear alcohol with 5 moles of ethylene oxide); Kyro ^™ sold by Procter & Gamble Company EOB (condensation product of a C ₁₃ -C ₁₅ alcohol with 9 moles of ethylene oxide); and Genapol LA030 or 050 (condensation product of a C ₁₂ -C ₁₄ alcohol with 3 or 5 moles of ethylene oxide) sold by Hoechst. The preferred range of HLB for these AE nonionic surfactants is 8-17, most preferably 8-14. Condensates with propylene oxide and butylene oxide can also be used.

Another preferred class of nonionic co-surfactants for use herein are the polyhydroxy fatty acid amide surfactants of the formula:

wherein R ¹ is H, or R ¹ is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² is C _5-31 hydrocarbyl, and Z has a straight hydrocarbyl chain, at least The 3 hydroxyl groups are directly attached to the chain of a polyhydroxyl hydrocarbon group, or an alkoxylated derivative thereof. Preferably, ^R1 is methyl, ^R2 is a straight chain _C11-15 alkyl or _C15-17 alkyl or alkenyl chain, such as coconut alkyl or mixtures thereof, and Z is in a reductive amination reaction Derived from reducing sugars such as glucose, fructose, maltose, lactose. General examples include C ₁₂ -C ₁₈ and C ₁₂ -C ₁₄ N-methyl glucamides. See US5194639 and US5298636. N-Alkoxy polyhydroxy fatty acid amides may also be used; see US5489393.

Also useful as nonionic co-surfactants of the present invention are alkyl polysaccharides, such as those disclosed in US4565647 (Llenado, issued January 21, 1986), which polysaccharides have a concentration of about 6-30, preferably about Hydrophobic groups of 10-16 carbon atoms and hydrophilic groups of polysaccharides such as polyglycosides containing about 1.3-10, preferably about 1.3-3, most preferably about 1.3-2.7 saccharide units. Any reducing sugar containing 5 or 6 carbon atoms can be used, for example, glucose, galactose, and galactosyl moieties can be used in place of the glucosyl moiety (optionally, the hydrophobic group to give glucose or galactose corresponding to glucoside or galactoside). The intersaccharide linkage can be, for example, between a position of the additional sugar unit and the 2-, 3-, 4-, and/or 6-position of the aforementioned sugar unit.

Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O) _t (glycosyl) _x

Wherein ^R is selected from: alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl contains about 10-18, preferably about 12-14 carbon atoms; n is 2 or 3, preferably 2; t is 0-10, preferably 0; x is about 1.3-10, preferably about 1.3-3, most preferably about 1.3-2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkyl polyethoxy alcohol is formed and then reacted with glucose, or a source of glucose, to form the glucoside (attached at the 1-position). Further glycosyl units are then attached between its 1-position and the 2-, 3-, 4-, and/or 6-position, preferably mainly the 2-position, of the aforementioned glycosyl units. Such compounds and their use in detergents are disclosed in EP-B-0070077, 0075996 and 0094118.

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

Condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as additional nonionic surfactants in the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of about 1500-1800 and exhibits water insolubility. The addition of polyoxyethylene moieties to the hydrophobic moiety increases the water solubility of the entire molecule and maintains the liquid nature of the product up to a polyoxyethylene content of about 50% by weight of the condensation product, which corresponds to a maximum of about 40 Moles of ethylene oxide condense. Examples of such compounds include certain of the commercially available Pluronic ^™ surfactants sold by BASF.

Nonionic surfactants also suitable for use in the nonionic surfactant system of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide and generally has a molecular weight of about 2500-3000. The hydrophobic moiety is condensed with ethylene oxide to such an extent that the condensation product contains about 40-80% by weight polyoxyethylene and has a molecular weight of about 5,000-11,000. Examples of such nonionic surfactants include certain of the commercially available Tetronic( ^TM) compounds sold by BASF.

Also preferred nonionic surfactants are amine oxide surfactants. The compositions of the present invention may include amine oxides of the general formula I below:

R ¹ (EO) _x (PO) _y (BO) _z N(O)(CH ₂ R') ₂ qH ₂ O (I)

It can generally be seen that the formula (I) provides one long chain moiety R ¹ (EO) _x (PO) _y (BO) _z and two short chain moieties CH ₂ R'. R' is preferably selected from hydrogen, methyl and _-CH2OH . Usually R ¹ is a primary or branched hydrocarbon group, which may be saturated or unsaturated, preferably R ¹ is a primary alkyl group. When x+y+z=0, R ¹ is a hydrocarbyl group having a chain length of about 8-18. When x+y+z is not equal to 0, R ¹ can be slightly longer, with a chain length of C ₁₂ -C ₂₄ . The general formula may also include amine oxides in which x+y+z=0, ^R1 = _C8 - _C18 , R'=H and q=0-2, preferably 2. These amine oxides are illustrated as follows: C _12-14 alkyl dimethyl amine oxide, hexadecyl dimethyl amine oxide, stearyl amine oxide and their hydrates, especially the dihydrate, as described in US5075501 and US5071594 as disclosed in , both of which are incorporated herein by reference.

The present invention also includes such amine oxides, wherein x+y+z is not equal to 0, especially x+y+z is equal to about 1-10, R ¹ is a primary alkyl group containing 8 to about 24 carbon atoms, preferably about 12-16 carbon atoms; In these embodiments, y+z is preferably 0, x is preferably about 1-6, more preferably about 2-4; EO represents ethyleneoxy; PO represents propyleneoxy; BO represents butenyloxy. Such amine oxides can be prepared by conventional synthetic methods, for example by reaction of an alkyl ethoxy sulfate with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.

The highly preferred amine oxides herein are solutions at room temperature. Amine oxides suitable for use herein are manufactured commercially by a number of manufacturers including Akzo Chemie, Ethyl Corp. and Procter & Gamble. For other amine oxide manufacturers see McCutcheon's compilation and Kirk-Othmer's review article.

Although R' is H in certain preferred embodiments, there is some tolerance for R' being slightly longer than H. Specifically, the invention also includes embodiments wherein R' is CH ₂ OH, such as cetyl bis(2-hydroxyethyl)amine oxide, tallow bis(2-hydroxyethyl)amine oxide, stearyl Bis(2-hydroxyethyl)amine oxide and oleyl bis(2-hydroxyethyl)amine oxide, dodecyldimethylamine oxide dihydrate.

(3) Cationic surfactants:

Non-limiting examples of cationic co-surfactants, generally in amounts of about 0.1-50% by weight, include: choline ester quaternary ammonium and alkoxylated quaternary ammonium (AQA) surfactant compounds, and the like.

Cationic co-surfactants useful as surfactant system components are choline ester-type quaternary ammonium surfactants which preferably have surfactant properties and include at least one ester (i.e. -COO-) linkage and at least one cationic charge Group of water-dispersible compounds. For example, suitable cationic ester surfactants, including choline ester surfactants, have been disclosed in US4228024, US4239660 and US4260529.

Preferred cationic ester surfactants are those compounds having the formula:

wherein R ₁ is a C ₅ -C ₃₁ linear or branched alkyl, alkenyl or alkaryl chain or M ^- N ⁺ (R ₆ R ₇ R ₈ )(CH ₂ )s; X and Y are independently is selected from COO, OCO, O, CO, OCOO, CONH, NHCO, OCONH and NHCOO, wherein at least one of X or Y is a COO, OCO, OCOO, OCONH or NHCOO group; R ₂ , R ₃ , R ₄ , R ₆ , R ₇ and R ₈ are each independently selected from alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl and alkaryl groups having 1-4 carbon atoms; and R ₅ is independently H or C ₁ -C ₃ alkyl; wherein the values of m, n, s and t are each independently in the range of 0-8, the values of b are in the range of 0-20, and the values of a, u and v are each independently 0 or 1, with the proviso that at least one of u or v must be 1; M is a counter anion.

R ₂ , R ₃ and R ₄ are preferably each independently selected from CH ₃ and —CH ₂ CH ₂ OH.

M is preferably selected from halide, methylsulfate, sulfate and nitrate, more preferably methylsulfate, chloride, bromide or iodide.

Preferred water-dispersible cationic ester surfactants are choline esters having the formula:

Wherein R ₁ is a C ₁₁ -C ₁₉ straight or branched alkyl chain.

Particularly preferred such choline esters include: stearyl choline ester quaternary methyl ammonium halide (R ¹ =C ₁₇ alkyl), palmitoyl choline ester quaternary methyl ammonium halide (R ¹ =C ₁₅ alkyl), meat Myristoylcholine ester quaternary methyl ammonium halide (R ¹ =C ₁₃ alkyl), lauroyl choline ester quaternary methyl ammonium halide (R ¹ =C ₁₁ alkyl), cocoyl choline ester quaternary methyl ammonium halide (R ¹ =C ₁₁ -C ₁₃ alkyl), tallowylcholine ester quaternary methyl ammonium halide (R ¹ =C ₁₅ -C ₁₇ alkyl), and any mixtures thereof.

The particularly preferred choline esters given above can be prepared by direct esterification of fatty acids of the desired chain length with dimethylaminoethanol in the presence of an acid catalyst. The reaction product is then ethoxylated with a methyl halide, preferably in a solvent such as ethanol, propylene glycol or preferably a fatty alcohol ethoxylate such as a C ₁₀ -C ₁₈ fatty alcohol with a degree of ethoxylation of 3-50 ethoxy groups per mole. Quaternization in the presence of compounds to form the desired cationic material. They can also be prepared by direct esterification of fatty acids of the desired chain length with 2-haloethanols in the presence of an acid catalyst material. The reaction product is then quaternized with trimethylamine to form the desired cationic material.

Other suitable cationic ester surfactants have the following structural formula, where d can be 0-20:

In preferred aspects, these cationic ester surfactants are hydrolyzable under laundry washing process conditions.

Cationic co-surfactants useful herein include alkoxylated quaternary ammonium (AQA) surfactant compounds (hereinafter "AQA compounds") having the formula:

Wherein R ¹ is an alkyl or alkenyl group containing about 8-18 carbon atoms, preferably 10-about 16 carbon atoms, most preferably about 10-14 carbon atoms; R ² is an alkyl or alkenyl group containing 1-3 carbon atoms Alkyl, preferably methyl; ^R3 and ^R4 can each vary independently and are selected from hydrogen (preferred), methyl and ethyl; ^X- is an anion sufficient to provide electrical neutrality, such as chloride, bromide, Methyl Sulfate, Sulphate or Similar. A and A' can each vary independently and are selected from C ₁ -C ₄ alkoxy, especially ethoxy (ie -CH ₂ CH ₂ O-), propoxy, butoxy and mixed ethoxy, respectively. p is 1 to about 30, preferably 1 to about 4; q is 1 to about 30, preferably 1 to about 4, most preferably - about 4; preferably both p and q are 1. See also: EP 2084, Procter & Gamble Company, published May 30, 1979, which describes cationic co-surfactants of the type useful herein.

AQA compounds wherein the hydrocarbyl substituent R ¹ is C ₈ -C ₁₁ , especially C ₁₀ , enhance the dissolution rate of laundry particles compared to higher chain length materials, especially under cold water conditions. Therefore, certain formulators may prefer C ₈ -C ₁₁ AQA surfactants. The AQA surfactants used in the preparation of finished laundry detergent compositions can range from about 0.1% to about 5% by weight, typically from about 0.45% to about 2.5% by weight.

In light of the foregoing, the following are non-limiting, specific descriptions of the AQA surfactants used herein. It should be understood that the degrees of alkoxylation of the AQA surfactants described herein are average values according to common practice for conventional ethoxylated nonionic surfactants. Therefore, non-integer total EO values such as "EO2.5", "EO3.5", etc. are normal. Symbol R ¹ R ² ApR ³ A′qR ⁴ AQA-1 C ₁₂ -C ₁₄ CH ₃ EO EO (also known as coconut methyl EO2) AQA-2 C ₁₂ -C ₁₆ CH ₃ (EO) ₂ EOAQA-3 C ₁₂ -C ₁₄ CH ₃ (EO) ₂ (EO) ₂ (coconut methyl EO4) AQA-4 C ₁₂ CH ₃ EO EOAQA-5 C ₁₂ -C ₁₄ CH ₃ (EO) ₂ (EO) ₃ AQA-6 C ₁₂ -C ₁₄ CH ₃ (EO) ₂ (EO) ₃ AQA-7 C ₈ -C ₁₈ CH ₃ (EO) ₃ (EO) ₂ AQA-8 C ₁₂ -C ₁₄ CH ₃ (EO) ₄ (EO) ₄ AQA-9 C ₁₂ -C ₁₄ C ₂ H ₅ (EO) ₃ (EO) ₃ AQA-10 C ₁₂ -C ₁₈ C ₃ H ₇ (EO) ₃ (EO) ₄ AQA-11 C ₁₂ -C ₁₈ CH ₃ (Propoxy) (EO) ₃ AQA-12 C ₁₀ -C ₁₈ C ₂ H ₅ (Isopropoxy) ₂ (EO) ₃ AQA-13 C ₁₀ -C ₁₈ CH ₃ (EO/PO) ₂ (EO ) ₃ AQA-14 C ₈ -C ₁₈ CH ₃ (EO) ₁₅ ^* (EO) ₁₅ ^* AQA-15 C ₁₀ CH ₃ EO EOAQA-16 C ₈ -C ₁₂ CH ₃ EO EOAQA-17 C ₉ -C ₁₁ CH ₃ -EO 3.5 Avg -AQA-18 C ₁₂ CH ₃ -EO 3.5 Avg -AQA-19 C ₈ -C ₁₄ CH ₃ (EO) ₁₀ (EO) ₁₀ AQA-20 C ₁₀ C ₂ H ₅ (EO) ₂ (EO) ₃ AQA-21 C ₁₂ -C ₁₄ C ₂ H ₅ (EO) ₅ (EO) ₃ AQA-22 C ₁₂ -C ₁₈ C ₃ H ₇ Bu (EO) ₂

* Ethoxy, optionally terminated with methyl or ethyl.

Preferred diethoxylated cationic surfactants herein are commercially available from Akzo Nobel Chemicals Company under the tradename ETHOQUAD.

Highly preferred bis-AQA compounds for use herein have the formula:

wherein R ¹ is C ₁₀ -C ₁₈ hydrocarbyl and mixtures thereof, preferably C ₁₀ , C ₁₂ , C ₁₄ alkyl and mixtures thereof, X is any suitable anion providing electrical balance, preferably chloride. Referring to the general AQA formula above, since in preferred compounds ^R1 is derived from coconut ( _C12 - _C14 alkyl) fraction fatty acids, ^R2 is methyl and ^ApR3 and ^A'qR4 are monoethoxy group, so this preferred type of compound is referred to herein as "coconut methyl EO2" or "AQA-1" in the table above.

Other preferred AQA compounds herein include compounds of the formula:

wherein ^R is C ₁₀ -C ₁₈ hydrocarbon group, preferably C ₁₀ -C ₁₄ alkyl, independently, p is 1 to about 3, q is 1 to about 3, R is C ₁ -C ₃ alkyl, preferably methyl , X is an anion, especially chloride.

Other compounds of the aforementioned type include those in which ethoxy (CH ₂ CH ₂ O) units (EO) are replaced by butoxy (Bu), isopropoxy [CH(CH ₃ )CH ₂ O] and [CH ₂ CH(CH ₃ O)] units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units instead.

Other additive components that may be used in the compositions of the present invention are described below, but are not intended to be limited to these components. While combinations of isopeptidases with these additive composition components can be provided as finished products in the form of liquids, gels, bars or the like using conventional techniques, the manufacture of the granular laundry detergents herein requires some special processing techniques in order to achieve the best performance. Therefore, for the convenience of formulators, the manufacture of laundry granules is separately described in the Particle Manufacture section (see below) in the next subsection.

Bleaching Compounds - Bleaching Agents and Bleach Activators - The detergent compositions herein preferably also contain a bleaching agent or a bleaching composition comprising a bleaching agent or one or more bleach activators. Amounts of bleaching agents will generally be about 1-30%, more typically about 5-20%, of detergent compositions, especially for fabric laundering. If present, the amount of bleach activator will generally be from about 0.1% to 60%, more typically from about 0.5% to 40%, of the bleaching composition comprising bleach plus bleach activator.

The bleaching agent useful herein can be any bleaching agent useful in detergent compositions for fabric laundering, hard surface cleaning, or other laundering purposes now known or to be known. These include oxygen bleaches as well as other bleaches. Perborate bleaches such as sodium perborate (eg, monohydrate or tetrahydrate) may be used herein.

Another class of bleaching agents which may be used without limitation includes percarboxylate bleaches and salts thereof. Suitable examples of such agents include magnesium monoperoxyphthalate hexahydrate, m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Magnesium salt. Such bleaches are disclosed in US4483781 (Hartman, issued November 20, 1984), US Patent Application 740446 (Burns et al., filed June 3, 1985), EP0133354 (Banks et al., published February 20, 1985) ) and US4412934 (Chung et al., issued Nov. 1, 1983). Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in US 4,634,551 (Burns et al., issued January 6, 1987).

Peroxygen bleach can also be used. Suitable peroxygen bleach compounds include: sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleaches (eg, OXONE, manufactured by DuPont Industries) can also be used herein.

Preferred percarbonate bleaches include dry particles having an average particle size of about 500-1000 microns, with no more than about 10% by weight of said particles smaller than about 200 microns and no more than about 10% by weight of The particles are larger than about 1250 microns. Optionally, the percarbonate can be coated with silicates, borates or water soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

A mixture of bleaches can also be used.

Peroxygen bleaches, perborates, percarbonates, etc. are preferably combined with a bleach activator which results in the in situ generation of the peroxyacid corresponding to the bleach activator in the aqueous solution (ie during the wash). Various non-limiting examples of activators are disclosed in US4915854 (Mao et al., issued April 10, 1990) and US4412934. Nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical, mixtures thereof may also be used. See US4634551 for other general bleaches and activators useful herein.

Highly preferred amido-derived bleach activators are those of the formula:

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

Wherein R ¹ is an alkyl group containing about 6-12 carbon atoms, R ² is an alkylene group containing 1-6 carbon atoms, R ⁵ is hydrogen or an alkyl group or aryl group containing about 1-10 carbon atoms , or alkaryl, L is any suitable leaving group. A leaving group is any group which is displaced from the bleach activator due to the nucleophilic attack of the bleach activator by the perhydrolysis anion. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators of the above formula include: (6-octanoylaminocaproyl)oxybenzenesulfonate, (6-nonanoylaminocaproyl)oxybenzenesulfonic acid as described in US4634551 incorporated herein by reference salt, (6-decanoylaminocaproyl)oxybenzenesulfonate and mixtures thereof.

Another class of bleach activators includes the benzoxazine-type activators disclosed by Hodge et al. in US 4,966,723, issued October 30, 1990, which is incorporated herein by reference. Highly preferred benzoxazine-type activators are:

A further class of preferred bleach activators includes acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formula:

wherein R is H or an ^alkyl , aryl, alkoxyaryl or alkaryl group containing 1 to about 12 carbon atoms. Highly preferred lactam activators include: benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecylenoyl caprolactam, benzoyl valerolactam Lactam, octanoyl valerolactam, decanoyl valerolactam, undecylenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also US Patent 4,545,784 (Sanderson, issued October 8, 1985), which is incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam adsorbed on sodium perborate.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be used herein. One class of non-oxygen bleaches of particular interest includes photoactivated bleaches such as sulfonated zinc and/or aluminum phthalocyanines. See US4033718, issued Jul. 5, 1977 to Holcombe et al. Detergent compositions, if used, will generally contain from about 0.025% to about 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanines.

The bleaching compounds can, if desired, be catalyzed with manganese compounds. Such compounds are known in the art and include, for example, the manganese-based catalysts disclosed in US Patent Nos. 5,246,621; 5,244,594; 5,194,416; 5,114,606; Preferable examples of these catalysts include: Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ -(PF ₆ ) ₂ , Mn ^III ₂ ( uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ -(ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1 , 4,7-triazacyclononane) ₄ -(ClO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4, 7-triazacyclononane) ₂ -(ClO ₄ ) ₃ , Mn ^IV (1,4,7,-trimethyl-1,4,7-triazacyclononane)-(OCH ₃ ) ₃ (PF ₆ ), and mixtures thereof. Other metal based bleach activators include those disclosed in US Patent Nos. 4,430,243 and 5,114,611. The use of manganese with various bleach-enhancing complex ligands is reported in the following US Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117;

As a matter of fact, and not by way of limitation, the compositions and methods herein can be adjusted to provide at least about 10 parts per million active bleach catalyst species in the wash aqueous solution, preferably from about 0.1 ppm to about 700 ppm in the wash liquor. , more preferably about 1-50 ppm catalyst species.

Cobalt bleach catalysts useful herein are known and described, for example, in ML Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg Mech., (1983), 2, pp. 1-94. The most preferred cobalt catalyst useful herein is cobalt pentaamine acetate having the formula [Co( _NH3 ) _5OAc ] _Ty , where "OAc" denotes the acetate moiety and "Ty" is the anion, especially cobalt pentaamine Amine acetate chloride, [Co(NH ₃ ) ₅ OAc]Cl ₂ ; and [Co(NH ₃ ) ₅ OAc](OAc) ₂ ; [Co(NH ₃ ) ₅ OAc](PF ₆ ) ₂ ; [ [Co(NH ₃ ) ₅ OAc](SO ₄ ); [Co(NH ₃ ) ₅ OAc](BF ₄ ) ₂ ; and [Co(NH ₃ ) ₅ OAc](NO ₃ ) ₂ (“PAC” herein ).

These cobalt catalysts are readily prepared by known methods, such as taught in the examples in the Tobe article and references cited therein, US4810410 (Diakun et al., issued March 7, 1989) , J.Chem2Ed.(1989), 66(12), 1043-45; Synthesis and Characterization of Inorganic Compounds (The Synthesis and Characterization of Inorganic Compounds), W.L.Jolly (Prentice-Hall; 1970), pp.461-3; Inorg .Chem., 18, 1497-1502(1979); Inorg.Chem., 21, 2881-2885(1982); Inorg.Chem., 18, 2023-2025(1979); Inorg.Sythesis, 173-176(1960 ); and Journal of Physical Chemistry, 54, 22-25 (1952).

As a matter of fact, and not by way of limitation, the compositions and methods herein can be adjusted to provide at least about 10 parts per million active bleach catalyst species in the wash solution, preferably about 0.01-25 ppm in the wash solution, more preferably Preferably from about 0.05 to 10 ppm, most preferably from about 0.1 to 5 ppm bleach catalyst material. To achieve such levels in wash liquors of automatic washing processes, the compositions herein generally contain from about 0.0005 to 0.2%, more preferably from about 0.004 to 0.08%, by weight of the cleaning composition, of a bleach catalyst, especially manganese or cobalt catalyst.

Enzymes - Detergent compositions of the present invention for a variety of purposes including removal of protein-based, carbohydrate-based or triglyceride-based stains from laundry, for preventing transfer of fugitive dyes in fabric washes and for fabric refreshment Preferably enzymes are included. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal, and yeast origin. The preferred choice is influenced by factors such as pH optimum activity and/or stability, thermostability and stability to active detergents, builders and the like. In this regard, bacterial and fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

As used herein, "detergent enzyme" refers to any enzyme having a cleaning, stain removal or other beneficial effect in laundry, hard surface cleaning or personal care detergent compositions. Preferred detergent enzymes are hydrolases, such as proteases, amylases and lipases. Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred for use in automatic washing are amylases and/or proteases, including the types currently available on the market and improved types which, through continuous improvement, are still somewhat bleach-reducing despite being more compatible with bleach. live sensitivity.

Enzymes are generally added to detergent or detergent additive compositions in an amount sufficient to provide a "cleaning effective amount". The term "cleaning effective amount" means an amount capable of producing cleaning, stain removing, soil removing, whitening, deodorizing or freshness improving effects on the laundry such as fabrics, tableware and the like. In practice with formulations currently on the market, typical amounts are up to about 5 mg by weight, more typically about 0.01-3 mg of active enzyme, per gram of detergent composition. In other words, the compositions herein generally contain 0.001-5% by weight, preferably 0.01-1% by weight, of a commercial enzyme preparation. Proteases are typically present in such commercial formulations in amounts sufficient to provide 0.005-0.1 Anson Units (AU) of activity per gram of composition. For certain detergents, such as automatic dishwashing detergents, it may be desirable to increase the active enzyme content of commercial formulations in order to minimize the total amount of non-catalytically active material provided and thus improve spotting/filming or other end results. Higher active levels are also desirable in highly concentrated detergent formulations.

Suitable examples of proteases are subtilisins obtained from certain strains of Bacillus subtilis and Bacillus licheniformis. A suitable protease is obtained from a Bacillus strain having maximum activity in the pH range of 8-12, developed by Novo Industries A/S of Denmark (hereinafter "Novo") and sold under the registered trademark ESPERASE. The preparation of this and similar enzymes is described in Novo, UK Patent Specification 1,243,784. Other suitable proteases include ALCALASE ^R and SAVINASE ^R from Novo, MAXATASE ^R from International Bio-Synthetics, Inc. (Netherlands) and Protease A disclosed in European Patent Application 130756A, January 9, 1985 and April 28, 1987 Protease B in EP303, 761A and EP130756A of 9 January 1985. See also the high pH protease from Bacillus sp. NCIMB40338 described in WO9318140A to Novo. Enzyme detergents comprising a protease, one or more other enzymes and a reversible protease inhibitor are described in WO9203529A to Novo. Other preferred proteases include those in WO9510591A to Procter & Gamble. When desired, proteases with reduced adsorption and increased hydrolysis are available as described in WO9507791 to Procter & Gamble. Recombinant trypsin-like proteases suitable for use in detergents herein are described in WO9425583 to Novo.

In more detail, a particularly preferred protease called "Protease D" is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by The above carbonyl hydrolase is equivalent to the +76 position, preferably also according to the numbering of Bacillus amyloliquefaciens subtilisin is equivalent to +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, One or more amino acid residue positions at +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274, with different amino acids replacing multiple Amino acid residues are as described in WO95/10615 (published April 20, 1995) by Genencor International.

Useful proteases are also described in the following PCT publications: WO95/30010, Procter & Gamble Company, published November 9, 1995; WO95/30011, Procter & Gamble Company, published November 9, 1995; WO 95/29979 of the Procter & Gamble Company.

Amylases suitable herein for especially but not limited to automatic dishwashing purposes include, for example, the alpha-amylases described in GB1296839 (Novo), RAPIDASE ^R (International Bio-Synthetics, Inc.) and TERMAMYL ^R (Novo) . Novo's FUNGAMYL ^R is particularly useful. Enzyme engineering to improve stability, eg oxidative stability, is known. See, eg, J. Biological Chem., Vol. 260, No. 11, June 1985, pp 6518-6521. Certain preferred embodiments of the present invention may utilize amylases having improved stability, especially improved oxidative stability, in detergents, such as automatic dishwashing type detergents, as measured relative to the 1993 commercially used TERMAMYL ^R reference point . These preferred amylases herein have the characteristics of "stability-enhanced" amylases characterized by at least one or more of the following measurable improvements in stability: e.g. Oxidative stability of hydrogen peroxide/tetraacetylethylenediamine; e.g. thermal stability at ordinary wash temperatures such as about 60° C.; or alkaline stability e.g. at a pH of about 8-11; all measurements are in relation to The reference amylases indicated above were comparatively determined. Stability can be determined using any prior art assay. See, eg, references disclosed in WO9402597. Stability-enhanced amylases are available from Novo or Genencor International.

A class of highly preferred amylases herein has the commonality of being derived from one or more Bacillus amylases, especially Bacillus alpha-amylases, using site-directed mutagenesis, and with one, two or more amylase strains Whether it is an intermediate precursor or not is irrelevant. Amylases having enhanced oxidative stability relative to the above referenced amylases are preferred for use in detergent compositions herein especially bleached, more preferably oxygen bleached (as opposed to chlorine bleached). Such preferred amylases include: (a) amylases according to WO94/02597, Novo, 3 February 1994, incorporated above, as further illustrated by mutants, wherein alanine or threonine are used , preferably a threonine substitution for the methionine residue at position 197 of a Bacillus licheniformis alpha-amylase known as ^TERMAMYL® , or a similar parental amylase, such as Bacillus amyloliquefaciens, Bacillus subtilis, or Bacillus stearothermophilus (b) As Genencor International submitted in the 207th American Chemical Society National Meeting on March 13-17, 1994 by C.Mitchinson entitled "Antioxidatively Resistant α-amylase (Oxidatively Resistant Stability-enhanced amylases described in the article α-Amylases). It is mentioned that bleaches in automatic dishwashing detergents inactivate alpha-amylases, but amylases with improved oxidative stability are made by Genencor from Bacillus licheniformis NCIB8061. Methionine (Met) was considered the most likely residue to be modified. Substitution of Met one at a time at positions 8, 15, 197, 256, 304, 366 and 438 resulted in specific mutants, particularly important M197L and M197T, the M197T variant being the most stably expressed variant. Stability was determined in CASCADE ^R and SUNLIGHT ^R ; (c) particularly preferred amylases herein include amylase variants with additional modifications in the intermediate parent described in WO9510603A and available as DURAMYL ^(R) from assignee Novo. Other particularly preferred oxidative stability-enhanced amylases include those described in WO9418314 to Genencor International and WO9402597 to Novo. Any other oxidative stability-enhanced amylase may be used, for example derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parental forms of available amylases. Other preferred amylase modifications are achievable. See WO9509909A to Novo.

Other amylases include those described in WO95/26397 and Novo Nordisk's co-pending application PCT/DK96/00056. Particular amylases for use in the detergent compositions of the present invention include alpha amylases characterized by having a specific activity at least 25% higher than that of Termamyl ^R at a temperature range of 25-55°C and at a pH range of 8-10 - Amylase, as determined by the Phadebas ^R alpha-amylase activity test. (The Phadebas ^R α-amylase activity assay described above is described on pages 9-10 of WO 95/26397.) Also included herein are α-amylases at least 80% homologous to the amino acid sequences shown in the SEQ ID list of references. Amylase. These enzymes are preferably incorporated into laundry detergent compositions at levels of 0.00018-0.060% pure enzyme, more preferably 0.00024-0.048% pure enzyme by weight of the total composition.

Cellulases usable in the present invention include bacterial and fungal cellulases, preferably with an optimum pH between 5-9.5. US4435307 (Barbesgoard et al., issued March 6, 1984) discloses fungal cellulase produced from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing mold belonging to the genus Aeromonas, and from marine Cellulase extracted from the hepatopancreas of a mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2075028; GB-A-2095275 and DE-OS-2247832. ^CAREZYME® and ^CELLUZYME® (Novo) are particularly useful. See WO9117243 (Novo).

Suitable lipases for detergent use include those produced by Pseudomonas microorganisms such as Pseudomonas stutzeri ATCC 19.154 as disclosed in British Patent GB 1372034. See also lipases in Japanese Patent Application No. 53,20487 (laid open February 24, 1987). This lipase is commercially available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the trade name Lipase P "Amano" or "Amano-P". Other suitable commercially available lipases include Amano-CES, lipases from Chromobacter viscosum such as Chromobacter viscosum var. lipolyticum NRRLB3673 (from Toyo Jozo Co., Tagata, Japan); and from US Biochemical Corp. (USA) and Disoynth Co Other Chromobacter viscosum lipases from .(Netherlands), and lipases from Pseudomonas gladioli. The LIPOLASE ^(R) enzyme obtained 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 (Novo). See also WO9205249 and RD94359044.

Although many lipases have been disclosed, so far only lipases obtained from Humicolalanuginosa and produced in Aspergillus oryzae as a host have found wide application as additives for fabric washing products. As mentioned above, it is commercially available from Novo Nordisk under the tradename Lipolase ^(TM) . Novo Nordisk has manufactured a number of variants for optimum soil removal performance of lipase. As described in WO92/05249, the D96L variant of the native Humicolalanuginosa lipase was improved by 4.4% in removal of lard stains compared to wild-type lipase (comparing these enzymes in the range of 0.075-2.5 mg protein per liter). times. Novo Nordisk, Research Publication No. 35944, published March 10, 1994, discloses that the lipase variant (D96L) can be added in an amount equivalent to 0.001-100 mg per liter of wash liquor (5-500000 LU/liter) of the lipase variant. The present invention provides improved fabric whiteness maintenance using low levels of D96L variants in detergent compositions containing isopeptidases in the manner disclosed herein, especially at levels of about 50-8500 LU per liter of wash liquor. benefits.

Cutinases suitable for use herein are described in WO8809367A to Genencor.

Peroxidases can be used with an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are generally used for "solution bleaching" or to prevent the transfer of dyes or pigments released during the wash operation from one wash to another in the wash solution. Known peroxidases include horseradish peroxidase, ligninase and haloperoxidases such as chloro- or bromo-peroxidase. Detergent compositions containing peroxidase are disclosed in WO89099813A (Novo, October 19, 1989) and WO8909813A (Novo).

Various enzymes and their incorporation into synthetic detergent compositions are also disclosed in WO9307263A and WO9307260A to Genencor International, WO8908694A to Novo and US3553139 (issued January 5, 1971 to McCarty et al.). Enzymes are also disclosed in US4101457 (Place et al., issued July 18, 1978) and US4507219 (Hughes et al., issued March 26, 1985). Enzyme materials for use in liquid detergent formulations and their incorporation into such formulations are disclosed in US4261868 (Hora et al., April 14, 1981). Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in US3600319 (Gedge et al., issued August 17, 1971) and in European Patent Applications EP199405 and EP200586 (Venegas, October 29, 1986). Enzyme stabilization systems are also described, for example, in US3519570. Useful Bacillus sp. AC13 for deriving proteases, xylanases and cellulases is described in WO9401532A (Novo).

Enzyme Stabilizing System - The enzyme-containing compositions herein may optionally contain about 0.001-10% by weight, preferably about 0.005-8% by weight, most preferably about 0.01-6% by weight of an enzyme stabilizing system. The enzyme stabilization system can be any enzyme stabilization system compatible with the washing enzyme. Such a system may be provided inherently with other formulation actives, or added separately, for example by the formulator or manufacturer of detergent ready enzymes. Such stabilizing systems may include calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition.

One method of stabilization is to use a water-soluble source of calcium and/or magnesium ions (which donate said ions to the enzyme) in the final composition. Calcium ions are generally slightly more effective than magnesium ions and are preferred herein if only one type of cation is used. Typical detergent compositions, especially liquid compositions, include about 1-30, preferably about 2-20, more preferably about 8-12 mmol of calcium ions per liter of final detergent composition, although there may be variations depending on these Factors: including the diversity, type and content of added enzymes. 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 Magnesium salts corresponding to the exemplified calcium salts. It is of course also useful to further increase the calcium and/or magnesium content, for example to enhance the degreasing action of certain types of surfactants.

Another method of stabilization is the use of borates. See US4537706 to Severson. When used, borate stabilizers comprise up to 10% or more of the composition, but more typically up to about 3% by weight boric acid or other borate compounds such as borax or orthoborate Suitable for liquid detergent use. Substituted boronic acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid or the like can be used in place of boric acid and, despite the use of such substituted boron derivatives, the total boron content of the detergent composition can be reduced.

Stabilizing systems of certain cleaning compositions, such as automatic dishwashing compositions, may also contain from 0 to about 10% by weight, preferably from about 0.01 to 6% by weight, of a chlorine bleach scavenger added to prevent the presence of Chlorine bleach substances in many water sources destroy and inactivate enzymes, especially under alkaline conditions. Although the chlorine content in water is very small, generally in the range of about 0.5ppm-1.75ppm, the chlorine available in the total amount of water in contact with enzymes during dish or fabric washing will be relatively large, so in use enzyme stability is sometimes problematic. Since perborate or percarbonate (which has the ability to react with chlorine bleach) may be present in certain compositions of the present invention in an amount separate from the enzyme stabilization system, it is generally not required Additional chlorine stabilizers were used, but improved results were obtained with chlorine stabilizers. Suitable chlorine scavenger anions are widely known and readily available and, if used, can be ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide Wait for the salt. Antioxidants such as carbamates, ascorbic acid, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or alkali metal salts thereof, monoethanolamine (MEA), and mixtures thereof may also be used. Also, special enzyme inhibition systems can be incorporated to maximize compatibility with different enzymes. Other conventional scavengers such as bisulfates, nitrates, chlorides, peroxide sources such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate as well as phosphates, condensed phosphates can be used if desired , acetates, benzoates, citrates, formates, lactates, malates, tartrates, salicylates, etc., and mixtures thereof. In general, since the function of chlorine scavenger can be performed by components listed separately for better recognition of their function (such as hydrogen peroxide source), the addition of chlorine scavenger is not absolutely necessary, except in the enzyme-containing practice of the present invention. The required level of compound to perform this function was not present in the protocol; even in this case, the scavenger was added only for optimal results. In addition, the formulator can use the normal skill of a chemist to avoid the use of enzyme scavengers or stabilizers that are formulated to be substantially incompatible with other reactive components. With regard to the use of ammonium salts, the salt can simply be mixed with the detergent composition but the salt tends to absorb water and/or release ammonia on storage. Thus, such materials, if present, are preferably preserved in the particles as described in US4652392 to Baginski et al.

Builders - Preferred builders for use in the compositions of the present invention, especially in granular form, are detergent builders selected from the group consisting of aluminosilicates and silicates, which are preferably included in the compositions herein in order to eg help control mineral, especially Ca and/or Mg hardness in the wash water or to help remove particulate soil from surfaces.

Suitable silicate builders include water-soluble and aqueous solid types and include chain, lamellar or three-dimensional structures as well as amorphous solid or unstructured liquid types. Preferred are alkali metal silicates, especially those liquids and solids having a _SiO2 : _Na2O ratio in the range of 1.6:1 to 3.2:1, including, especially for automatic dishwashing purposes, sold by PQ Corp. under the tradename BRITESIL ^R is a solid aqueous 2-ratio silicate sold such as BRITESIL H2O; and layered silicates such as the layered sodium silicates described in US 4,664,839 (HPRieck, issued May 12, 1987). NaSKS-6, sometimes abbreviated "SKS-6", is a crystalline layered, aluminum-free, delta- _Na2SiO5 form silicate sold by Hoechst and is particularly _preferred for use in granular laundry compositions. Their preparation can be seen in DE-A-3417649 and DE-A-3742043. Other phyllosilicates, such as those having the general formula _{NaMSixO2x + 1yH2O} , wherein M is sodium or hydrogen, x is 1.9-4, preferably 2, and y is 0-20, preferably 0, can also be or Also used in this article. Sheet silicates from Hoechst include: NaSKS-5, NaSKS-7 and NaSKS-11 as alpha, beta and gamma forms. Other silicates are also useful, such as magnesium silicate, which can be used in granular formulations as a crispening agent, as a bleach stabilizer, and as a component of suds control systems.

Also suitable herein are those having a chain structure and having the general anhydride formula xM ₂ O·ySiO ₂ ·zM'O, where M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5-2.0 and z/x is 0.005-1.0, representing the composition of a synthetic crystalline ion exchange material or a hydrate thereof.

Aluminosilicate builders are particularly useful in granular detergents, but may also be incorporated into liquid, paste or gel compositions. Suitable for the purposes of the present invention are those having the empirical formula [M _z (AlO ₂ ) _z (SiO ₂ ) _v ]·xH ₂ O, wherein z and v are integers of at least 6 and the molar ratio of z to v is from 1.0 to 0.5 , x is an integer of 15-264. Aluminosilicates can be crystalline or amorphous, and can be naturally occurring or synthetically derived. A method of producing aluminosilicates is disclosed in US3985669 (Krummel et al., issued October 12, 1976). Preferred synthetic crystalline aluminosilicate ion exchange materials are available under the names zeolite A, zeolite P (B), zeolite X and, as a variant of zeolite P, the so-called zeolite MAP. Natural types can be used, including clinoptilolite. Zeolite A having the formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]xH ₂ O, where x is 20-30, especially 27, may also be used. Dehydrated zeolites (x = 0-10) can also be used. Preferably, the particle diameter of the aluminosilicate is 0.1-10 microns.

Detergent builders instead of or in addition to the silicates and aluminosilicates described above may also optionally be included in the compositions herein, for example to help control minerals in the wash water, especially Ca and/or Mg hardness may aid in the removal of particulate dirt from surfaces. Builders can function by various mechanisms, including forming soluble or insoluble complexes with hardness ions by ion exchange, and providing surfaces that are more conducive to the precipitation of hardness ions than the surfaces of items being cleaned. Builder levels can vary widely depending on the end use and physical form of the composition. Built detergents generally contain at least about 1% builder. Liquid formulations generally contain about 5-50%, more typically 5-30%, by weight, builder. Granular formulations generally contain from about 10 to 80%, more typically from 15 to 50%, by weight of the detergent composition, of builder. However, lower or higher levels of builders are not excluded. For example certain detergent additives or high surfactant formulations may be underbuilded.

Suitable builders herein are selected from: phosphates and polyphosphates, especially sodium salts; carbonates; bicarbonates; sesquicarbonates and carbonate minerals other than sodium carbonate or sodium sesquicarbonate ; organic mono-, di-, tri- and tetracarboxylates in the form of acid, sodium, potassium or alkanolammonium salts, especially water-soluble non-surfactant carboxylates; and oligomeric or water-soluble low molecular weight polymers Carboxylates, including aliphatic and aromatic types; and phytic acid. It may be with borates, for example for pH buffering purposes, or with sulphates, especially sodium sulphate and other fillers important to the engineering of detergent compositions containing stable surfactants and/or builders or carrier to supplement.

Builder mixtures may be used, sometimes referred to as "builder systems", which generally comprise two or more conventional builders, optionally supplemented with chelating agents, pH buffers or fillers, the latter materials It is usually stated separately when describing the amount of material of the present invention. Preferred builder systems are typically formulated at a surfactant to builder weight ratio of from about 60:1 to about 1:80, relative to the amount of surfactant and builder in the detergents of the present invention. Certain preferred laundry detergents have this ratio in the range of 0.90:1.0 to 4.0:1.0, more preferably 0.95:1.0 to 3.0:1.0.

Where permitted by law, often preferred phosphorus-containing detergent builders include, but are not limited to: alkali metal, ammonium, and alkanolammonium salts of polyphosphates, such as tripolyphosphates, pyrophosphates, glassy Polymetaphosphates and phosphonates.

Suitable carbonate builders include the alkaline earth metal and alkali metal carbonates disclosed in German Patent Application No. 2321001 (published November 15, 1973), but sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other Carbonate minerals such as trisodium bicarbonate or any _conventional double salt of sodium and calcium carbonate such as when it is anhydrous with the composition _2Na2CO3CaCO3 , and even calcium carbonate, including calcite, aragonite _and Vaterite, especially in forms with high surface area relative to dense calcite, can be useful, for example, as seed crystals or in syndet soap bars.

Suitable organic builders include polycarboxylate compounds, including the water-soluble nonsurfactant dicarboxylates and tricarboxylates. More generally, builder polycarboxylates will have a plurality of carboxylate groups, preferably at least 3 carboxylates. Carboxylate builders can be formulated in acid, partially neutralized, neutral or overbased form. When in salt form, alkali metals such as sodium, potassium and lithium or alkanolammonium salts are preferred. Polycarboxylate builders include ether polycarboxylates such as oxydisuccinates, see US3128287 (Berg, April 7, 1964) and US3635830 (Lamberti et al., January 18, 1972); US4663071 (Bush et al., May 5, 1987) "TMS/TDS" builders; and other ether carboxylate builders, including cyclic and alicyclic compounds, such as those described in the following U.S. Patents: US3923679, US3835163, US4158635, US4120874 and US4102903.

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

Citrate builders, such as citric acid and its soluble salts, are particularly important carboxylate builders, e.g. for heavy duty liquid detergents, due to their availability from renewable sources and their biodegradability . Citrates may also be used in granular compositions, especially in combination with zeolites and/or layered silicates. Oxydisuccinates are also particularly useful in such compositions and combinations.

Alkali metal phosphates such as sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used when permitted, especially in soap bar formulations for handwashing operations. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates such as those in US3159581; US3213030; US3422021; US3400148 and US3422137, which have Ideal antifouling properties.

Certain detersive surfactants or their short chain homologues also have builder action. For the purposes of formulation calculations, these materials were attributed to detersive surfactants when they possessed surfactant capability. Preferred types for builder function are illustrated below: 3,3-Dicarboxy-4-oxa-1,6-hexanedioates and related compound. Succinic acid builders include _C5 - _C20 alkyl and alkenyl succinic acids and salts thereof. Succinate builders also include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate salt etc. Lauryl succinate is described in European Patent Application 8600690.5/0200263, published November 5, 1986. Fatty acids such as C ₁₂ -C ₁₈ monocarboxylic acids may also be incorporated into the compositions as surfactant/builder materials alone or in combination with the aforementioned builders, especially citrate and/or succinate builders , in order to provide additional builder activity. Other suitable polycarboxylates are disclosed in US 4,144,226 (Crutchfield et al., March 13, 1979) and US 3,308,067 (Diehl et al., March 7, 1967). See also US3723322 to Diehl.

Other types of inorganic builder materials that can be used have the formula (M _x ) _i Ca _y (CO ₃ ) _z where x and i are integers from 1 to 15, y is an integer from 1 to 10, and z is from 2 to 25 An integer of M _i is a cation, at least one of which is water-soluble, and satisfies the formula Σ _i = 1-15 (valence state of x _i multiplied by M _i ) + 2y = 2z, resulting in a formulation with a neutral or "balanced" charge . These builders are referred to herein as "mineral builders". Water of hydration or non-carbonate anions may be added provided the overall charge is balanced or neutral. The charge or valence effects of these anions should be added to the right side of the above formula. Preferably there is a water soluble cation selected from the group consisting of hydrogen, water soluble metals, hydrogen, boron, ammonium, silicon and mixtures thereof, more preferably sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium and potassium being very preferred. Non-limiting examples of non-carbonate anions include those selected from the group consisting of chloride, sulfate, fluoride, oxygen, hydroxide, silica, chromate, nitrate, borate, and mixtures thereof. Such preferred builders in their simplest form are selected from: _Na2Ca ( _{CO3 ) 2} , _K2Ca ( _CO3 ) ₂ , _Na2Ca2 ( _CO3 ) ₃ , NaKCa( _CO3 ) ₂ , NaKCa ₂ (CO ₃ ) ₃ , K ₂ Ca ₂ (CO ₃ ) ₃ and mixtures thereof. A particularly preferred builder material described herein is _Na2Ca ( _CO3 ) ₂ in its crystalline modified form. Suitable builders of the above types are also exemplified by the following materials, which include any one or combination of the following minerals, natural or synthetic: acaciasite, uranite, zeolite Y, carbon Bismuth calcium stone, carbon boron magnesium calcium stone, yellow rhodium strontium cerite, hydropotassium calcium carbonate calcium stone, cancryptite, cericite, carbon silica soda calcium stone, potassium cannonite, Y-type yttrium carbonic acid strontite, carbon Potassium Calcite, Ferrisurite, Ferrisurite, Caroborite, Monoclinic Soda Lime, Girvasite, Gregoryite, Sulphurite, Kamphaugite Y, Kettnerite, Khanneshite, LepersonniteGd, Licanite, Y-type Carbon Barium yttrium ore, micro-alkaline cancryptite, carbon tellurite, Nicarbon soda limestone, Nicarbon soda limestone, RemonditeCe, Potassium cannonite, plate carbonite, soda calcium carbonate, carbon silicon aluminum lead stone , Soda Mayenite, Sulfurite, Cooperite, Cancryptite Sulfate, Zemkorite. Preferred material forms include nirvanite, sorrelite and sorrelite.

Polymeric Soil Release Agents - Known polymeric soil release agents, hereinafter "SRA", may optionally be employed in the detergent compositions of the present invention. If used, SRA will generally comprise 0.01-10.0%, typically 0.1-5%, preferably 0.2-3.0%, by weight of the composition.

Preferred SRAs generally have a hydrophilic portion that makes the surface of hydrophobic fibers such as polyester and nylon hydrophilic, and deposits on the hydrophobic fibers and remains adhered thereto until the wash and rinse cycle is complete, thereby acting as an anchor for the hydrophilic portion the hydrophobic part. This enables easier cleaning of the soil present after treatment with the soil release agent in the subsequent washing process.

SRAs may comprise various charges such as anionic or even cationic species (see US4956447), as well as uncharged monomeric units, and may be linear, branched or even star-shaped in structure. They may include capping moieties that are particularly effective in controlling molecular weight or modifying physical or surface active properties. For application to different fiber or fabric types and for diversification of detergent or detergent additive products, the structure and charge distribution can be adjusted. Preferred SRAs include oligomeric terephthalates, which are generally prepared by a process involving at least one transesterification/oligomerization reaction, usually with a metal catalyst such as titanium (IV) alkoxylate. Such esters may be prepared using additional monomers capable of being incorporated into the ester structure through 1, 2, 3, 4 or more positions (without, of course, forming a densely crosslinked overall structure).

Suitable SRAs include sulfonated products of substantially linear ester oligomers consisting of an oligoester backbone of terephthaloyl groups and oxyalkyleneoxy repeat units and sulfonated ends derived from allyl groups covalently attached to the backbone. The base moiety is composed, for example, as described in US4968451 (J.J. Scheibel and E.P. Gosselink, issued November 6, 1990). Such ester oligomers can be prepared by (a) ethoxylating allyl alcohol; (b) combining the product of (a) with terephthalic acid in a 2-step transesterification/oligomerization process reacting methyl ester ("DMT") and 1,2-propanediol ("PG"); and (c) reacting the product of (b) with sodium metabisulfite in water. Other SRAs include the non-ionically terminated 1,2-propylene/polyoxyethylene terephthalate polyesters of US4711730 (Gosselink et al., issued December 8, 1987), e.g. by poly(ethylene glycol) methyl ether , DMT, PG, and those prepared by transesterification/oligomerization of poly(ethylene glycol) ("PEG"). Other examples of SRAs include: US4721580 (Gosselink, issued January 26, 1988) partially and fully anion-terminated oligomeric esters, such as those derived from ethylene glycol ("EG"), PG, DMT and 3,6- Oligomers of sodium dioxa-8-hydroxyoctane sulfonate; non-ionically terminated block polyester oligomeric compounds of US4702857 (Gosselink, issued on October 27, 1987), for example from DMT, methyl (Me ) end-capped PEG and EG and/or PG, or DMT, EG and/or PG, Me end-capped PEG and dimethyl 5-sulfonate isophthalate; and US4877896 (Maldonado, Gosselink et al., Issued on October 31, 1989), especially sulfoaroyl-terminated terephthalates, which are SRAs commonly used in laundry and fabric conditioning products, examples are monosodium m-sulfobenzoate An ester composition prepared from salt, PG and DMT, optionally but preferably also including added PEG (eg PEG3400).

SRA also includes: simple copolymer blocks of ethylene or propylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate, see US3959230 (Hays, May 1976 25) and US3893929 (Basadur, issued Jul. 8, 1975); cellulose derivatives such as hydroxyether fiber polymers available from Dow as METHOCEL; C ₁ -C ₄ alkyl cellulose and C ₄ hydroxyalkyl Cellulose, see US4000093 (Nicol et al., issued December 28, 1976). Suitable SRAs characterized by poly(vinyl ester) hydrophobic moieties include grafted poly(vinyl esters) such as C ₁ -C ₆ vinyl esters, preferably poly(vinyl acetate), grafted onto a polyalkylene oxide backbone. branch copolymers. See European Patent Application 0219048 published April 22, 1987 by Kud et al. Commercially available examples include SOKALAN SRA such as SOKALAN HP-22 from BASF, Germany. Other SRAs are polyoxyethylene terephthalic acid containing 10-15% by weight ethylene terephthalate and 80-90% by weight derived from polyoxyethylene glycol with an average molecular weight of 300-5000. Polyesters with ester repeating units. Commercial examples include Dupont's ZELCON5126 and ICI's MILEASE T.

Another preferred SRA is an oligomer having the empirical formula (CAP) ₂ (EG/PG) ₅ (T) ₅ (SIP) ₁ containing terephthaloyl (T), sulfoisophthaloyl (SIP ), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and which are preferably terminated with capping groups (CAP), preferably modified isethionate, as oligomers It comprises 1 sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a defined ratio, preferably about 0.5:1 to 10:1, and 2 capping units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate. On an oligomer weight basis, the SRA preferably also contains 0.5-20% crystallinity-reducing stabilizers, such as anionic surfactants such as linear sodium dodecylbenzene sulfonate or selected from xylene, cumene and tosylate or mixtures thereof, these stabilizers or modifiers are added to the synthesis vessel as taught in US5415807 (Gosselink, Pan, Kellet and Hall, issued May 16, 1995). Suitable monomers for the above formula SRA include sodium 2-(2-hydroxyethoxy)-ethanesulfonate, DMT, dimethyl 5-sulfonate isophthalate, EG and PG.

Yet another class of preferred SRAs are oligoesters comprising: (1) a backbone comprising: (a) at least one unit selected from the group consisting of dihydroxysulfonate, polyhydroxysulfonate, at least trihydroxysulfonate The functional groups thus form ester linkages leading to units of the branched oligomer backbone, and mixtures thereof; (b) at least one terephthaloyl unit; and (c) at least one unsulfonated unit which is 1,2- and (2) one or more capping units selected from the group consisting of nonionic capping units, anionic capping units such as alkoxylated, preferably ethoxylated isethionates , alkoxylated propane sulfonates, alkoxylated propane disulfonates, alkoxylated phenol sulfonates, sulfoaroyl derivatives and mixtures thereof. Preferred are esters with the following empirical formula:

{(CAP)x(EG/PG)y’(DEG)y”(PEG)y”’(T)z(SIP)z’(SEG)q(B)m}

where CAP, EG/PG, PEG, T and SIP are as defined above, (DEG) means di(oxyethylene)oxy units, (SEG) means units derived from sulfoethyl ether of glycerol and related moiety units , (B) represents at least a trifunctional group and thus forms an ester bond leading to a branched chain unit of the branched oligomer backbone, x is about 1-12, y' is about 0.5-25, y "is 0-about 12, y "' is 0 to about 10, the sum of y'+y"+y"' is about 0.5-25, z is about 1.5-25, z' is 0 to about 12, the sum of z+z' is about 1.5-25, and q is about 0.05 -12; m is about 0.01-10; and x, y', y", y"', z, z', q and m represent the average number of moles of the corresponding units per mole of the ester, and the molecular weight of the ester In the range of about 500-5000.

Preferred SEG and CAP monomers for the above esters include: sodium 2-(2-,3-dihydroxypropoxy)ethanesulfonate ("SEG"), 2-{2-(2-dihydroxyethoxy ) Sodium ethoxy}ethanesulfonate ("SE3") and its homologues and mixtures thereof and products of ethoxylated and sulfonated allyl alcohol. Preferred SRA esters of this class include the products of the transesterification and oligomerization of 2-{2-(2-dihydroxyethoxy)ethoxy}ethanesulfonate with a suitable Ti(IV) catalyst sodium sulfonate and/or sodium 2-[2-{2-(2-dihydroxyethoxy)ethoxy}ethoxy]ethanesulfonate, DMT, 2-(2-,3-dihydroxypropoxy base) sodium ethanesulfonate, EG and PG; which can be referred to as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13, where CAP is (Na ^+- O ₃ S [ _CH2CH2O ]3.5)- and B are units derived from _glycerol , and the EG/PG molar ratio is about 1.7:1, as determined by conventional gas chromatography after complete hydrolysis.

There is also a class of SRAs including: (I) nonionic terephthalate esters that link polymeric ester structures with diisocyanate coupling agents, see US4201824 (Violland et al.) and US4240918 (Lagasse et al.); SRA with carboxylate end groups prepared by converting the terminal hydroxyl groups to trimellitate into known SRAs. With proper selection of the catalyst, the trimellitic anhydride forms linkages to the polymer end groups through the ester of the isolated carboxylic acid of the trimellitic anhydride rather than by opening the anhydride linkages. Nonionic or anionic SRAs can be used as starting materials as long as they have hydroxyl end groups that can be esterified. See US4525524 (Tung et al); (III) SRAs of anionic terephthalate groups of urethane-linked variants, see US4201824 (Violland et al); (IV) poly(vinylcaprolactam) and related compounds such as ethylene Copolymers of monomers of pyrrolidone and/or dimethylaminoethyl methacrylate, including nonionic and cationic polymers, see 4579681 (Ruppert et al.); (V) graft copolymers, except those available from BASF Other than the SOKALAN type, which are prepared by grafting acrylic monomers onto sulfonated polyesters. These SRAs certainly have soil release and anti-redeposition activity similar to known cellulose ethers: see EP279134A (Rhone-Poulenc Chemie, 1988); (VI) Vinyl monomers such as acrylic acid and vinyl acetate in proteins such as casein (VII) Polyester-polyamide SRA prepared by condensation of adipic acid, caprolactam and polyethylene glycol, especially for the treatment of polyamide fabrics, see Bevan et al. DE2335044 (Unilever N.V., 1974). Other useful SRAs are described in US Patents 4,240,918, 4,787,989, 4,525,524 and 4,877,896.

Clay Soil Removal/Anti-Redeposition Agents - The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01 to 10.0% by weight of the water-soluble ethoxylated amines; liquid detergent compositions typically contain from about 0.01 to 5% by weight.

The most preferred soil release and antiredeposition agents are ethoxylated tetraethylenepentamines. Illustrative ethoxylated amines are further described in US 4,597,898 (VanderMeer, issued Jul. 1, 1986). Another preferred class of clay soil removal-antiredeposition agents are the cationic compounds disclosed in European Patent Application 111965 (Oh and Gosselink, published June 27, 1984). Other clay soil removal/anti-redeposition agents that can be used include the ethoxylated amine polymers disclosed in European Patent Application 111984 (Gosselink, published June 27, 1984); disclosed in European Patent Application 112592 (Gosselink, and the amine oxides disclosed in US4548744 (Connor, issued October 22, 1985). Other clay soil removal and/or anti-redeposition agents known in the art may also be used in the compositions herein. See US4891160, VanderMeer, issued January 2, 1990 and WO95/32272, published November 30,1995. Another class of preferred anti-redeposition agents includes carboxymethylcellulose (CMC) materials. These materials are well known in the art.

Polymeric Dispersants - Polymeric dispersants can advantageously be used in the compositions herein at levels of from about 0.1% to about 7% by weight, especially when zeolite and/or layered silicate builders are present. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. While not intending to be bound by theory, it is believed that when used in combination with other builders, including low molecular weight polycarboxylates, the polymeric dispersants enhance overall detergent builder performance.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Monomers that can be polymerized to form suitable polymeric polycarboxylates include: acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylene Malonate. The presence in the polymeric polycarboxylates herein of monomeric segments containing no carboxylate groups such as vinyl methyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% (weight).

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

Acrylic/maleic based copolymers can also be used as a preferred component of the dispersant/anti-redeposition 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 in the range of about 2,000-100,000, more preferably about 5,000-75,000, most preferably about 7,000-65,000. The ratio of acrylate to maleate segments in such copolymers generally ranges from about 30:1 to 1:1, preferably from about 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers include, for example, alkali metal, ammonium and substituted ammonium salts. Such soluble acrylate/maleate copolymers are known materials and are described in European Patent Application 66915 (published December 15, 1982) and EP193360 (published September 3, 1986), which also describes This polymer contains hydroxypropyl acrylate. Other dispersants that are also useful include maleic acid/acrylic acid/vinyl alcohol terpolymers. Such materials are also disclosed in EP193360 and include for example a 45/45/10 terpolymer of acrylic acid/maleic acid/vinyl alcohol.

Another polymeric material that can be included is polyethylene glycol (PEG). PEG can exhibit dispersant properties as well as function as a clay soil removal-anti-redeposition agent. Typical molecular weights for this purpose are in the range of about 500-100,000, preferably about 1,000-50,000, more preferably about 1,500-10,000.

Polyaspartates and polyglutamates can also be used, especially with zeolite builders. Dispersants such as aspartate preferably have a molecular weight (average) of about 10,000.

Brighteners - Any optical brighteners or other brightening or whitening agents known in the art can be incorporated into the detergent compositions herein, generally at a level of from about 0.01% to about 1.2% by weight. Commercially available optical brighteners that may be useful in the present invention can be divided into subgroups which include, but are not necessarily limited to, stilbenes, pyrazolines, coumarins, carboxylic acids, methinecyanines, dibenzothiophene-5, 5-dioxides, pyrroles, derivatives of 5- and 6-membered heterocycles, and various other reagents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Jones Wiley & Sons, New York Publishing (1982).

Specific examples of optical brighteners useful in the compositions of the present invention are those taught in US 4,790,856, Wixon, issued December 13, 1988. These brighteners include Verona's PHORWHITE series of brighteners. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM available from Ciba-Geigy; Artic White CC and Artic White CWD; 2-(4-Styryl-phenyl)-2H -Naphtho[1,2-d]triazole; 4,4'-bis-(1,2,3-triazol-2-yl)-stilbene; 4,4'-bis(styryl)biphenyl ; and aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethylaminocoumarin; 1,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenyl-pyrazole 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 (issued to Hamilton on February 29, 1972).

Dye Transfer Inhibiting Agents - The compositions of the present invention may also include one or more materials effective to inhibit the transfer of dyes from one fabric to another during the laundering process. Typical such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof . If used, these agents generally comprise from about 0.01 to 10%, preferably from about 0.01 to 5%, and more preferably from about 0.05 to 2%, by weight of the composition.

More specifically, preferred polyamine N-oxide polymers for use herein contain units of the formula: RA _x -P; where P is a polymerizable unit to which the NO group may be attached or the NO group A group may form part of a polymerizable unit or an NO group may be attached to both units; A is one of the following structures: -NC(O)-, -C(O)O-, -S-, -O- , -N=; x is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or a mixture thereof, to which the nitrogen atom of the NO group can be attached Or the NO group is part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

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

Wherein R ₁ , R ₂ , R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or a mixture thereof, x, y and z are 0 or 1; the nitrogen atom of the NO group can be connected or form Part of any of the above groups. The amine oxide units of the polyamine N-oxides have a pKa<10, preferably pKa<7, more preferably pKa<6.

Any polymer backbone can be used so long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers in which one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymer generally has a ratio of amine to amine N-oxide of 10:1 to 1:1,000,000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by suitable copolymerization or by suitable degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. Generally, the average molecular weight is in the range of 500-1,000,000; more preferably 1,000-500,000; most preferably 5,000-100,000. A preferred class of materials may be referred to as "PVNO".

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

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as "PVPVI" types) are also preferred for use herein. The average molecular weight of PVPVI is preferably in the range of 5,000-1,000,000, more preferably 5,000-200,000, and most preferably 10,000-20,000. (The average molecular weight range is determined by light scattering as described by Barth et al., in Chemical Analysis, Vol 113, "Modern Methods of Polymer Characterization", the disclosure of which is incorporated herein For reference.) The molar ratio of N-vinylimidazole to N-vinylpyrrolidone of the PVPVI copolymer is generally 1:1-0.2:1, more preferably 0.8:1-0.3:1, most preferably 0.6:1-0.4: 1. These copolymers may be linear or branched.

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

The detergent compositions herein may also optionally contain from about 0.005% to about 5% by weight of certain types of hydrophilic optical brighteners which also provide dye transfer inhibition. If used, the compositions herein preferably include from about 0.01% to about 1% by weight of such optical brighteners.

Hydrophilic optical brighteners useful in the present invention are those compounds having the following structural formula:

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

When _R in the above formula is anilino, _R is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4,4',-bis[(4-anilino -6-(N-2-Bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbene disulfonic acid and disodium salt. This particular brightener is sold under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

When _R in the above formula is anilino, _R is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4'-bis[ (4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbene disulphonic acid disodium salt. This particular brightener is sold under the tradename Tinopal-5BM-GX by Ciba-Geigy Corporation.

When _R in the above formula is anilino, R is _morpholino and M is a cation such as sodium, the brightener is 4,4'-bis[(4-anilino-6-morpholino- s-triazin-2-yl)amino] 2,2'-stilbene disulfonic acid, sodium salt. This particular brightener is sold under the tradename Tinopal-AMS-GX by Ciba-Geigy Corporation.

Certain optical brighteners selected for use in the present invention provide particularly effective dye transfer inhibiting performance benefits when used in combination with selected polymeric dye transfer inhibiting agents as hereinbefore described. Compared with these two detergent composition components when used alone, the above-mentioned selected polymeric material (for example, PVNO and/or PVPVI) and the above-mentioned selected optical brightener (for example, Tinopal UNPA-GX, Tinopal 5BM -GX and/or Tinopal AMS-GX) provide significantly better dye transfer inhibition in aqueous washes. Without being bound by theory, it is believed that the brighteners described above work in such a way that due to their high affinity for fabrics in the wash liquor, they deposit relatively quickly on these fabrics. The extent to which brighteners are deposited on fabrics in the wash solution can be defined by a parameter known as the "exhaustion coefficient". The consumption factor is generally the ratio of a) the brightener material deposited on the fabric to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are most suitable for use in the present invention to inhibit dye transfer.

It should be understood, of course, that other conventional optical brightener type compounds may optionally be used in the compositions of the present invention to provide conventional fabric "brightness" benefits rather than true dye transfer inhibition. Such use is routine and known to detergent formulators.

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. Without intending to be bound by theory, it is believed that the benefits of these materials are due in part to their exceptional ability to remove iron and manganese ions from wash solutions by forming soluble chelates.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate. Triethylenetetraamine hexaacetate, diethylenetriaminepentaacetate and hydroxyethyl diglycine, and 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 ethylenediaminetetrakis (methylene phosphonates) as DEQUEST . Preferably, these amino phosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms.

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

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

The compositions herein may also contain water-soluble methylglycine diacetic acid (MGDA) salt (or acid form) as a chelating agent or as a co-builder with, for example, insoluble builders such as zeolites, layered silicates, etc. agent.

If utilized, these chelating agents will generally comprise from about 0.1% to about 15% by weight of the detergent compositions herein. More preferably, if used, the chelating agent comprises from about 0.1% to about 3.0% by weight of the above compositions.

Suds Suppressors - Compounds that reduce or inhibit suds formation can be added to the compositions of the present invention. Suds suppression is particularly important in so-called "high concentration wash processes" as described in US Patents 4,489,455 and 4,489,574 and in front-loading European-type washing machines.

Various materials can be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, eg, Kirk Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Vol. 7, pp. 430-447 (Jone Wiley & Sons, Inc. 1979). A particularly important class of suds suppressors includes monocarboxylic fatty acids and soluble salts thereof. See US2954347 (Wayne St. John, issued September 27, 1960). The monocarboxylic fatty acids and salts thereof useful as suds suppressors generally have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts, such as sodium, potassium and lithium, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant suds suppressors. They include, for example, high molecular weight hydrocarbons such as paraffins, fatty acid esters (eg, fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ₁₈ -C ₄₀ ketones (eg, stearyl ketone), and the like. Other suds suppressors include: N-alkylated aminotriazines such as tri- to hexa-alkyl melamines or as products of cyanuric chloride with 2 or 3 moles of primary or secondary amines containing 1 to 24 carbon atoms Formed di- to tetra-alkyldiamine triazine chlorides, propylene oxide, and monostearyl phosphates such as monostearyl phosphate and dialkali metal monostearyl phosphates (such as K, Na and Li) and phosphates. Hydrocarbons such as paraffins and halogenated paraffins can be used in liquid form. Liquid hydrocarbons are liquids at room temperature and atmospheric pressure and have a pour point of about -40°C to about 50°C and a minimum boiling point of not less than about 110°C (at atmospheric pressure). It is also known to use waxy hydrocarbons, preferably having a melting point below about 100°C. Hydrocarbons constitute a preferred class of suds suppressors for use in detergent compositions. Hydrocarbon suds suppressors are described, for example, in US 4,265,779 (Gandolfo et al., issued May 5, 1981). Thus, hydrocarbons include saturated or unsaturated aliphatic, cycloaliphatic, aromatic and heterocyclic hydrocarbons having from about 12 to about 70 carbon atoms. As used in this suds suppressor discussion, the term "paraffin" is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred class of non-surfactant suds suppressors includes silicone suds suppressors. This category includes the use of polyorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and compositions of polyorganosiloxanes with silica particles, wherein polyorganosiloxane Organosiloxanes are chemisorbed or fused onto silica. Silicone suds suppressors are well known in the art and are disclosed, for example, in US4265779 (Gandolfo et al., issued May 5, 1981) and European Patent Application 89307851.9 (Starch, M.S., published February 7, 1990) .

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

Mixtures of siloxanes and silylated silicas are disclosed, for example, in German patent application DOS2124526. Silicone antifoam and suds control agents in granular detergent compositions are disclosed in US 3,933,672 (Bartolotta et al.) and US 4,652,392 (Baginski et al., issued March 24, 1987).

Illustrative silicone-based suds suppressors for use herein are suds suppressing amounts of suds control agents consisting essentially of:

(i) a polydimethylsiloxane fluid having a viscosity of about 20-1500 cs (25° C.);

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

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

In preferred silicone suds suppressors for use herein, the solvent used for the continuous phase is made from specific polyethylene glycol or polyethylene glycol-polypropylene glycol copolymers or mixtures thereof (preferred), or poly Made of propylene glycol. The primary silicone suds suppressors are branched/crosslinked and preferably non-linear.

To further illustrate this point, a typical liquid laundry detergent composition with suds control optionally includes about 0.001-1% (weight), preferably about 0.01-0.7% (weight), more preferably about 0.05-0.5% (weight ), the silicone suds suppressor comprises: (1) a non-aqueous emulsion of the main antifoam agent, which is (a) polyorganosiloxane, (b) resinous silicon Oxane or siloxane compounds that produce siloxane resins, (c) finely divided filler materials, and (d) catalysts that promote the reaction of mixture components (a), (b) and (c) to form silanolates mixture; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or polyethylene glycol having a solubility in water of greater than about 2% by weight at room temperature and having no polypropylene glycol - Polypropylene glycol copolymer. Similar amounts can be used in granular compositions, gels, and the like. See also US4978471 (Starch, issued December 18, 1990), and US4983316 (Starch, issued January 8, 1991), US5288431 (Huber et al., issued February 22, 1994), and US4639489 and US4749740 (Aizawa et al., column 1, line 46-column 4, line 35).

Silicone suds suppressors herein preferably include polyethylene glycol and polyethylene/polypropylene glycol copolymers, all having an average molecular weight below about 1000, preferably between about 100-800. The polyethylene glycol and polyethylene glycol/polypropylene glycol copolymers herein have a solubility in water at room temperature of greater than about 2%, preferably greater than about 5% by weight.

Preferred solvents herein are polyethylene glycol and polyethylene glycol/polypropylene glycol copolymers having an average molecular weight of less than about 1000, more preferably between about 100-800, most preferably between about 200-400, preferably PPG200/PEG300. Preferably the weight ratio of polyethylene glycol:polyethylene glycol-polypropylene glycol copolymer is between 1:1-1:10, most preferably between 1:3-1:6.

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

Other suds suppressors useful herein include secondary alcohols such as 2-alkyl alkanols and mixtures of the above alcohols with silicone oils such as the silicones disclosed in US4798679, 4075118 and EP150872. The secondary alcohols include C ₆ -C ₁₆ alkyl alcohols having a C ₁ -C ₁₆ chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the tradename ISOFOL12. A mixture of secondary alcohols is available from Enichem under the trade name ISALCHEM123. Mixed suds suppressors generally comprise alcohol + silicone mixtures in a weight ratio of 1:5 to 5:1.

For detergent compositions for use in automatic washing machines, suds should not be formed to such an extent that they overflow the washing machine. When used, the suds suppressor is preferably present in a "foam suppressing amount". By "suds suppressing amount" is meant that the formulator of the composition can select the amount of suds control agent such that suds control is sufficient, resulting in a low sudsing laundry detergent for use in automatic washing machines.

The compositions herein generally include 0 to about 10% suds suppressor. When used as suds suppressors, monocarboxylic fatty acids and their salts are generally present in levels up to about 5% by weight of the detergent compositions. Preferably from about 0.5% to about 3% fatty monocarboxylate suds suppressor is used. Silicone suds suppressors are generally used at levels up to about 2.0% by weight of the composition, although higher levels can also be used. This upper limit is practical, primarily due to the efficiency with which cost is kept to a minimum and lower amounts effectively control foamability. Silicone suds suppressors are preferably used in an amount of about 0.01-1%, more preferably about 0.25-0.5%. As used herein, these weight percent values include any silica that may be used in combination with the polyorganosiloxane, as well as any additional materials that may be used. Monostearyl phosphate suds suppressors are typically used at levels of from about 0.1% to about 2% by weight of the composition. The amount of hydrocarbon suds suppressor used is generally about 0.01-5.0%, although higher amounts can be used. Alcohol suds suppressors are generally used in amounts of 0.2-3% by weight of the final product composition.

Alkoxylated Polycarboxylates - Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described on pages 4 and following of WO91/08281 and PCT90/01815, both of which are incorporated herein by reference. These materials chemically contain polyacrylates with 1 ethoxyl 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-like structure. Its molecular weight can vary, but is generally about 2,000-50,000. Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10% by weight of the compositions herein.

Fabric Softeners - In the compositions of the present invention, various through-the-wash fabric softeners may optionally be used, especially fine-grained smectite clays in US4062647 (Storm and Nirschl, issued December 13, 1977), and Other softener clays known in the art are generally used at levels of about 0.5-10% by weight to launder fabrics while providing fabric softener benefits. Clay softeners may be used in combination with amine and cationic softeners as disclosed in, for example, US4375416 (Crisp et al., issued March 1, 1983) and US4291071 (Harris et al., issued September 22, 1981).

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 essential oils including components such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam essential oil, sandalwood oil, pine oil, cedarwood etc complex mixture. The final fragrance can comprise a very complex mixture of such components. The final perfume will generally comprise from about 0.01 to 2% by weight of the detergent compositions herein, and the individual perfume components can comprise from about 0.0001 to 90% of the final perfume composition.

Several fragrance formulations are described in Example XXI below. Non-limiting examples of perfume ingredients useful herein include: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene , methyl ionone, γ methyl ionone, methyl cedryne, methyl dihydrojasmonate, methyl 1,6,10-trimethyl-2,5,9-cyclododecatriyne -1-yl ketone, 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3,4-tetralin, 4-acetyl-6-tert-butyl- 1,1-Dimethyl-1,2-dihydroindane, p-hydroxyphenylbutanone, benzophenone, methyl β-naphthyl ketone, 6-acetyl-1,1,2,3,3,5 -Hexamethyl-1,2-indane, 5-acetyl-3-isopropyl-1,12,6-tetramethyl-1,2-indane, 1-dodecanal, 4- (4-Hydroxy-4-methylpentyl)-3-cyclohexene-1-carbaldehyde, 7-hydroxy-3,7-dimethyloctanal, 10-undecene-1-al, isohexene Cyclohexyl formaldehyde, formyl tricyclodecane, condensation products of hydroxycitronellal and methyl anthranilic acid, condensation products of hydroxycitronellal and indole, condensation products of phenylacetaldehyde and indole, 2- Methyl-3-(p-tert-butylphenyl)-propionaldehyde, ethyl vanillin, hedione, hexylcinnamaldehyde, amylcinnamaldehyde, 2-methyl-2-(p-isopropylphenyl )-propionaldehyde, coumarin, gamma decanolactone, cyclopentadecanol anhydride, 16-hydroxy-9-hexadecenolide, 1,3,4,6,7,8-hexahydro- 4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran, β-naphthol methyl ether, ambroxane, dodecahydro-3a,6,6,9a-tetra Methylnaphtho[2,1b]furan, cedrol, 5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol, 2-ethyl- 4-(2,2,3-Trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, caryophyllenol, tricyclodecenyl propionate, tricyclodecanyl acetate Alkenyl esters, benzyl salicylate, cedryl acetate, and p-(tert-butyl)cyclohexyl acetate.

Particularly preferred perfume materials are those perfumes 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-tert-butylphenyl)-propanal, 7-acetyl-1,2,3,4,5,6,7, 8-Octahydro-1,1,6,7-tetramethylnaphthalene, benzyl salicylate, 7-acetyl-1,1,3,4,4,6-hexamethyl-1,2,3 , 4-tetralin, p-tert-butylcyclohexyl acetate, methyl dihydrojasmonate, β-naphthol methyl ether, methyl β-naphthyl ketone, 2-methyl-2-(p-isopropylbenzene base)-propionaldehyde, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-γ-2-benzopyran, dodeca Hydrogen-3a,6,6,9a-tetramethylnaphtho[2,1b]furan, anisaldehyde, coumarin, cedrol, vanillin, cyclopentadecanol anhydride, tricyclodecenyl acetate and Tricyclodecenyl Propionate.

Other fragrance materials include: essential oils, balsams, and resins from various sources including, but not limited to: balsam peru, frankincense resin, styrax, cistus resin, nutmeg, cinnamon oil, benzoin resin, coriander and lavender. Other fragrance chemicals include: phenyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, acetic acid 2-(1,1-dimethylethyl)- Cyclohexanol esters, benzyl acetate, and eugenol. A carrier such as diethyl phthalate may be used in the final fragrance composition.

Other Components - Various other components useful in detergent compositions may be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, for liquid Solvents for formulations, solid fillers for stick compositions, etc. If high sudsing is desired, suds boosters such as C ₁₀ -C ₁₆ alkanolamides can be added to the composition, typically in an amount of 1-10% by weight. C ₁₀ -C ₁₄ monoethanols and diethanolamides illustrate general types of such suds boosters. It is also advantageous to use such suds boosters with the high sudsing co-surfactants mentioned above, such as amine oxides, betaines and sultaines. If desired, water-soluble magnesium and/or calcium salts such as _MgCl2 , _MgSO4 , _CaCl2 , _CaSO4, etc. may be added, typically in an amount of 0.1-2%, to provide additional foam and to enhance grease removal performance.

The various detersive components used in the compositions of the present invention may optionally be further stabilized by absorbing said components onto a porous hydrophobic substrate and then coating said substrate with a hydrophobic coating. Preferably, the detersive components are mixed with a surfactant before being absorbed into the porous matrix. In use, the detersive component is released from the substrate into the aqueous wash liquor where it performs its intended detersive function.

To illustrate this technique in more detail, porous hydrophobic silica (trade name SIPERNAT D10, DeGussa) was mixed with a protease solution containing 3-5% _C13-15 ethoxylated alcohol (EO7) nonionic surfactant . Typically, the enzyme/surfactant solution is 2.5 times the weight of silica. The obtained powder is dispersed in silicone oil (various silicone oils with a viscosity in the range of 500-12500 can be used) under stirring. The resulting silicone oil dispersion is emulsified or otherwise incorporated into the final detergent matrix. In this way, components used in detergents, including liquid laundry detergent compositions, such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and Hydrolyzable surfactants.

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

The detergent compositions herein are preferably formulated such that the pH of the wash water for use in aqueous cleaning operations is between about 6.5-11, preferably about 7.5-10.5. The pH of the liquid dishwashing product formulation is preferably between about 6.8-9.0. Laundry products typically have a pH of 9-11. Techniques for controlling pH at recommended usage levels include the use of buffers, bases, acids, etc. and are well known to those skilled in the art.

Form of the Composition - The compositions of the present invention can take a variety of physical forms, including granular, tablet, bar and liquid forms. In particular, the composition is a so-called concentrated granular detergent composition which is suitable for being added to a washing machine by means of a dispensing device which is placed in the drum of the washing machine together with the soiled linen.

The average particle size of the components of the granular composition according to the invention should preferably be such that no more than 5% of the particles have a diameter greater than 1.7 mm and no more than 5% of the particles have a diameter smaller than 0.15 mm.

The term mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The resulting weight fraction is plotted against the pore size of the sieve. The average particle size is the pore size through which 50% by weight of the sample passes.

The bulk density of the granular detergent compositions according to the invention will generally be at least 600 g/l, more preferably from 650 to 1200 g/l. Bulk density is determined by means of a simple funnel and measuring cup arrangement consisting of a conical funnel rigidly mounted on a base and fitted with a flap valve at its lower end to allow the contents of the funnel to empty into a container placed below the funnel. Axially aligned conical measuring cups. The funnel is 130mm high, and the inner diameters of the upper and lower ends are 130mm and 40mm respectively. It is mounted so that the lower end is 140mm above the base. The measuring cup has an overall height of 90mm, an inner height of 87mm and an inner diameter of 84mm. Its nominal volume is 500ml.

For measurement, the funnel is filled with powder by hand pouring, the flap valve is opened and the powder is allowed to flow out of the measuring cup. The filled measuring cup is removed from the base and excess powder is removed through its upper edge with a straight-edged tool such as a knife. The filled measuring cup is then weighed and the value obtained by multiplying the powder weight by 2 provides the bulk density (g/l). Repeat the assay if necessary.

Agglomerate Particles - The cleaning system herein is preferably present in granular compositions in the form of agglomerate particles, which may be in the form of tablets, pellets, pellets, strips, ribbons, but are preferably granules Form. The most preferred method of processing the granules is by agglomerating powders (eg aluminosilicates, carbonates) with high surfactant pastes and controlling the particle size of the resulting agglomerates within specified limits. Such a method comprises combining an effective amount of powder with a high surfactant active paste in one or more agglomerators such as pan agglomerators, Z-blade mixers, or more preferably in series mixers such as those described by Schugi (Holland) BV, 29 Chroomstraat 8211AS, Lelystad, Netherlands and those produced by Gebruder Lodige Maschinenbau GmbH, D-4790 Paderbron 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer such as Lodige CB (trade name) is used.

Typically high surfactant active pastes are used which contain 50-95% by weight, preferably 70-85% by weight, of surfactant. The paste can be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity but low enough to avoid degradation of the surfactant used. The operating temperature of the paste is generally 50-80°C.

Laundry Laundry Process - Machine Laundry Processes herein generally comprise treating soiled garments in a washing machine with an aqueous wash liquor having dissolved or dispersed therein an effective amount of the machine laundry detergent composition of the present invention. With respect to an effective amount of detergent composition, it means that 40-300 g of product is dissolved or dispersed in 5-65 liters of wash solution, which is the typical product dosage and wash solution normally used in conventional machine washing laundry methods volume.

As noted above, the isopeptidases are used herein in cleaning compositions, preferably in combination with a detersive surfactant, in an amount effective to achieve at least an immediate improvement in cleaning performance. In fabric laundry compositions, the above "use levels" can vary depending not only on the type and severity of soils and stains, but also on the wash water temperature, wash water volume and type of washing machine.

For example, in an American-type automatic washing machine with an upper vertical shaft using about 45-83 liters of water in the wash bath, a wash cycle of about 10-14 minutes and a wash water temperature of about 10-50°C, it is preferred to include about 2 - 625 ppm, preferably about 2-550 ppm, more preferably about 10-235 ppm of surfactant. Based on the use ratio of about 50-150ml per wash load, for heavy duty liquid laundry detergents, the concentration (weight) in the product converted to surfactant is about 0.1-40%, preferably about 0.1-35%, more Preferably about 0.5-15%. For dense ("compact") granular laundry detergents (density greater than about 650 g/l), this translates to a surfactant concentration (by weight) of about 0.1 -50%, preferably about 0.1-35%, more preferably about 0.5-15%. Based on a use rate of about 80-100 g per load, for a spray-dried granular (i.e. "fluffy"; density below about 650 g/l) detergent, the concentration (by weight) converted to surfactant in the product is About 0.07-35%, preferably about 0.07-25%, more preferably about 0.35-11%.

For example, in a front-loading horizontal-axis automatic washing machine using about 8-15 liters of water in the wash bath, a wash cycle of about 10-60 minutes and a wash water temperature of about 30-95°C, it is preferred to include about 3-14000 ppm, preferably about 3-10000 ppm, more preferably about 15-4200 ppm of surfactant. Based on the use ratio of about 45-270ml per wash load, for heavy-duty liquid laundry detergents, the concentration (weight) in the product converted into surfactant is about 0.1-50%, preferably about 0.1-35%, more Preferably about 0.5-15%. Based on a use rate of about 40-210 g per wash load, this translates to a surfactant concentration (by weight) of about 0.12 for dense ("compact") granular laundry detergents (density greater than about 650 g/l) -53%, preferably about 0.12-46%, more preferably about 0.6-20%. Based on a use rate of about 140-400 g per load, for a spray-dried granular (i.e. "fluffy"; density below about 650 g/l) detergent, the concentration (by weight) converted to surfactant in the product is About 0.03-34%, preferably about 0.03-24%, more preferably about 0.15-10%.

For example, in a Japanese type automatic washing machine with an upper vertical shaft using about 26-52 liters of water in the wash bath, a wash cycle of about 8-15 minutes and a wash water temperature of about 5-25°C, it is preferred to include about 0.67 - 270 ppm, preferably about 0.67-236 ppm, more preferably about 3.4-100 ppm of surfactant. Based on the use ratio of about 20-30ml per wash load, for heavy duty liquid laundry detergents, the concentration (weight) in the product converted to surfactant is about 0.1-40%, preferably about 0.1-35%, more Preferably about 0.5-15%. For dense ("compact") granular laundry detergents (density greater than about 650 g/l), this translates to a surfactant concentration (by weight) of about 0.1 in the product, based on a use rate of about 18-35 g per wash load -50%, preferably about 0.1-35%, more preferably about 0.5-15%. Based on a use rate of about 30-40 g per load, for spray-dried granular (i.e. "fluffy"; density below about 650 g/l) detergents, the concentration (by weight) in the product converted to surfactant is About 0.06-44%, preferably about 0.06-30%, more preferably about 0.3-13%.

From the above it can be seen that the amount of isopeptidase used in machine laundry can vary depending on the habits and practices of the user, the type of washing machine, etc. In this respect, however, a hitherto unknown advantage of isopeptidases is their ability to provide at least immediate improvements in performance on various soils and stains, even when used in relatively low levels in the final composition The same is true when.

In a preferred aspect of use, the dispensing device is used in a washing method. The dispensing device is filled with detergent product and is used to introduce the product directly into the drum of the washing machine before the wash cycle begins. Its volumetric capacity should be such that it can contain enough detergent product as is normally used in the washing process.

Once the washing machine is loaded with clothes, the dispensing unit containing the detergent product is placed into the drum. At the beginning of a washing cycle of the washing machine, water is introduced into the drum and the drum rotates periodically. The design of the dispensing device should be such that it can contain dry detergent product which is then released during the wash cycle as it is agitated (due to the rotation of the drum) and also as a result of contact with the wash water.

To facilitate the release of detergent product during washing, the device may have a plurality of apertures through which detergent product may pass. Alternatively, the device can be made of a material that is permeable to liquids but not solid products, which can release the dissolved product. Preferably, the detergent product is released rapidly at the beginning of the wash cycle to provide a temporary localized high concentration of product in the drum of the washing machine during the wash cycle.

Preferred dispensing devices are reusable and are designed in such a way that the integrity of the container is maintained both in the dry state and during a wash cycle. Particularly preferred dispensing devices for use in the compositions of the invention have been described in the following patents: GB-B-2157717, GB-B-2157718, EP-A-0201376, EP-A-0288345 and EP-A-0288346 . A particularly preferred dispensing device for granular laundry products is also described by J. Bland in Manufacturing Chemist, November 1989, pages 41-46, of the type commonly referred to as "granulette". Another preferred dispensing device for use with the detergent compositions herein is disclosed in PCT patent application WO 94/11562.

Particularly preferred dispensing devices are disclosed in European Patent Application Publication Nos. 0343069 and 0343070. The latter application discloses a device comprising a flexible sheath in the form of a bag extending from a support ring defining an orifice leading to the bag with sufficient product for one wash cycle in the washing process. A portion of the wash medium flows into the bag through the orifice, dissolves the product, and the solution then flows out through the orifice into the wash medium. The support ring is provided with shielding means to prevent the outflow of wet undissolved product, the means generally comprising a radially extending wall or similar structure extending from a central hub in a spoked wheel configuration, wherein the wall has the form of a helix.

Alternatively, the dispensing device may be a flexible container, such as a bag or a box. The bag may be a fibrous structure coated with a water-impermeable protective material to retain its contents, such as disclosed in European Patent Application 0018678. Alternatively, it may be formed from a water-insoluble synthetic polymeric material with edge seals or closures designed to rupture in aqueous media, as disclosed in European Published Patent Application Nos. 0011500, 0011501, 0011502 and 0011968 . A convenient form of water frangible closure comprises a water soluble adhesive which is placed along one side of a bag formed of a water impermeable polymeric film such as polyethylene or polypropylene and seals it.

The liquid compositions of the present invention are preferably in "concentrated form"; in this case, the liquid detergent compositions of the present invention contain lower amounts of water compared to conventional liquid detergents. The water level is less than 50%, preferably less than 30% by weight of the detergent composition.

Said concentrated product offers advantages to the consumer, who gets a product that can be used in lower quantities, and the producer, who gets lower shipping costs.

Liquid compositions are particularly effective when applied directly to soils and stains in a pretreatment step prior to laundering of fabrics.

The detergent compositions of the present invention can also be used as detergent additive products. Such additive products are intended to supplement or enhance the performance of conventional detergent compositions.

The detergent compositions of the present invention include compositions for cleaning articles such as fabrics, fibers, hard surfaces, etc., such as hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, automatic and Non-automatic dishwashing compositions.

Composition packaging

Commercially available embodiments of the bleaching compositions may be packaged in any suitable container including those constructed from paper, paperboard, plastics material and any suitable laminate. A preferred packaging embodiment is described in European Patent Application 94921505.7.

In the following examples, the abbreviations used for the various components in the composition have the following meanings:

LAS: Sodium linear _C12 alkylbenzene sulfonate

Isopeptidase: called "destabilase" (SEQ ID No.7)

isopeptidase

C45AS: Sodium C ₁₄ -C ₁₅ Linear Alkyl Sulfate

CxyEzS: _C1x - _C1y branched alkylsulfide condensed with z moles of ethylene oxide

Sodium Sodium Acid

CxyEz: C1x _-1y branched primary alcohol condensed with average Z moles of ethylene oxide

QAS: R ₂ ·N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), R ₂ =C ₁₂ -C ₁₄

TFAA: C ₁₆ -C ₁₈ Alkyl N-methyl Glucamide

STPP : Anhydrous sodium tripolyphosphate

Zeolite A: the primary particle size of formula Na ₁₂ (AlO ₂ SiO) ₁₂ .27H ₂ O is 0.1-10

Micron Sodium Aluminosilicate Hydrate

NaSKS-6: crystalline layered silicate _{of the} formula δ- _Na2Si2O5

Carbonate: anhydrous sodium carbonate with particle size between 200-900μm

Sodium bicarbonate: anhydrous sodium bicarbonate with particle size between 400-1200μm

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

Sodium Sulfate : Anhydrous Sodium Sulfate

MA/AA : 1:4 maleic acid/acrylic acid copolymer, the average molecular weight is about

70000

CMC : Sodium Carboxymethyl Cellulose

Protease: sold under the tradename Savinase by NOVO Industries A/S

The activity of 4KNPU/g protease

Cellulase: marketed under the tradename Carezyme by NOVO Industries A/S

A cellulase with an activity of 1000 CEVU/g

Amylase: sold by NOVO Industries A/S under the trade name Termamyl 60T

Amylolytic enzyme sold with an activity of 60KNU/g

Lipase: marketed under the tradename Lipolase by NOVO Industries A/S

                                         

PB4: Sodium perborate four with the nominal formula NaBO ₂ 3H ₂ O H ₂ O ₂

Hydrate

PB1: anhydrous sodium perborate bleach with nominal formula _{NaBO2 · H2O2}

Percarbonate: sodium percarbonate with the nominal formula 2Na ₂ CO ₃ .3H ₂ O ₂

NaDCC : Sodium Dichloroisocyanurate

NOBS : Nonanoyloxybenzenesulfonate in the sodium salt form

TAED : Tetraacetylethylenediamine

DTPMP : Diya sold under the trade name Dequest2060 by Monsanto

                                  Ethyltriamine Penta(Methylene Phosphonate)

Photoactivated Bleach: Sulfonated Zinc Phthalocyanine Encapsulated in Dextrin-Soluble Polymer

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

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

                                                    

HEDP ： 1,1-Hydroxyethane diphosphonic acid

SRP1 : Sulfobenzene with oxyethyleneoxy and terephthaloyl backbone

Formyl-terminated esters

Polysiloxane anti-foaming agent: a polydiethylene oxide containing a siloxane-oxyalkylene copolymer as a dispersant

       Methylsiloxane suds control agent, said suds control agent and said

The ratio of dispersant is 10:1-100:1

DTPA : Diethylenetriaminepentaacetic acid

In the following examples, all contents are percentages by weight of the composition. The following examples illustrate the invention without limiting or otherwise defining its scope. All parts, percentages and ratios used herein are expressed as percent by weight unless otherwise indicated.

Example 1

The following laundry detergent compositions AF were prepared in accordance with the present invention. These compositions can be used in machine or hand washing methods, including as a pre-soak prior to machine laundry methods. A B C D. E. f Isopeptidase 0.26 0.26 0.26 0.26 0.26 0.26 C25E3 3.4 3.4 3.4 3.4 3.4 3.4 LAS 20 20 15 17 twenty two 14 QAS - - 0.8 - - 0.8 Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1 carbonate 13.0 13.0 13.0 27.0 27.0 27.0 Silicate 1.4 1.4 1.4 3.0 3.0 3.0 sodium sulfate 26.1 26.1 26.1 26.1 26.1 26.1 PB4 - - - 9.0 9.0 9.0 TAED - - - 1.5 1.5 1.5 DETPMP 0.25 0.25 0.25 0.25 0.25 0.25 HEDP 0.3 0.3 0.3 0.3 0.3 0.3 protease 0.26 0.26 0.26 0.26 0.26 0.26 Amylase 0.1 0.1 0.1 0.1 0.1 0.1 MA/AA 0.3 0.3 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 Photoactivated Bleach (ppm) 15ppm 15ppm 15ppm 15ppm 15ppm 15ppm Brightener ¹ 0.09 0.09 0.09 0.09 0.09 0.09 spices 0.3 0.3 0.3 0.3 0.3 0.3 Polysiloxane Antifoam Agent 0.5 0.5 0.5 0.5 0.5 0.5 Other/minor components to 100% Density, g/l 850 850 850 850 850 850

Example 2

The following granular laundry detergent compositions with a bulk density of 750 g/l were prepared according to the invention: G h I Isopeptidase 0.26 0.85 0.85 C45AS - 2.24 3.89 C25AE3S - 0.76 1.18 C45E7 325 - 5.0 C25E3 - 5.5 - QAS 0.8 2.0 2.0 STPP 10.7 - - Zeolite A 10.7 19.5 19.5 SKS-6 - 10.6 10.6 carbonate 6.1 21.4 21.4 Bicarbonates - 2.0 2.0 Silicate 6.8 - - sodium sulfate 39.8 - 14.3 PB4 5.0 12.7 8.0 TAED 0.5 3.1 - DETPMP 0.25 0.2 0.2 HEDP - 0.3 0.3 protease 0.26 0.85 0.85 Lipase 0.15 0.15 0.15 cellulase 0.28 0.28 0.28 Amylase 0.1 0.1 0.1 MA/AA 0.8 1.6 1.6 CMC 0.2 0.4 0.4 Photoactivated Bleach (Ppm) 15ppm 27ppm 27ppm Brightener ¹ 0.08 0.19 0.19 bleach ² - 0.04 0.04 spices 0.3 0.3 0.3 Polysiloxane Antifoam Agent 0.5 2.4 2.4 Minor components/other components to 100%

Example 3

The following detergent formulations according to the invention were prepared: J K L m LAS 15.0 14.0 14.0 18.0 Isopeptidase 0.8 1.0 0.5 0.5 TFAA - 1.0 - - C25E5/C45E7 - 2.0 - 0.5 C45E3S - 2.5 - - Zeolite A 30.0 18.0 30.0 22.0 Silicate 9.0 5.0 10.0 8.0 carbonate 13.0 7.5 - 5.0 Bicarbonates - 7.5 - - DTPMP 0.7 1.0 - - SRP 1 0.3 0.2 - 0.1 MA/AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2 protease 0.8 1.0 0.5 0 5 Amylase 0.8 0.4 - 0.25 Lipase 0.2 0.1 0.2 0.1 cellulase 0.15 0.05 - - Photoactivated Bleach (ppm) 70ppm 45ppm - 10ppm Brightener 1 0.2 0.2 0.08 0.2 PB1 6.0 2.0 5.0 3.0 NOBS 2.0 1.0 - - Polyethylene oxide, MW5,000,000 - 0.2 - 0.2 Bentonite - - - 10.0 Balance (moisture and other components) 100 100 100 100

Example 4

The following high density detergent formulations of the present invention were prepared: N o Agglomerates C45AS 11.0 14.0 Isopeptidase 1.4 1.4 Zeolite A 15.0 10.0 carbonate 4.0 8.0 MA/AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 spray on C25E5 5.0 5.0 spices 0.5 0.5 dry addition C ₂₀ SADS 6.0 3.0 HEDP 0.5 0.3 SKS-6 13.0 6.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 20.0 20.0 SRP1 0.3 0.3 protease 1.4 1.4 Lipase 0.4 0.4 cellulase 0.6 0.6 Amylase 0.6 0.6 Polysiloxane Antifoam Agent 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 - Balance (moisture and other components) 100 100 Density (g/l) 850 850

Example 5

A liquid detergent composition was prepared according to the following formula:

% by weight of detergent composition A B C D. C ₂₅ AE3S 2 8 7 5 Isopeptidase 0.5 0.5 0.5 0.5 C ₁₂ -C ₁₄ Alkyl Dimethylamine Oxide - - - 2 C ₂₅ AS 15 12 8 8 C ₂₄ N-methylglucamide 5 4 3 3 C ₂₄ AE5 6 1 1 1 C ₁₂ -C ₁₈ fatty acids 11 4 4 3 citric acid 1 3 3 2 DTPMP 1 1 1 0.5 MEAs 8 5 5 2 NaOH 1 2.5 1 1.5 PG 14.5 13.1 10.0 8 EtOH 1.8 4.7 5.4 1 Amylase (300KNU/g) 0.1 0.1 0.1 0.1 Lipase D96/L (100KNU/g) 0.15 0.15 0.15 0.15 Protease (35g/l) 0.5 0.5 0.5 0.5) Endoenzyme 0.05 0.05 0.05 0.5 cellulase 0.09 0.09 0.09 0.9 terephthalate-based polymers 0.5 - 0.3 0.3 boric acid 2.4 2.8 2.8 2.4 Sodium xylene sulfonate - 3 - - 2-Butyl octanol 1 1 1 1 branched polysiloxane 0.3 0.3 0.3 0.3 water and minor components to 100%

^* SEASA is an isethionate ethoxylated ester of an alpha-sulfonated _C16 / _C18 fatty acid.

The above liquid detergent compositions (A-D) were found to be very effective in removing various stains and soils from fabrics under various conditions of use.

Example 6-11

The following is a heavy duty liquid laundry detergent composition according to the present invention. Example Number: 6 7 8 9 10 11 isterinase 0.6 0.9 0.9 1.2 1.2C25 AS 10 8.0-5.0 5.0C35AE3S/C25AE3S 2.0 9.0-7.0C24 N-methyl glucosamide 6.0 5 0 4.5 3.7 4.0 4.0C35 E7              6.0    1.0    -      -      -      -C25 AE2.5S          -      -      12.0   12.0   -      -C23 E9              -      -      2.0    1.0    5.0    5.0C10 APA             -      1.5    -      2.0    -      2.5C24脂肪酸           7.5    1.1    2.0    4.0    5.0    5.0C48脂肪酸           3.0    3.5    -      -      - -Pugeonic acid 1.0 3.5 3.0 3.0 3.0 3.0 protease (34g/#) 0.6 0.6 0.9 0.9 1.2 1.2 lipase 0.1 0.1 0.1 0.2 0.2 amylase (300kmu/g) 0.1 0.1 0.1 0.03 0.05.05 0.2 0.2 0.2 endrazy 0.1 0.---0.1 0.1 0.1---boric acid 3.0 3.0 3.5 4.0 4.0Mea 8.0 4.0 1.5 7.0naoh 1.0 4.0 3.0 1.0pg 12.0 12.0 7.5 7.0 7.0ETOH 1.0 1.0 3.5 3.5 6.0 6.0Na TS                                                                         

The production of heavy duty liquid detergent compositions, especially those designed for fabric laundering, containing a non-aqueous carrier medium can be carried out as disclosed in more detail hereinafter. In another method, such non-aqueous compositions can be prepared according to the disclosure of the following patent documents: US4753570, US4767558, US4772413, US4889652, US4892673, GB-A-2158838, GB-A-2195125, GB-A-2195649 , US4988462, US5266233, EP-A-225654 (6/16/87), EP-A-510762 (10/28/92), EP-A-540089 (5/5/93,) EP-A-540090 ( 5/5/93), US4615820, EP-A-565017 (10/13/93), EP-A-030096 (6/10/81), which are incorporated herein by reference. Such compositions may contain various particulate detersive ingredients (including bleach, as disclosed above) stably suspended therein. Such non-aqueous compositions thus comprise a liquid phase, and optionally but preferably a solid phase, as described in more detail hereinafter and in the cited literature. The isopeptidases are incorporated into the compositions in the methods and levels described hereinabove to prepare other laundry detergent compositions.

liquid phase

The liquid phase will generally comprise from about 35% to about 99% by weight of the detergent compositions herein. More preferably, the liquid phase comprises from about 50% to about 95% by weight of the composition. Most preferably, the liquid phase comprises about 45-75% by weight of the compositions herein. The liquid phase of the detergent compositions herein essentially contains a relatively high concentration of a particular type of anionic surfactant in combination with a particular type of non-aqueous liquid diluent.

(A) Basic anionic surfactants

The anionic surfactants used primarily as an essential component of the non-aqueous liquid phase are selected from the group consisting of alkali metal salts of alkylbenzenesulfonic acids in a linear or branched configuration in which the alkyl group contains about 10-16 carbon atoms. (See US2220099 and US2477383, both of which are incorporated herein by reference.) Particularly preferred are sodium and potassium linear alkylbenzene sulfonates (LAS) wherein the average number of carbon atoms in the alkyl group is about 11-14 . Sodium C ₁₁ -C ₁₄ LAS is particularly preferred.

The alkylbenzene sulfonate anionic surfactant is dissolved in the non-aqueous liquid diluent which constitutes the second essential component of the non-aqueous phase. To form the structured liquid phase required for suitable phase stability and acceptable rheological properties, the alkylbenzenesulfonate anionic surfactant is typically present in an amount of about 30-65% of the liquid phase. More preferably, the alkylbenzenesulfonate anionic surfactant comprises from about 35% to about 50% by weight of the non-aqueous liquid phase of the compositions herein. Use of this anionic surfactant at these concentrations corresponds to an anionic surfactant concentration in the total composition of about 15-60%, more preferably about 20-40% by weight of the composition.

(B) Non-aqueous liquid diluent

To form the liquid phase of the detergent composition, the alkylbenzenesulfonate anionic surfactants described hereinabove are mixed with a non-aqueous liquid diluent comprising 2 essential components. The 2 components are a liquid alcohol alkoxylate material and a non-aqueous low polarity organic solvent.

i) Alcohol Alkyl Hydrogenate

An essential component of the liquid diluent used to form the compositions herein includes an alkoxylated fatty alcohol material. Such materials are themselves also nonionic surfactants. Such materials correspond to the general formula:

R ¹ (C _m H _2m O) _n OH

Wherein R ¹ is C ₈ -C ₁₆ alkyl, m is 2-4, and n is in the range of about 2-12. Preferably ^R1 is an alkyl group, which may be primary or secondary, containing about 9-15 carbon atoms, more preferably about 10-14 carbon atoms. It is also preferred that the alkoxylated fatty alcohol is an ethoxylated material containing from about 2 to about 12 ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol component of the liquid diluent often has a hydrophilic-lipophilic balance (HLB) in the range of about 3-17. More preferably the material has an HLB in the range of about 6-15, most preferably about 8-15.

Examples of fatty alcohol alkoxylates useful as one of the essential components of the non-aqueous liquid diluent in the compositions herein include those prepared from 12 to 15 carbon atoms and containing about 7 moles of ethylene oxide. Such materials are sold by the Shell Chemical Company under the trade names Neodol 25-7 and Neodol 23-6.5. Other useful Neodols include: Neodol 1-5, an ethoxylated fatty alcohol having about 5 moles of ethylene oxide having an average of 11 carbon atoms in the alkyl chain; Neodol 23-9, having about 9 moles of ethylene oxide Ethoxylated C ₁₂ -C ₁₃ primary alcohols of alkanes and Neodol 91-10, C ₉ -C ₁₁ primary alcohols with about 10 moles of ethylene oxide. Alcohol ethoxylates of this type are also sold under the tradename Donanol by Shell Chemical Company. Dobanol 91-5 is an ethoxylated C ₉ -C ₁₁ fatty alcohol with an average of 5 moles of ethylene oxide, and Donoal 25-7 is an ethoxylated C ₁₂ with an average of 7 moles of ethylene oxide per mole of fatty alcohol -C ₁₅ fatty alcohol.

Other examples of suitable ethoxylated alcohols include the linear primary alcohol ethoxylates Tergitol 15-S-7 and Tergitol 15-S-9, both sold by Union Carbide Corporation. The former is a mixed ethoxylation product of C ₁₁ -C ₁₅ straight chain primary alkanol and 7 moles of ethylene oxide, and the latter is a mixture of C ₁₁ -C ₁₅ straight chain primary alkanol and 9 moles of ethylene oxide Mix ethoxylation products.

Other types of alcohol ethoxylates useful in the compositions of the present invention are high molecular weight nonionic surfactants such as Neodol 45-11, which is the ethylene oxide condensation product of similar higher aliphatic alcohols having 14 - 15 carbon atoms, the number of oxirane groups per mole is about 11. Such products are sold by Shell Chemical Company.

The alcohol alkoxylate component, which is used primarily as part of the liquid diluent in the non-aqueous compositions herein, is generally present in an amount from about 1% to about 60% of the liquid phase composition. More preferably the alcohol alkoxylate component comprises about 5-40% of the liquid phase. Most preferably, the predominantly used alcohol alkoxylate component comprises from about 5% to about 30% of the liquid phase of the detergent compositions. Use of the alcohol alkoxylate in the liquid phase at such concentrations corresponds to an alcohol alkoxylate concentration in the total composition by weight of the composition of about 1-60%, more preferably about 2-40%, most preferably About 5-25%.

ii) Non-aqueous, low-polarity organic solvents

A second essential component of the liquid diluent which forms part of the liquid phase of the detergent compositions herein comprises a non-aqueous, low polarity organic solvent. The term "solvent" as used herein refers to the non-surface-active carrier or diluent portion of the liquid phase of a composition. While some of the essential and/or optional components of the compositions herein may actually be dissolved in the "solvent" containing liquid phase, other components will appear as particles dispersed in the "solvent" containing liquid phase. exist. The term "solvent" therefore does not imply that the solvent material is capable of actually dissolving all detergent composition components added thereto.

The non-aqueous organic materials used herein as solvents are liquids of low polarity. For the purposes of the present invention, a "low polarity" liquid is one that has very low, if any, solubility for peroxygen bleach, sodium perborate, or sodium percarbonate, one of the preferred types of particulate material for use in the compositions herein. tendency. Therefore relatively polar solvents such as ethanol should not be used. Suitable types of low polarity solvents useful in the non-aqueous liquid detergent compositions herein include: non-vicinal _C4 - _C8 alkylene glycols, alkylene glycol mono-lower alkyl ethers, Low molecular weight polyethylene glycol, low molecular weight methyl ester and amide, etc.

A preferred class of nonaqueous low polarity solvents for use in the compositions herein include: non-vicinal _C4 - _C8 branched or linear alkylene glycols. Such materials include: hexanediol (4-methyl-2,4-pentanediol), 1,6-hexanediol, 1,3-butanediol and 1,4-butanediol. Hexylene glycol is most preferred.

Another class of preferred non-aqueous low polarity solvents for use herein include: mono-, di-, tri- or tetra _-C2 - _C3 alkylene glycol mono _-C2 - _C6 alkyl ethers. Specific examples of such compounds include diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are particularly preferred. Such compounds have been marketed under the tradenames Dowanol, Carbitol and Cellosolve.

Another class of preferred non-aqueous low polarity organic solvents useful herein includes low molecular weight polyethylene glycols (PEG). Such materials are those having a molecular weight of at least about 150. PEGs with molecular weights in the range of about 200-600 are most preferred.

Yet another class of preferred non-polar, non-aqueous solvents includes low molecular weight methyl esters. Such materials are those of the general formula: R ¹ —C(O)—OCH ₃ , where R ¹ is in the range of 1 to about 18. Examples of suitable low molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate and methyl dodecanoate.

Of course, the non-aqueous low polarity organic solvents used should be compatible and non-reactive with other composition ingredients such as bleaches and/or activators used in the liquid detergent compositions herein. Such solvent components are typically used in amounts of about 1-70% by weight of the liquid phase. More preferably, the non-aqueous low polarity organic solvent comprises about 10-60% by weight of the liquid phase of the composition, most preferably about 20-50%. Use of the organic solvent in such concentrations in the liquid phase corresponds to a solvent concentration in the total composition of about 1-50%, more preferably about 5-40%, most preferably about 10-30% by weight of the composition.

iii) Alcohol alkoxylate to solvent ratio

The ratio of alcohol alkoxylate to organic solvent in the liquid diluent can be used to modify the rheological properties of the final detergent composition. Typically the weight ratio of alcohol alkoxylate to organic solvent is in the range of about 50:1 to 1:50. More preferably, this ratio is in the range of about 3:1-1:3.

iv) Concentration of liquid diluent

With regard to the concentration of alkylbenzenesulfonate anionic surfactant, the total amount of liquid diluent in the non-aqueous liquid phase herein is determined by the type and amount of other composition components and by the desired properties of the composition. The liquid diluent generally comprises about 35-70% of the non-aqueous liquid phase of the compositions herein. More preferably the liquid diluent comprises about 50-65% of the non-aqueous liquid phase. This corresponds to a non-aqueous liquid diluent concentration in the total composition of about 15-70%, more preferably about 20-50% by weight of the composition.

solid phase

The non-aqueous detergent compositions herein also essentially comprise from about 1 to 65% by weight, more preferably from about 5 to 50% by weight, of a solid phase of particulate material dispersed and suspended in the liquid phase. Typically such particulate material will have a particle size in the range of about 0.1-1500 microns. More preferably such materials have a particle size in the range of about 5-200 microns.

The particulate material for use herein may comprise one or more types of detergent composition components which are in particulate form substantially insoluble in the non-aqueous liquid phase of the composition. Such particulate materials which may be used are detailed below:

Composition preparation and use

The non-aqueous liquid detergent compositions herein may be prepared by admixing the essential and optional components of the composition in any convenient order, and by mixing, e.g. stirring, the resulting mixture of components to form the phase stable compositions herein. . In the general method of preparing the compositions, the essential and certain preferred optional ingredients are mixed in a specific order and under specific conditions.

In step 1 of the above general preparation method, a mixture of the 2 essential components of an alkylbenzenesulfonate anionic surfactant and a non-aqueous diluent is formed by heating a mixture of these materials to a temperature of about 30-100°C .

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

In the third process step, the liquid phase mixture of materials is cooled to a temperature of about 0-35°C. This cooling step functions to form a structured surfactant-containing liquid base into which the particulate material of the detergent compositions herein can be added and dispersed.

In a 4th process step, the particulate material is added by mixing it with a liquid base maintained under shear stirring conditions. When more than one particulate material is to be added, it is preferred to observe a specific order of addition. For example, substantially all of the optional surfactant may be added as solid particles in the form of particles having a particle size in the range of about 0.2-1000 microns while shear agitation is maintained. Subsequent to the addition of any optional surfactant particles, substantially all of the organic builder such as citrate and/or fatty acid and/or particles of an alkalinity source such as sodium carbonate can be added while continuing to mix the composition components Maintain under shear stirring conditions. At this point, other optional components in solid form can then be added to the composition. Stirring of the mixture is continued and, if desired, can be increased at this point to form a uniform dispersion of insoluble solid phase particles in the liquid phase.

After some or all of the above solid materials have been added to the stirred mixture, granules of bleaching agent can be added to the composition while maintaining the mixture under shear agitation. Desirable bleach stabilization benefits can be obtained by adding the bleach material last or after all or most of the other components, and especially after the alkalinity source particles have been added. If enzyme pellets are added, they are preferably added last to the non-aqueous liquid matrix.

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

As a variation on the method of preparing the compositions described above, one or more solid components may be added to the agitated mixture as a slurry of particles premixed with a minor portion of one or more liquid components. Thus, a pre-mixture of a small portion of alcohol alkoxylate and/or non-aqueous low polarity solvent with particles of organic builder material and/or particles of inorganic alkalinity source and/or particles of bleach activator, respectively, can be formed and It is added as a slurry to the stirred mixture of composition components. The addition of the above slurry premix should precede the addition of bleach and/or enzyme granules which themselves may form part of the premix slurry in a similar manner.

Compositions of the invention prepared as described above can be used to form aqueous laundering solutions for fabric laundering and bleaching. It is generally preferred to add an effective amount of the above compositions to water in a conventional fabric laundering automatic washing machine to form such an aqueous wash/bleach solution. The aqueous wash/bleach solution so formed is then contacted, preferably under agitation, with the fabrics to be washed and bleached therewith.

An effective amount of the liquid detergent compositions herein when added to water to form an aqueous wash/bleach solution can include an amount sufficient to form about 500-7000 ppm of the composition in aqueous solution. More preferably, about 800-3000 ppm of the detergent compositions of the present invention are provided in the aqueous wash/bleach solution.

Example 12

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

Table I

Component Wt.% Range (%wt.) Liquid Phase C ₁₂ Sodium Linear Alkylbenzene Sulfonate (LAS) 25.3 18-35 Isopeptidase 0.4 0.01-1C _12-14 , EO5 Alcohol Ethoxylate 13.6 10- 20 hexanediol 27.3 20-30 fragrance 0.4 0-1.0 solid protease 0.4 0-1.0 trisodium citrate anhydrous 4.3 3-6 sodium perborate 3.4 2-7 sodium nonanoyloxybenzenesulfonate (NOBS) 8.0 2- 12 Sodium carbonate 13.9 5-20 Diethyltriaminepentaacetic acid (DTPA) 0.9 0-1.5 Brightener 0.4 0-0.6 Foam suppressor 0.1 0-0.3 Minor component balance...

The resulting composition is a stable anhydrous heavy duty liquid laundry detergent which provides excellent stain and soil removal performance when used in normal fabric laundering operations. With respect to hand dishwashing liquids, the following examples further illustrate the invention.

Example 13 Component % (wt.) Range (% wt.) Isopeptidase 0.5 0.01-1C _12-13 Alkyl ammonium sulfate 7.0 2-35C ₁₂ -C ₁₄ Ethoxy (1) sulfate 20.5 5-35 Coconut Amine Oxide 2.6 2-5 Betaine/Tetronic 704 ^** 0.87-0.10 0-2 (Mixture) Alcohol Ethoxylates C ₈ E ₁₁ 5.0 2-10 Ammonium Xylene Sulfonate 4.0 1-6 Ethanol 4.0 0-7 Ammonium Citrate 0.06 0-1.0 Magnesium Chloride 3.3 0-4.0 Calcium Chloride 2.5 0-4.0 Ammonium Sulfate 0.08 0-4.0 Hydrogen Peroxide 200ppm 10-300ppm Fragrance ^0.18 0-0.5 Maxatase® Protease 0.50 0-1.0 Water and Minor Components ……………Balance…………… ^** Coconut Alkyl Betaine

Sequence Listing (1) Information of SEQ ID NO: 1:

(i) Sequential features:

(A) Length: 557 base pairs

(B) Type: nucleic acid

(C) Chain type: single chain

(D) Topological configuration: linear

(ii) Molecule type: DNA (genomic)

(iii) Sequence description: SEQ ID NO: 1GAACTGGCAA TCTTAATATC TCACTA ATG AAT TAC GTT ATC TTT GTG GTC TTA 53

                                                                                                                    , 

1               5GTG GCA CTT TAC GTC ATC GAG GTA GCG AAG TGC ACC GTC CCA TCC GAT         101Val Ala Leu Tyr Val Ile Glu Val Ala Lys Cys Thr Val Pro Ser Asp10                 15                   20                  25TGC TTG AGG TGC ATT TGC CAG GTA GAG GGA TGT AAC AAT GAG ATT GGA 149Cys Leu Arg Cys Ile Cys Gln Val Glu Gly Cys Asn Asn Glu Ile Gly

30 35 40AGG TGC GCA GCA GCA GGA AGT CTG AGC TGT GGT CCT TAG ATC 197ARG CYS GLY MET ALA GLE ALA GLE ALA GLE Leu Serle

45 50 55AAG GAG CCC TAC AGG AGG Att GAC TGT GGA AGG CCA GGA GGA GGA TAG 245LYS GLU Pro Tyr ARG ILE ARG Pro GLY GLY GLY GLY Ty Ty Ty Ty Ty Ty Ty TY TY TY TY TY TIR bi's's

60 65 70CAG TGC AAG GAG GAG GCA TGT GAA AGG TGT GTC CAC GCT TAC 293GLN CYS GLU LYS Ala Cys Val His Ala Tyr Tyr

75                  80                  85ATG GAC AGG TAT GCC AGA AGG TGT ACT GGA GGA CGC CAA CCG ACC TGC         341Met Asp Arg Tyr Ala Arg Arg Cys Thr Gly Gly Arg Gln Pro Thr Cys90                  95                 100                 105CAA GAC TAC GCC AAA ATT CAC AAC ATG GGA CCG AAC GGA TGC CAA TCT 389Gln Asp Tyr Ala Lys Ile His Asn Met Gly Pro Asn Gly Cys Gln Ser

110 115 120TCA AAC AAC CAC TAC TAC TGG GAT AAT GTC AGG AGA TGT TGT TGA 434SER Asn His Tyr Ty ASN Val

125 135AgGAAGAAGGGGAacaacaaca TTGCCTCAAG GTGGCCAAGAAGAGGGGTGTGA 494TGTAAAAAAAAAAGNCA TTTTTTTTTTAAATAC CAAATGAAAATGAATGAATGAATGAATGAATGAATGAATGAATGAATAAATAAATAATAAAAT.

(i) Sequential features:

(A) Length: 136 amino acids

(B) Type: amino acid

(D) Topological configuration: linear

(ii) Molecule type: protein

(III) Sequence description: SEQ ID NO: 2MET Asn Tyr Val Ile PHE Val Val Leu Val Ala Leu Tyr Val Ile Glu1 5 10 15VAL ALA LYS ThR Val ASP CYS Leu ARG CYS Ile Cys Ile Cys Gln Gln

20 25 25 30Val Glu Gly Cys Asn Asn Glu Ile Gly Arg Cys Gly Met Asp Ala Gly

35 40 45Sar Leu Ser Cys Gly Pro Tyr Gln Ile Lys Glu Pro Tyr Arg Ile Asp

50 55 60CYS GLY ARG Pro GLY GLY GLY TYR GLN GLN GLN CYS GLU LYS ALA65 70 75 80CLU ARG CYS Val His Ala Tyr Met Ala ARA ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG ARG Arg

85 90 95Cys Thr Gly Gly Arg Gln Pro Thr Cys Gln Asp Tyr Ala Lys Ile His

100 105 110Asn Met Gly Pro Asn Gly Cys Gln Ser Ser Asn Asn His Tyr Trp Asp

115 120 125Asn Val Arg Arg Cys Leu Gly *

130 135(3) Information of SEQ ID NO: 3:

(i) Sequential features:

(A) Length: 571 base pairs

(B) Type: nucleic acid

(C) Chain type: single chain

(D) Topological configuration: linear

(ii) Molecule type: DNA (genomic)

(iii) Sequence description: SEQ ID NO: 3CTTGAGCTGA ACTGACAATC TTAATATCTC ACTG ATG AAT TAC GTT ATC TTT 52

                Met Asn Tyr Val Ile Phe

1 5GTG GTC TTA GCA CTT TAC GTC GAG GCG AAGC GTC ACC GTT 100VAL VAL ALA Leu Tyr Val Ile Glu Val Ala Lys Cys

10 15 20CCA TCC GAC TTG AGT TGC ATT TGC GAG GAG GAG GAG GAC AAA 148pro Ser AS Leu Serle Cys Ile Cys GLU GLU GLY CYS ASP LYS

25 30 35gag att GGC GGC GGC GGC GCA GCA GGA AGT CTGC TGT GGT GGT GGT CCT

40                  45                  50TAC CAG ATC AAG GAG CCC TAC TGG ATT GAC TGT GGA AGT CCA GGA GCA        244Tyr Gln Ile Lys Glu Pro Tyr Trp Ile Asp Cys Gly Ser Pro Gly Ala55                  60                  65                  70GGA TAC CAG GAG TGC ACT AAG GAG AAG GCA TGT TCC GAA ACG TGT GTC 292Gly Tyr Gln Glu Cys Thr Lys Glu Lys Ala Cys Ser Glu Thr Cys Val

75 80 85NAC NCT TAC AGG TAC AGG TAT NCC AGG TGT ACT CGA GGN NAA 340xaa Tyr Met ARG TYR XAA THR ARG GLY XAA

90 95 100CCG ACC TGC CAA GAC TAC GCC AAA Att Cac AAC ATG GGA CCG AAC GGG 388Pro ThR CYS GLN ALA LYS ILE Nis Ile Nis ASN GLY

105 110 115TGC AGA CGT AGC AGC ACC TAC TAC TGG AAC AAA GCC AAT GCG TGT CTG 436CY ARG THR Serp Asn Lys Ala Cys Leu

    120             125                 130AAC TGAACAAGAC ATTATCGTCA GCTTCAGTCT GCCATCGTCT TTAAAGATGG             489Asn135NNGCTCTCAA ATTCTAAATT GTAAAGAGAT TTCTACAGAC AGAATTATTA GTTGAATTTT      549TAATAAATTA TATTAAAATT GT                                               571(4) SEQ ID NO：4的信息：

(i) Sequential features:

(A) Length: 135 amino acids

(B) Type: amino acid

(D) Topological configuration: linear

(ii) Molecule type: protein

(III) Sequence description: SEQ ID NO: 4MET Asn Tyr Val Ile PHE Val Val Leu Val Ala Leu Tyr Val Ile Glu1 5 10 15VAL Ala LYS ThR Val ASP CYS Leu Serle Cys Ile Cys Glu Glu

20 25 25 30Val Glu Gly Cys Asp Lys Glu Ile Gly Arg Cys Gly Asp Asp Ala Gly

35 40 45Ser Leu Ser Cys Gly Pro Tyr Gln Ile Lys Glu Pro Tyr Trp Ile Asp

50 55 60Cys Gly Ser Pro Gly Ala GLY TYR GLN GLU CYS THR LYS GLU LYS ALA65 70 75 80CYS SER CYS VAA XAA TYR MET ARG TYR XAA Thr ARG

85 90 95Cys Thr Arg Gly Xaa Xaa Pro Thr Cys Gln Asp Tyr Ala Lys Ile His

100 105 110Asn Met Gly Pro Asn Gly Cys Arg Arg Thr Ser Asn Thr Tyr Trp Asn

115 120 125Lys Ala Asn Ala Cys Leu Asn

130 135(5) Information of SEQ ID NO: 5:

(i) Sequential features:

(A) Length: 630 base pairs

(B) Type: nucleic acid

(C) Chain type: single chain

(D) Topological configuration: linear

(ii) Molecule type: DNA (genomic)

(iii) Sequence description: SEQ ID NO: 5AGTAATGAAA ATTCACCTTT CGGACAAGG ATG ATC ATT GCA ATT TAT GTT TCC 53

                                                                                     

1 5CTA GCT CTT CTT CTA ATC GCC TCT GAG GAG GAG GAG AGC CAA TTC Act Gat 101leu Ala Leu Leu Ile Ala Ser Val Gln Phe Thr ASP

10 15 20TCT TGC CTT CTT CTT CTT Att TGC AAG GAA GAA GGA TGT GAC AGT CAA ATT 149SER CYS Leu ARG CYS LYS Val Val Gly Cysp Serle25 35 40GGA AAGA AGGA AGAGA TG TG TG TG TG that GTG TG -GTG TG that TAC CAG 197Gly Lys Cys Gly Met Asp Val Gly Ser Leu Ser Cys Gly Pro Tyr Gln

45 50 55att AAG AAG AAA CCG TAC TAC TGG ATT GGT GGT GGA AAA CCA GGG GGA GGA GGT TAC 245ile LYS Pro Tyr Ty -ILE ASP CYs

60 65 70GAA TCA TGC AAA AAA AAT AAA GCC TGT TCA GAG ACT TGT GCT 293GLU Ser Cys Thr Lysn Lys Ala Cys Sergs Val ARG ALA

75 80 85TAC Atg Agg Tat GGA ACC TGC TGC ACA GGT GGA CGA ACC CCA ACC 341Tyr Met Lys ARG Tyr Phe Cys THR GLY GLY GLY ARG THR Pro ThR

90 95 100TGC CAG GCT GCT GCT AGG Att Cat AAC GGT GGA CCA CGC GGT TGC AAG 389CYS GLN ALA ALA ARG iLe

105 110 115 120AGT TCT GCT GCT GGT GGT GGT TGG AAC AAG GTA CAG AAA TGT TGT TTG Aga 437ser Ser Ala ThR Val GLN LYS Leu ARG

            125                 130                 135TGAATTCGAA ATCTTTGAGT AGCNCCTGTC TTACATTTGA AAGGCCTTTT AATTCAAAAT      497TATTTTGGGA ATCNAATGAT TTTAAACATT TATTTGAAAT TATTCNGAAA TAGAAACAAC      557TATAAATTGC TCCAAGAATT GTATAATCAT GAAGTGTTTG AAAGCTGTTT TCTGAAATAA      617ACTTCCCATA AAT                                                               630(6)SEQ ID NO：6的信息：

(i) Sequential features:

(A) Length: 136 amino acids

(B) Type: amino acid

(D) Topological configuration: linear

(ii) Molecule type: protein

(III) Sequence description: SEQ ID NO: 6MET ILA Ile Ala Ile Tyr Val Seru Ala Leu Leu Ile Ala Sering

20 25 30Val Glu Gly Cys Asp Ser Gln Ile Gly Lys Cys Gly Met Asp Val Gly

35 40 45Ser Leu Ser Cys Gly Pro Tyr Gln Ile Lys Lys Pro Tyr Trp Ile Asp

50 55 60CYS GLE LYS Pro Gly Gly GLY TYR GLU Ser Cys THR LYS ALA65 70 75 80CYS Serg Ala Tyr Met LYS ARG TYR GLY THR PHE

85 90 95Cys Thr Gly Gly Arg Thr Pro Thr Cys Gln Asp Tyr Ala Arg Ile His

100 105 110Asn Gly Gly Pro Arg Gly Cys Lys Ser Ser Ala Thr Val Gly Tyr Trp

115 120 125Asn Lys Val Gln Lys Cys Leu Arg

130 135(7) Information of SEQ ID NO: 7:

(i) Sequential features:

(A) Length: 115 amino acids

(B) Type: amino acid

(D) Topological configuration: linear

(ii) Molecule type: protein

(iii) Sequence Description: SEQ ID NO: 7Thr Val Pro Ser Asp Cys Leu Arg Cys Ile Cys Gln1 5 5 10Val Glu Gly Cys Asn Asn Glu Ile Gly Arg Cys sply Gly A Met

15 20 25Ser Leu Ser Cys Gly Pro Tyr Gln Ile Lys Glu Pro Tyr Trp Ile Asp

 30                  35                  40Cys Gly Arg Pro Gly Gly Gly Tyr Gln Gln Cys Thr Lys Glu Lys Ala45                  50                  55                  60Cys Ser Glu Tnr Cys Val His Ala Tyr Met Asp Arg Tyr Ala Arg Arg

65 70 75Cys Thr Gly Gly Arg Gln Pro Thr Cys Gln Asp Tyr Ala Lys Ile His

80 85 90Asn Met Gly Pro Asn Gly Cys Gln Ser Ser Asn Asn His Tyr Trp Asp

95 100 105Asn Val Arg Arg Cys Leu Gly

110 115

Claims (10)

1. cleaning combination, it contains the isopeptidase of isopeptidase live vol.

2. laundry detergent composition, it comprises:

A) 0.0001-5% weight, the isopeptidase of preferred 0.001-2% weight; With

B) the detergent composition binder component of 95-99.9999% weight.

3. laundry detergent composition, it comprises:

A) 0.1-80% weight, the detergent surfactant of preferred 1-50% weight;

B) 0.0001-5% weight, the isopeptidase of preferred 0.001-2% weight; With

C) the detergent composition binder component of 0.1-99.8% weight.

4. laundry detergent composition, it comprises:

A) the active detersive enzyme of 0.0001-2% weight, it is preferably selected from proteolytic enzyme, cellulase, lipase, amylase, peroxidase and its mixture;

B) 0.0001-5% weight, the isopeptidase of preferred 0.001-2% weight; With

C) the detergent composition binder component of 0.1-99.8% weight, it is preferably selected from detergent surfactant, washing assistant and its mixture.

5. granular detergent composition, it comprises:

A) SYNTHETIC OPTICAL WHITNER of 0.1-50% weight;

B) washing assistant that is selected from silico-aluminate, silicate and its mixture of 1-80% weight;

C) the active detersive enzyme of 0.0001-2% weight, it is selected from proteolytic enzyme, amylase, lipase, cellulase and its mixture;

D) 0.0001-5% weight, the isopeptidase of preferred 0.001-2% weight; With

E) the detergent composition binder component of 0.1-99.8% weight.

6. according to each laundry detergent composition of claim 1-5, it contains washing assistant, detergent surfactant or its mixture, and wherein washing assistant is selected from silico-aluminate, silicate, phosphoric acid salt, phosphonate and its mixture; And wherein tensio-active agent is selected from alkyl alkoxylated vitriol, alkyl-sulphate, linear alkyl sulfonate surfactant, cats product, nonionogenic tenside, amphoterics, zwitterionics and its mixture.

7. according to each laundry detergent composition of claim 1-6, said composition is a granulous.

8. the method for a laundering of textile fabrics, this method is included in will need the aqueous solution of fabric that cleans and the isopeptidase that contains the isopeptidase live vol to contact in the washing machine.

9. the method for a laundering of textile fabrics, this method are included in and will need the fabric that cleans in the washing machine and contain each the aqueous solution of the composition that contains isopeptidase of with good grounds claim 1-7 and contact.

10. method of hand-washing fabric, this method comprise that the fabric that needs are cleaned is immersed in the aqueous solution of the isopeptidase that contains the isopeptidase live vol.