JP2001509540A - Cleaning compositions containing cytochromes - Google Patents

Abstract

  (57) [Summary] The present invention relates to cleaning compositions, including laundry, dishwashing, hard surface cleaners and oral / dental cleaning compositions, containing cytochromes, especially cytochrome P450. The composition provides effective and efficient cleaning of colored and / or daily body spots and / or soils and sanitization of treated surfaces. In particular, the compositions of the present invention, when formulated as laundry detergent compositions, clean and whiten fabric utility articles.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION

The present invention provides a washing, dishwashing, hard surface cleaner containing cytochrome enzymes,
Cleaning compositions, including oral / dental cleaning compositions.

[0002]

BACKGROUND OF THE INVENTION

The performance of a cleaning product for use in a cleaning or cleaning process is determined by a number of factors, including the ability to remove soil and prevent redeposition of soil or soil degradation products on an object during cleaning. Colored stains / soils are often difficult to effectively remove from soiling. Highly stained stains and stains, i.e. those derived from fruits and / or vegetables, are particularly difficult stains to remove. The stains and stains are α-, β
-And-gamma-carotene and carotenoid compounds such as lycopene and xanthophylls, porphyrins such as chlorophyll, and colored substances based on flavonoid pigment and dye components. This latter group of natural flavonoid-based dye components consists of highly colored anthocyanin dyes and pigments based on pelargonidin, cyanidin, delphidine and their methyl esters, and anthoxanthines. These compounds are the source of most orange, red, purple and blue colors that occur in fruits, and include all berries, cherries, reds and black currants, grapefruits, passion fruits, oranges, lemons,
It is abundant in apples, pears, pomegranates, red cabbage, red turnips and even flowers. Derivatives of cyanidin are less than 80% in colored leaves, less than 70% in fruits and 5 in flowers.
Present within 0%. Examples of such soils include tea, coffee, spices such as curry and paprika, orange, tomato, banana, tea, mango, broccoli, carrot, beetroot, spinach soil and grass.
Ballpoint pen inks are also known to be colored stains that are highly difficult to remove. In addition, the complex nature of daily "body" stains typically found in pillowcases, t-shirts, collars and socks indicates the difficulty of continuous and careful cleaning with detergents. These stains are difficult to completely and completely remove the residue that accumulates on the fabric and turns black and yellow. Daily body dirt, bathtub,
It is also found on sanitary and kitchen surfaces such as toilets and dishes. The objects include fabrics, hard surfaces, dishes, such as plastic, glass or ceramic, teeth and mouth. Traditionally, high levels of bleaching compounds are incorporated into detergent compositions, optionally together with bleach precursors and / or bleach enhancers. Bleach is a compound that is a precursor of hydrogen peroxide, which is formed during the washing operation.
Perborate and percarbonate are the most important examples of such hydrogen peroxide precursors. In view of the foregoing, there is a clear need to provide cleaning compositions having excellent cleaning performance. Accordingly, it is an object of the present invention to provide a cleaning composition that provides effective and efficient cleaning of colored and / or daily body stains and / or stains. Another object is to provide a cleaning composition for cleaning utility textiles to whiten them. The above objective has been achieved by formulating a cleaning composition comprising cytochromes, particularly cytochrome P450. It has been found that enzyme bleaches based on cytochromes, and in particular cytochrome P450, exhibit a bleach-like effect in cleaning compositions on an unexpectedly wide range of performances, such as cleaning of dark spots, whiteness maintenance and stain removal. I knew it. It has also been found that the cleaning composition of the present invention can make the treated surface sanitary. It has further been found that the performance of the cleaning compositions of the present invention is enhanced by the addition of other enzyme bleach systems, conventional activated bleach systems, metallocatalyst-based bleach systems and / or other detergent enzymes.

In a preferred embodiment, the present invention further relates to laundry and / or fabric care compositions comprising cytochromes, in particular cytochrome P450, for cleaning and whitening textile products. In a second aspect, the invention relates to a dishwashing or household cleaning composition comprising cytochromes, in particular cytochrome P450, and in a third aspect, the invention relates to an oral / dental care composition comprising cytochromes, in particular cytochrome P450. Cytochrome enzymes are mainly used in the medical field mainly in the medical field (US Pat.
04198, RU2063758) and the field of biotechnology (J0902)
8373, RU2063985). In particular, cytochrome P
450 enzymes are described, for example, in recently published WO 97/01349, WO 96/09.
No. 042, WO 96/04789 and WO 95/34679 have been described for the pharmaceutical field. Cytochrome P450 is cytotoxic (US 5,525,482
), For testing the safety of compounds (J08056695) or for identifying specific drugs (WO95 / 30766). However, cytochromes, especially cytochrome P, in cleaning compositions
The use of 450 was not previously known.

[0004]

[Summary of the Invention]

The present invention relates to cleaning compositions, including laundry, fabric care, dishwashing, hard surface cleaners, oral / dental cleaning compositions, containing cytochromes, particularly cytochrome P450. The composition provides effective and efficient cleaning of colored and / or daily body spots and / or soils and sanitization of treated surfaces. In particular, the compositions of the present invention, when formulated as laundry detergent compositions, clean and whiten fabric utility articles.

[0005]

DETAILED DESCRIPTION OF THE INVENTION

An essential component of the cleaning composition of the present invention is cytochrome, particularly cytochrome P4.
50, and its electron transfer system. The cleaning composition of the present invention provides effective and efficient cleaning of colored and daily body stains and / or stains, particularly when formulated as a laundry detergent composition, to clean and whiten fabric utility products. I understood. Without being bound by theory, it is believed that "daily body stains" contain sebum secreted by the human body. Sebum is thought to contain large amounts of saturated and unsaturated fatty acids, sterols and sterol esters (The physiology a
nd Pathology of the skin, Vol. 9, A. Jarret (1986)). Fragmentation of the substrate by the cytochrome enzyme and formation of ionizable or hydrophilic substituents render the enzyme reaction product more soluble and easier to remove from soil. Without being bound by theory, cytochrome reacts with a wide range of organic compounds to oxidatively break carbon-carbon bonds; hydrocarbon hydroxylation; alkene epoxidation and oxygenation; arene epoxidation; N-, S- and O-dealkylation; N- and S-oxidation; oxidative and reductive dehalogenation; oxidation of alcohols and aldehydes; dehydrogenation reactions; dehydration; reduction of N-oxides and epoxides; It is believed that such a reaction can be catalyzed. Colored plant and fruit stains also contain highly colored color bodies associated with cell wall components. These natural dyes are based on highly conjugated polyaromatic compounds. It is believed that the color of these materials is degraded by cytochrome oxidation based on the destruction of the color-forming conjugate system in the compound. In addition, the cleaning composition of the present invention makes the treated surface sanitary.

[0006] Sanitary treatment includes all positive effects obtained by inhibiting or inhibiting microbial activity on fabrics and other surfaces, such as preventing malodor generation and bacterial / fungal growth.
For example, it prevents malodor generation in storage and wear fabrics, storage utensils, especially plastic kitchenware, and toilets. In particular, the compositions of the present invention inhibit or at least inhibit the growth of bacteria and / or fungi on wet fabrics that have been laundered and awaited to prevent malodor formation. In addition, the growth of bacteria and / or fungi on hard surfaces such as tiles and their silicone joints, sanitary equipment is prevented.

[0007] The sanitary treatment potential of the cleaning compositions of the present invention is increased by the addition of chemical sanitizing agents such as triclosan and / or hexemidine. Parfum
s Cosmetiques Actualites, No. 125, Nov, 1995, 51-4 describes suitable chemical sanitizing agents. The sanitary treatment effect of the cleaning composition of the present invention is Tuber.Lung.Dis. 1994 Aug, 75
(4), 286-90; J. Clin. Microbiol. 1994 May, 32 (5), 1261-7; J. Clin. Microbiol. 199
It can be assessed by the minimum inhibitory concentration (MIC) as described in 2 Oct, 30 (10), 2692-7.

Cytochrome Enzymes Cytochrome enzymes are heme-containing proteins involved in the transmission of reducing equivalents associated with reversible changes in the oxidation state of prosthetic groups. The change in the oxidation state depends on the central iron atom Fe
It is involved in the reversible equilibrium of one electron between the (II) and Fe (III) states.
The term "heme" is commonly understood as "tetrapyrrole chelate of iron". Four major groups of cytochromes are currently known:-cytochrome a: cytochromes whose heme prosthetic group is heme a, the iron chelate of cytoporphyrin IX. Examples are a1 (Nitrobacter agilis) and aa3 (two heme groups: low spin a and high spin a3). -Cytochrome b: a cytochrome with photoheme (iron chelate of cytoporphyrin IX) as a prosthetic group, but lacking a covalent bond between porphyrin and protein. Examples are b1 (E. coli); b2 (yeast; EC 1.1.2.3); b
B5 (animal microsomes, cytoplasm of erythrocytes); b6 or B-563 (green plants, photosynthetic bacteria); b7 (Arum species); b8 (E. coli); b '
B-562 (white blood cells); b-559 (green plant); P450-superfamily. -Cytochrome c: a cytochrome having a covalent thioether chain between one or both vinyl side chains of the photoheme side chain and the protein. Examples are c, c1 and c2 (eukaryotic mitochondria); c3 (anaerobic sulfate and sulfur reducing bacteria); c-55
2 (E. coli); c4 (Azotobacter and Pseudomonas species); c5 (Azotobacte
r species); c6 (algae); c-551 (Pseudomonas); c-555 (green bacterium Chlo
robium). -Cytochrome d: a cytochrome having a tetrapyrrole chelate of iron as the prosthetic group, in which the degree of conjugation of the double bond is lower than in the case of porphyrin. An example is d (aerobic bacteria; E. coli and Areobacter species). Cytochromes of the above class are mixed complexes, for example the bc complex in green plants (also called cytochrome f); bd
Complex (Photobacterium phosphoreum and E. coli); cd1 complex (bacterium Pseu
domonas-, Paracoccus- and Thiobacillus species).

[0009] Other metal ions, such as vanadium, molybdenum, nickel and cobalt, can replace iron with a heme group. Cytochrome enzymes are preferably used according to the present invention at a pure enzyme level of 0.0001 to 2%, more preferably 0.001 to 0.5%, most preferably 0.005 to 0.1% by weight of the composition. Formulated in the composition. The preferred cytochrome for special applications is alkaline cytochrome, ie, 7
An enzyme having an enzyme activity of at least 10%, preferably at least 25%, more preferably at least 40% of its maximum activity at a pH of １２12. Further preferred cytochromes are those enzymes which have their maximum activity at a pH of 7-12.

[0010] Cytochromes suitable for the purposes of the present invention are or are all prokaryotic and eukaryotic natural cytochromes. An example is below (Microbial Enzyme
s for oxidation of organic molecules, F.Sima Sariaslani in Critical Revie
ws in Biotechnology, Vol. 9, Issue 3 (1989)). Examples are: Prokaryotes:-Bacteria: Pseudomonas putida, Pseudomonas putida PpG777, Pseudom
onas putida 777 var. incognita, Bacillus megaterium ATCC13368
, Bacillus megaterium ATCC 14581, E. coli cloning, Rhodococcus
rhodcoccus ATCC 19067 (formerly Corynebacterium strain 7EIC), Noc
ardia NH1, Acinetobacter calcoacetica, Xanthobacter species and Moraxella
Species-Actinomyces: Saccharoployspora erythraea, Streptomyces setonii, St
1. reptomyces griseolus and Streptomyces griseus (ATCC13273) Eukaryotes: Cyanidinium caldarium (red algae), Apergillus ochraceus, Cunninghamella
bainieri, Saccharomyces cerevisiae, Fusariom oxysporum, Candida tropic
alis, Nectria haematococca.

Preferred for the purposes of the present invention are cytochrome P450 enzymes. P450
The superfamily cytochromes are characterized as a class of cytochrome b group heme-thiolate proteins. Due to their characteristic mode of action of oxygen transport, the cytochrome P450 family is an exception to the mode of electron transport characteristic of cytochromes. Cytochrome P450 is a unique multicomponent heme enzyme that plays a central role in the oxidation reactions of biological systems and has therefore been studied in detail. For example, Cr
itical Review in Biotechnology, Vol.9, Issue 3 (1989), pp.215-227, FSSaria
slani and H. Dalton-Chem. Rev., Vol. 96, No. 7 (1996), 2841-2087, M. Sono, MPRo
ach, EDCoulter and JHDawson. These enzymes perform NAD (P) H-dependent oxidation of diverse sequences of organic molecules via cleavage of dioxygen (molecular oxygen) to produce one molecule of water and oxidized substrates, while others Similar to classical monooxygenase. Cytochrome P450 substrates are diverse, including physiological substrates such as steroids, hydrocarbons, vitamins and fatty acids, and xenobiotics such as drugs, pesticides and carcinogens. Some reactions, such as hydroxylation, dehalogenation,
Dealkylation, N-oxide reduction, N-oxidation, epoxidation, deamination, desulfurization, and sulfoxidation are catalyzed by cytochrome P450 (FIG. 3, Chem. Rev.,
Vol.96, No.7 (1996), p.2845).

[0012] Suitable cytochrome P450s are described in reference EC 1.14.13, EC 1.1
It is an enzyme included in the EC classification of 4.14, EC1.14.15 and EC1.14.99. Examples are: 1.14.13.11 trans-cinnamic acid 4-monooxygenase 1.14.13.17 cholesterol 7α-monooxygenase 1.14.13.28 3,9-dihydroxypterocarpan 6a -Monooxygenase 1.14.13.30 leukotriene-b4 20-monooxygenase 1.14.13.37 methyltetrahydroprotoberberine 14-monooxygenase 1.14.13.41 tyrosine N-monooxygenase 1.14.13. 42 hydroxyphenylacetonitrile 2-monooxygenase 1.14.13.47 limonene 3-monooxygenase 1.14.13.48 limonene 6-monooxygenase 1.14.13.49 limonene 7-monooxygenase 1.14.13. 5 Isoflavone 3'-hydroxylase 1.14.13.53 Isoflavone 2'-hydroxylase 1.14.14.1 Non-specific monooxygenase 1.14.15.1 Camphor 5-monooxygenase 1.14.15.3 Alkane 1-monooxygenase 1.14.15.4 steroid 11β-monooxygenase 1.14.15.6 cholesterol monooxygenase (side-chain cleavage) 1.14.99.9 steroid 17α-monooxygenase 1.14.9. 10 Steroid 21-monooxygenase 1.14.99.22 Ecdysone 20-monooxygenase 1.14.9.28 linalool 8-monooxygenase

A preferred cytochrome P450 for the present invention is cytochrome P450 bm3, which catalyzes the hydroxylation of saturated and monounsaturated fatty acids, alcohols and amides.
It is an enzyme type. These enzymes do not require an electron carrier because they are unique freestanding cytochrome P450s, consisting of both a heme group with a P450 domain and the flavin protein NADPH-cytochrome P450 reductase. Furthermore, these enzymes have significantly larger substrate binding domains than other cytochrome P450s. Enzyme homologs similar to the cytochrome enzymes of the present invention are also contemplated. “Homolog”
The term (eg, presoaked in 5 × SSC, in a solution of 20% formamide, 5 × Denhardt's solution, 50 mM sodium phosphate, pH 6.8 and 50 μg of denatured sonicated calf thymus DNA for 1 hour at ４０40 ° C. Under certain conditions), under the same conditions as in the DNA encoding for the cytochrome enzyme having this amino acid sequence, in a similar solution supplemented with 100 μM ATP, followed by hybridization at ４０40 ° C. for 18 hours. It is meant to indicate the polypeptide encoded by the DNA that hybridizes to the probe. The term refers to the addition of one or more amino acid residues at one or both of the C- and N-termini of the native sequence, substitution of one or more amino acid residues at one or more sites in the native sequence, one of the native amino acid sequences Or deletion of one or more amino acid residues at both ends or at one or more sites in the native sequence, or a deletion of one or more amino acid residues at one or more sites in the native sequence.
The meaning includes derivatives of cytochrome enzyme sequences obtained by insertion of the above amino acid residues. The above enzymes may be of any suitable origin, such as of plant, animal, bacterial, fungal and yeast origin. The origin may also be mesophilic or extremophilic (cryophilic, eutrophic, thermophilic, barophilic, alkaline, acidophilic, halophilic, etc.). Purified or unpurified forms of these enzymes may also be used. At present, it is customary to modify wild-type enzymes by protein / genetic engineering techniques to maximize performance efficacy with the cleaning compositions of the present invention. For example, variants are designed to increase the compatibility of the enzyme with the common components of such compositions. On the other hand, the optimal pH for enzyme variants
Variants may be designed such that bleed or chelant stability, catalytic activity, etc., are tailored to a particular cleaning application. In particular, attention should be paid to amino acids that are susceptible to oxidation in terms of bleach stability and surface charge in terms of surfactant compatibility. The isoelectric point of such enzymes may be modified by substitution of some charged amino acids, for example, increasing the isoelectric point helps to improve compatibility with anionic surfactants. Enzyme stability can be further enhanced, for example, by forming additional salt bridges and reinforcing calcium binding sites to increase the stability of the chelants.

Electron Transfer Systems Cytochrome-based enzyme bleaching systems require the presence of an electron transfer system consisting of an electron donor compound and an electron carrier. The electron donor compound is an essential element of the cleaning composition of the present invention, and is usually 10 ^-6 to 15% by weight of the total composition, preferably 10 ^{-5 to} 5%, more preferably 0.00.
It is incorporated into the cleaning compositions of the present invention at a level of 01-1%. The weight ratio of pure cytochrome enzyme to electron donor compound is preferably between 10: 1 and 1: 100.
0, more preferably 2: 1 to 1: 100, most preferably 1: 1 to 1:10. Possible electron donor compounds are NADH: nicotinamide adenine dinucleotide (reduced), NADPH: nicotinamide adenine dinucleotide phosphate (reduced) and / or sodium sulfite, as described in US Pat. No. 5,362,856 of the University of Toronto Innovations Found. It is. Electron carriers that cooperate with cytochromes are flavin proteins, proteins with reducing disulfide groups, iron proteins, copper proteins, molybdenum proteins, nickel proteins, vanadium proteins and quinone proteins. Flavin proteins usually have one of two prosthetic groups, FMN: flavin mononucleotide and FAD: flavin adenine dinucleotide, and these proteins have oxidoreductase activity. Iron proteins are mostly iron-sulfur proteins, such as rubredoxin and / or ferredoxin reductase. The electron carrier is usually 0.00% of the total composition.
01 to 2% by weight, preferably 0.001 to 0.5%, more preferably 0.005%
At a level of ０．１0.1% is incorporated into the cleaning compositions of the present invention. The weight ratio of pure cytochrome enzyme to electron carrier is preferably 10: 1 to 1: 1000,
More preferably, it is 2: 1 to 1: 100, and most preferably, it is 1: 1 to 1:10.
These NAD (P) H, reduced flavin or flavin proteins, or other suitable electron acceptors, compatible with cytochrome enzymes can be enzymatically (re) formed through an enzymatic reaction: oxidoreductase AH + NADP ⁺ >>>>> A ⁺⁺ NADPH Oxidoreductase using NAD (P) ⁺ as electron acceptor in enzymatic oxidation of organic substrates is suitable. This substrate may be the reaction product of the main reaction of cytochrome itself. Suitable oxidoreductases are: -E. C. 1.1.1. x: an alcohol acting member such as alcohol dehydrogenase, eg 1.1.1.2 forms an aldehyde reaction product; C. 1.2.1. x: aldehyde-acting members such as aldehyde dehydrogenase, eg 1.2.1.4, form organic acids; C. 1.8.1.2: Sulfite reductase which converts hydrogen sulfide in sulfurous acid; a single enzyme or a mixture of eg alcohol- and aldehyde-dehydrogenases can be applied.

Similarly, most cytochrome P450 systems are multicomponent and require the involvement of another protein for transfer of reducing equivalents from NAD (P) H to the terminal cytochrome P450 component. These systems were divided into two types based on the nature and composition of their redox components. Type I strains identified in the eukaryotic cytoplasmic reticulum are:
FAD- and FMN that transfer reduced electrons from NADPH to cytochrome P450
-Contains a reductase. Types detected in mitochondrial and bacterial systems
Type II, Critical Review in Biotechnology, Vol. 9, Issue 3 (1989), FSSarias
Lani and H. Dalton, page 216, consisting of a FAD-containing reductase that transfers electrons from NAD (P) H to terminal cytochrome P450 mediated by the small redox iron-sulfur (ferredoxin) protein AS illustrated in FIG. In catalyzing the monooxygenation reaction, the cytochrome P450 enzyme uses NADP or NADP as an electron donor according to the following reaction scheme (R is a substrate to be oxidized).
H can be used: RH + O ₂ + NAD (P) H + H ⁺ → ROH + H ₂ O + NAD (P) ⁺

Detergent Component The cleaning composition of the present invention may also contain additional detergent components. The exact nature of these additional components, and their level of incorporation, will depend on the physical form of the composition and the nature of the cleaning operation in which it is used. The cleaning composition preferably further contains other enzyme bleach systems, conventional activated bleach systems, metallocatalyst-based bleach systems and / or other detergent enzymes. In a preferred embodiment, the present invention relates to laundry and / or fabric care compositions containing cytochromes (Examples 1-18). In a second aspect, the invention relates to dishwashing or household cleaning compositions (Examples 19-28) comprising a sanitary treatment formulation, and in a third aspect, the invention relates to oral / dental care compositions (Examples 29-31). ).

[0017] The cleaning composition according to the present invention is in liquid, paste, gel, bar soap, tablet, spray, foam, powder or granular form. Granular compositions may be in "compact" form, and liquid compositions may be in "concentrated" form. The compositions of the present invention include, for example, hand and machine dishwashing compositions, hand and machine laundry detergent compositions, such as laundry additive compositions, and compositions suitable for soaking and / or pretreating soiled fabrics, rinsing additions. It is formulated as a fabric softener composition, and a composition for typical domestic hard surface cleaning operations. Such cytochrome-containing compositions may be formulated as oral / dental care compositions. When formulated as a composition for use in a manual dishwashing process, the composition of the present invention preferably comprises a surfactant and preferably an organic polymeric compound, a foam enhancer, a Group II metal ion, a solvent, a hydrotrope and And other detergent compounds selected from additional enzymes. When formulated as a composition suitable for use in a washing machine process, the composition of the present invention preferably comprises both a surfactant and a builder compound, and preferably an organic polymer compound, a bleach, an additional enzyme, It further contains one or more detergent components selected from foam inhibitors, dispersants, lime soap dispersants, soil suspending and redeposition inhibitors, and corrosion inhibitors. Laundry compositions can also contain softening agents as additional detergent components. Such compositions containing cytochromes, when formulated as laundry detergent compositions, provide fabric cleaning, stain removal, whiteness maintenance, flexibility, color appearance.
(color appearance), dye transfer inhibition and sanitary treatment. The compositions of the present invention can also be used as detergent additive products. Such additive products are to reinforce or enhance the performance of conventional detergent compositions. If necessary, the density of the laundry detergent composition is 4% for the composition measured at 20 ° C.
It is 00 to 1200 g / L, preferably 600 to 950 g / L. The "compact" form of the composition is best reflected in terms of density and composition in terms of the amount of inorganic filler salt; inorganic filler salts are conventional components of detergent compositions in powder form; conventional detergent compositions In such products, the filler salt is present in a substantial amount, typically 17-35% by weight of the total composition.

In a compact composition, the filler salt does not exceed 15% by weight of the total composition;
Preferably it is present in an amount not exceeding 10%, most preferably not exceeding 5% of the composition. The inorganic filler salt as meant in the present composition is selected from the alkali and alkaline earth metal salts of sulfates and chlorides. A preferred filler salt is sodium sulfate.

The liquid detergent composition according to the invention may be in “concentrated form”, in which case the liquid detergent composition according to the invention contains a small amount of water compared to conventional liquid detergents. Typically, the water content of the concentrated liquid detergent is preferably less than 40% by weight of the detergent composition, more preferably less than 30%, and most preferably less than 20%.

Conventional detergent enzyme cleaning compositions, in addition to cytochrome enzymes, provide cleaning performance and / or
Or, it may further include one or more enzymes that exert a fabric care effect. The combination of cytochromes and detergent enzymes provides improved cleaning with colored and / or daily body stains and / or stains, and improved fabric utility cleaning and whitening when formulated as a laundry composition I found out. The enzymes include cellulase, hemicellulase, peroxidase, protease, glucoamylase, amylase, xylanase, lipase, phospholipase, esterase, cutinase, pectinase, keratanase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, There is an enzyme selected from malanases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases or mixtures thereof. A preferred combination is a cleaning composition having a cocktail of common enzymes such as proteases, amylases, lipases, cutinases and / or cellulases together with one or more plant cell wall degrading enzymes. Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they have an optimum pH of 5-12 and 50 CEVU (Cellulose Viscosi
ty Unit) or more. Suitable cellulases are described in US Pat. No. 4,435,307 to Barbesgoard et al., J61078384 and WO96 / 02653.
Which discloses fungal cellulases produced from Humicola insolens, Trichoderma, Thielavia and Sporotrichum, respectively. E
P739982 describes a cellulase isolated from a novel Bacillus species. Suitable cellulases are GB-A-2,075,028, GB-A-2,095,
275, DE-OS-2,247,832 and WO 95/26398. Examples of such cellulases are the strains of Humicola insolens (Humicola grisea va
r. thermoidea), especially cellulase produced by Humicola strain DSM1800. Another suitable cellulase is a cellulase from Humicola insolens having a molecular weight of about 50 kDa, an isoelectric point of 5.5 and containing 415 amino acids; a 〜43 kD from Humicola insolens DSM1800 exhibiting cellulase activity. Endoglucanase. Preferred endoglucanase components are described in PCT Patent Application W
It has the amino acid sequence disclosed in O91 / 17243. September 2, 1994
Trichoderma as described in Genencor's WO 94/21801 published on 9th.
EGIII cellulases from longibrachiatum are also suitable cellulases. Particularly suitable cellulases are those having a color care effect. Examples of such cellulases are described in European Patent Application No. 91202 filed Nov. 6, 1991.
No. 879.2 (Novo). Carezyme and Ce
lluzyme (Novo Nordisk A / S) is particularly useful. See also WO 91/17244 and WO 91/21801. Other cellulases suitable for fabric care and / or cleaning properties are WO 96/34092, WO 96/17994 and WO 9
5/24471. The above cellulases are usually incorporated into detergent compositions at active enzyme levels of 0.0001 to 2% by weight of the detergent composition.

[0021] Another preferred enzyme that may be included in the detergent compositions of the present invention is lipase.
Lipase enzymes suitable for detergents include those produced by microorganisms of the genus Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154 disclosed in GB 1,372,034. Suitable lipases include the microorganism Pseudomonas fluorescent IAM1057, which shows a positive immune cross-reactivity with lipase antibodies.
Some are produced by This lipase is commercially available from Amano Pharmaceutical Co. Ltd. in Nagoya, Japan under the trade name Lipase P "Amano".
-P ". Other suitable commercially available lipases include Amano-CES, Chromobacter visc
osum, for example, Chromobacter viscosum var.lipol from Toyo Brewing Co., Ltd., Takata, Japan
lipase from yticum NRRLB 3673; Chromobacter viscosum lipase from USBiochemical Corp., USA and Disoynth Co., Netherlands; Pseudomonas gl
There is a lipase from adioli. Particularly suitable lipases are M1 Lipase ^R and Lip
a lipase such as omax ^{R (Gist-Brocades)} and Lipolase ^R and Lipolase Ultra ^{R (Novo),} it was found that they are very effective when used in conjunction with the compositions of the present invention. Novo Nordisk EP258068, WO92 / 05249 and WO95 / 22615, Unilever WO94 / 03578, WO95 / 35
The lipolytic enzymes described in 381 and WO 96/00292 are also suitable.
Also suitable are special types of lipases, ie cutinases [EC 3.1.1.50], which are considered lipases that do not require surfactant activity. Addition of cutinase to the detergent composition,
For example, WO-A-88 / 09367 (Genencor), WO90 / 09446 (Plan
t Genetic System), WO94 / 14963 and WO94 / 14964 (Unil
ever). The lipase and / or cutinase is present in an amount of 0.0001 to 2% by weight of the detergent composition.
At a pure enzyme level, typically in detergent compositions.

Suitable proteases are subtilisins (subtilisins BPN and BPN ') obtained from certain strains of B. subtilis and B. licheniformis. One suitable protease is obtained from the Bacillus strain and has a maximum activity in the pH range from 8 to 12,
Developed by Novo Industries A / S in Denmark and sold as ESPERASE ^(R)
And referred to as "Novo". The production of this and similar enzymes is from Novo G
B1, 243, 784. Other suitable proteases include Novo's
ALCALASE ^(R) , DURAZYM ^(R) and SAVINASE ^(R) , and MAXATAS of Gist-Brocades
E ^(R) , MAXACAL ^(R) , PROPERASE ^(R) and MAXAPEM ^(R) (Protein Engineering Max
acal). Proteolytic enzymes include modified bacterial serine proteases, such as
For example, European Patent Application No. 87 / 303761.8 filed on Apr. 28, 1987.
1986, which relates to a modified bacterial serine protease that is hereinafter referred to as "Protease B" and hereinafter referred to as "Protease A". One is described in Venegas European Patent Application No. 199,404 published on 29th. Lysine replaces arginine at position 27, tyrosine replaces valine at position 104, and serine replaces 12
A variant of the alkaline serine protease from Bacillus in which asparagine is substituted at position 3 and alanine is substituted for threonine at position 274, hereinafter referred to as "protease C", is suitable. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637 published May 16, 1991. In particular, genetically modified variants of protease C are also included in the present invention.

A preferred protease, referred to as “Protease D”, is a carbonyl hydrolase variant having an amino acid sequence that is not found in nature, and is described in WO 95/10591.
And USSN 08/3, filed October 13, 1994, by C. Ghosh et al.
According to the numbering of Bacillus amyloliquefaciens subtilisin as described in the patent application entitled "Bleaching Compositions Containing Protease Enzymes" at 22,677, preferably +99, +101, +103, +104, +107, +123.
, +27, +105, +109, +126, +128, +135, +156, +
166, +195, +197, +204, +206, +210, +216, +2
+7 in combination with one or more amino acid residue positions corresponding to those selected from the group consisting of 17, +218, +222, +260, +265 and / or +274.
At the position corresponding to position 6, it is derived from a precursor carbonyl hydrolase by using different amino acids instead of a plurality of amino acid residues in the carbonyl hydrolase. Patent application EP251446 and WO91 / protease described in 06637, BLAP protease described in WO91 / 02792 ^(R), and W
Those variants described in O95 / 23221 are also suitable for the present invention.

See also high pH protease from Bacillus sp. NCIMB 40338 described in Novo WO 93 / 18140A. Enzyme detergents containing proteases, one or more other enzymes and a reversible protease inhibitor are available from Novo WO 92 / 03529A.
It is described in. If desired, proteases with reduced adsorptivity and improved hydrolyzability are available as described in Procter & Gamble, WO 95/07791. Recombinant trypsin-like proteases for detergents suitable for the present invention are described in Novo WO 94/25583. Other suitable proteases are described in Unilever, EP 516200. The proteolytic enzyme is present in an amount of 0.0001 to 2%, preferably 0.00% by weight of the composition.
Pure enzyme levels of from 0.01 to 0.2%, more preferably 0.005 to 0.1%, are incorporated into the detergent compositions of the present invention.

Amylases (α and / or β) are included for removal of carbohydrate-based soils.
You can have. Novo Nordisk A / S, released February 3, 1994
WO 94/02597 describes a cleaning composition containing a mutant amylase.
It is described. Novo Nordisk A / S W published on April 20, 1995
See also O95 / 10603. Other amylases known for cleaning compositions
There are both α- and β-amylases. Alpha-amylase is known in the art
US Pat. No. 5,003,257, EP 252,666, WO 91/003
53, FR2,676,456, EP285,123, EP525,610, E
P368,341 and British Patent Specification No. 1,296,839 (Novo)
Something was done. Other suitable amylases were published on August 18, 1994.
WO94 / 18314, Genencor's W published February 22, 1996.
Stability improving amylase described in O96 / 05295 and published in April 1995
Added to the immediate parent of Novo Nordisk A / S, which was disclosed in the opened WO 95/10603
Amylase variants with modification. EP 277216, WO 95/2639
7 and amylases described in WO 96/23873 (all Novo Nordisk)
Is also appropriate. Examples of commercially available α-amylase products include Genencor's Purafect Ox Am^R, All Novo N
Termamyl commercially available from ordisk A / S Denmark^R, Ban^R, Fungamyl^Rand
 Duramyl^RIt is. WO 95/26397 describes other suitable amylases: Phadebas ^R As determined by the α-amylase activity assay, a temperature range of 25-55 ° C. and 8
At pH values in the range of -10, Termamyl^RDescribes an α-amylase characterized by having a specific activity at least 25% higher than the specific activity of α-amylase. WO96 /
Variations of the above enzymes described in 23873 (Novo Nordisk) are suitable. Activation
Have improved properties in terms of temperature and the combination of thermal stability and high activity levels.
Other amylolytic enzymes are described in WO 95/35382. The amylolytic enzyme is present in an amount of 0.0001 to 2% by weight of the composition, preferably 0.001%.
018-0.06%, more preferably 0.00024-0.048% pure enzyme
At a level, it is incorporated into the detergent composition of the present invention.

The enzyme may be of any suitable origin, such as of plant, animal, bacterial, fungal and yeast origin. The origin may also be mesophilic or extremophilic (cryophilic, eutrophic, thermophilic, barophilic, alkaline, acidophilic, halophilic, etc.). Purified or unpurified forms of these enzymes may also be used. Variants of the natural enzyme are also included in the definition. Variants are obtained, for example, by protein and / or genetic engineering, chemical and / or physical modification of the native enzyme. It is also customary to express the enzyme by a host organism into which the genetic material involved in the production of the enzyme has been cloned. The enzymes are usually incorporated into detergent compositions at a pure enzyme level of 0.0001 to 2% by weight of the detergent composition. Enzymes may be separate components (eg, globules, granules, stabilizing liquids, etc. containing one enzyme) or as a mixture of two or more enzymes (eg,
(Co-granules). Another suitable detergent component that can be added is an enzymatic oxidation scavenger, which comprises
Co-pending European Patent Application No. 92870018, filed Jan. 31, 992.
No. 6 is described in the specification. An example of such an enzymatic oxidation scavenger is ethoxylated tetraethylene polyamine. The various enzyme substances and their means of incorporation into synthetic detergent compositions are also described by Genencor I.
WO 9307263A and WO 9307260A from nternational, WO from Novo
89086694A, and US 3,553, McCarty et al.
139. The enzyme was purchased from Place et al., US Pat.
U.S. Pat. No. 4,507,219 to Hughes, 101,457 and March 26, 1985.
However, it is further disclosed. Enzymatic substances useful in liquid detergent formulations and their incorporation into such formulations are described in US Pat. No. 4,261, April 14, 1981 to Hora et al.
868. Enzymes useful in detergents can be stabilized by various techniques. Enzyme stabilization technology is described in US Pat.
319, October 29, 1986, EP 199,405 and EP of Venegas.
200,586. Enzyme stabilization systems, for example, US3
519,570. A useful Bacillus sp. AC13 that produces proteases, xylanases and cellulases is described in Novo WO9401532A.

Bleach A preferred additional optional detergent component that may be included in the cleaning compositions of the present invention is a conventional activation-other enzyme- and / or metallocatalyst-based bleach system. The combination of cytochromes with other bleaching systems provides improved cleaning with colored and / or daily body stains and / or soil, improved fabric utility cleaning and whitening when formulated as a laundry composition. It turned out to exert. The bleach component for use in the present invention can be any bleach useful in cleaning compositions, including oxygen bleaches and others known in the art. Bleaches suitable for the present invention include activated or deactivated bleaches. For example, bleaching agents such as hydrogen peroxide, PB1, PB4, and percarbonate having a particle size of 400-800 microns. These bleach components can include one or more oxygen bleaches and, depending on the bleach selected, one or more bleach activators. When present, the oxygen bleaching compound is typically present at a level of about 1 to about 25%.

The hydrogen peroxide releasing agent is tetraacetylethylenediamine (TAE), which is perhydrolized to form peracid as an active bleaching species and exerts an improved bleaching effect.
D), nonanoyloxybenzenesulfonate (NOBS, US Pat. No. 4,412,9)
34), 3,5-trimethylhexanoloxybenzenesulfonate
(Described in ISONOBS, EP120,591), pentaacetylglucose
(PAG) or phenol sulfonate esters of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in WO 94/28106). Co-pending European Patent Application 9187020
Acylated citrate esters as disclosed in 7.7, and Procte
r & Gamble co-pending patent applications USSN 60 / 022,786 (filed July 30, 1996) and 60 / 028,122 (October 15, 1996)
Asymmetrical acyclic imido bleach activators of the formula:

Embedded image In the above formula, R ₁ is a C ₇ -C ₁₃ linear or branched saturated or unsaturated alkyl group, R ₂ is a C ₁ -C ₈ linear or branched saturated or unsaturated alkyl group, and R ₃ is C ₁ -C ₄ straight or branched chain saturated or unsaturated alkyl group.

One category of usable oxygen bleaches includes polycarboxylic acid bleaches and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxidedecanedioic acid. Such bleaches are disclosed in U.S. Patent No. 4,483,781, U.S. Patent Application No. 740,446, European Patent Application No. 0,133,354 and U.S. Patent No. 4,412,934. Have been. Highly preferred bleaches include US Pat. No. 4,634,551.
Also included are 6-nonylamino-6-oxoperoxycaproic acid as described in US Pat. Another category of bleaches that can be used is halogen bleaches. Examples of hypohalous acid bleaches include, for example, trichloroisocyanuric acid, sodium and potassium dichloroisocyanurates, N-chloro and N-bromoalkanesulfonamides. Such substances are usually added at 0.5 to 10% by weight, preferably 1 to 5% by weight of the final product. Useful bleaching agents, including bleach activators and peroxygen bleaching compounds, and peroxy acids, for use in detergent compositions according to the present invention, are described in our co-pending application USSN 08 / 136,626, PCT / US95 /
07823, WO95 / 27772, WO95 / 27773, WO95 / 277
74 and WO 95/27775. Hydrogen peroxide may also be present at the beginning or during the washing and / or rinsing process with the addition of an enzyme system capable of generating hydrogen peroxide (ie, the enzyme and its substrate). Such an enzyme system is disclosed in EP patent application 91202655.6, filed Oct. 9, 1991.

[0030] The peroxidase enzyme is used in combination with hydrogen peroxide, an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide, and the like, and a bleach enhancer. They are used for "solution bleaching", i.e. to prevent dyes or pigments that have fallen off the substrate during the washing operation from migrating to other substrates in the washing liquor. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, haloperoxidases such as chloro and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89/099813, and in European Patent Application EP 91202882.6 filed on Nov. 6, 1991 and on Feb. 2, 1996.
It is disclosed in EP 968700133.8 filed on date 0. Laccase enzymes are also suitable. Enhancers are usually included at levels of 0.1 to 5% by weight of the total composition. Preferred enhancers are the substituted phenothiazines and phenoxazines 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (WO94). / 12621), and substituted syringates (C3-C5 substituted alkyl syringates) and phenols. Sodium percarbonate or perborate is the preferred source of hydrogen peroxide. The peroxidases described above are typically incorporated into detergent compositions at an active enzyme level of 0.0001 to 2% by weight of the detergent composition. Metal-containing catalysts for use in the bleach compositions include cobalt-containing catalysts, such as pentaamine cobalt (III) acetate, and manganese-containing catalysts, such as EPA549271,
EPA 549272, EPA 458 397, US 5,246,621, EPA 4
58398, EPA458583, US 5,194,416 and US 5,11
No. 4,611. A bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is disclosed in Patent Application No. 94870206.3.
It is described in the specification.

A preferred metal-containing catalyst for the purposes of the present invention is a transition metal complex of a macropolycyclic hard ligand. The term "macropolycyclic hard ligand" is sometimes abbreviated as "MRL" in the following description. The amount used is a catalytically effective amount, suitably about 1
ppb or more, for example, within about 99.9%, more typically about 0.001 ppm or more, preferably about 0.05 to about 500 ppm ("ppb" stands for parts / billion by weight and "ppm" Represents parts / million by weight). Suitable transition metals, such as Mn, are described below. The term “macrocyclic” refers to M
It means that RL is both macrocycle and polycyclic. "Polycyclic" means at least bicyclic. As used herein, the term “hard”
It includes "having a superstructure" and "crosslinked.""Hard" has been defined as the exact opposite meaning for soft: see DHBusch., Chemical Reviews, (1993), 93,847-860, which is incorporated by reference. More specifically, as used herein, "rigid" is the same as MRL except that it lacks the superstructure found in MRL (especially the linking or preferably bridging portion) (in the main ring, This means that it must be stiffer than a macrocycle (having the same ring size and type and number of atoms) ("parent macrocycle"). In comparing the hardness of macrocycles with and without superstructure, practitioners use macrocycles in free form (not metal bonded). It is well known that hardness is useful in comparing macrocycles; suitable techniques for determining, measuring or comparing hardness include computer methods (eg, Zimmer
, Chemical Reviews, (1995), 95 (38), 2629-2648 or Hancock et al., Inorganic.
a Chimica Acta, (1989), 164, 73-84). Determining which macrocycles are harder than others can often be done by simply creating a molecular model, so knowing the configurational energies in an absolute sense or calculating them accurately is generally Is not mandatory. An excellent comparative measurement of hardness in one macrocycle versus another can be made using inexpensive personal computer-based computer techniques, such as ALCHEMY III from Tripos Associates. Tripos has more expensive commercial software that can perform absolute measurements as well as comparisons, while SHAPES may be used (see Zimmer, supra). One observation that is important in the context of the present invention is that it is optimal for the purposes of the present invention when the parent macrocycle is distinctly soft compared to the crosslinked form. So, unexpectedly,
Rather than starting with a rigid parent macrocycle, it is preferred to crosslink them with a parent macrocycle having at least four donor atoms, such as a cyclam derivative. Another observation is that crosslinked macrocycles are significantly more favorable than macrocycles that have been crosslinked in other ways.

Preferred MRLs are a special type of crosslinked ultra-hard ligand. “Crosslinking”
Is non-limitingly exemplified in 1.11 below. In 1.11 the bridge is -C
H ₂ CH ₂ — moiety. It bridges N ¹ and N ⁸ in the illustrated structure. By comparison, the bridge "the same side", for example if introduced between the N ¹ and N ¹² in 1.11, not sufficient in building "crosslinking", therefore not preferred. Suitable metals for the hard ligand complex include Mn (II), Mn (III), Mn (IV), Mn (
V), Fe (II), Fe (III), Fe (IV), Co (I), Co (II), Co (III), N
i (I), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II)
, Cr (III), Cr (IV), Cr (V), Cr (VI), V (III), V (IV), V (V),
Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (II), Ru
(II), Ru (III) and Ru (IV). Preferred with the transition metal bleach catalyst of the present invention.
New transition metals include manganese, iron and chromium. Preferred oxidation states include (I
There are I) and (III) oxidation states. Manganese (II) in both low spin configuration and high spin complex is included. It should be noted that complexes such as low spin Mn (II) complexes are rather unusual among all coordination chemistries. The designation (II) or (III) represents a coordination transition metal having the required oxidation state, and the coordination metal atom is neither a free ion nor one having only water as a ligand. Generally, as used herein, "ligand" refers to a moiety that is capable of directly covalently bonding to a metal ion. The ligands may be charged or neutral, and may be from simple monovalent donors such as chloride or simple amines that form a single coordination bond and a single point of attachment to the metal; Oxygen or ethylene, which is said to form a three-membered ring and has two possible points of attachment; determined by the number of available sites on the metal and the number of lone pairs or other binding sites on the free ligand; Within the maximum number, including the larger portions, such as ethylenediamine or aza macrocycles, that form single bonds to one or more metals. Many ligands can have multiple points of attachment, forming bonds other than simple donor bonds.

The ligands useful in the present invention are in several groups: MRLs, preferably bridged macropolycycles (preferably one MRL is present in useful transition metal complexes, but is a preferred mononuclear transition metal complex). If not, more may be present, for example two); any other ligand generally different from MRL (usually 0-4, preferably 1
~ 3 such ligands); belonging to ligands which temporarily bind to a metal as part of the catalytic cycle, the latter of which is typically water, hydroxide, oxygen or peroxide. About. The third group of ligands is not essential in defining a metal bleach catalyst that is a stable, isolable chemical compound that is well characterized. A ligand that binds to a metal via a donor atom each having at least one lone pair of electrons available for donation to the metal has a donor capacity or a possible conformational number at least equal to the number of donor atoms. (denticity). Generally, the donor capacity may be fully working or only partially working. In general, MRLs can be seen as a result of adding additional structural stiffness to a particularly selected “parent macrocycle”. More generally, the MRL (and corresponding transition metal catalyst) suitably comprises: (a) at least one macrocycle main ring with 4 or more heteroatoms, and (b) preferably (I) a bridged superstructure, such as a linking moiety; (ii) a crosslinked superstructure, such as a crosslinking linking moiety; and (iii) a covalently bonded macrocycle rigidity selected from the group consisting of: It consists of a non-metallic superstructure. The term "superstructure" is used herein as defined in the document by Busch et al .; see, for example, the document of Busch, "Chemical Reviews".

The preferred superstructure not only increases the stiffness of the parent macrocycle, but also favors the folding of the macrocycle, so that it
) Is coordinated to the metal in some form. A suitable superstructure is significantly simpler, for example using connecting parts as shown below at 1.9 and 1.10.

Embedded image Wherein n is an integer, for example 2-8, preferably less than 6, typically 2-4; or

Embedded image Wherein m and n are integers from about 1 to 8, more preferably 1 to 3; Z is N or CH; T is a compatible substituent such as H, alkyl, trialkylammonium, halogen, Nitro, sulfonate and the like. The aromatic ring of 1.10 may be replaced by a saturated ring, in which case the atoms of Z attached to the ring are N, O, S
Or C.

Without being limited by theory, preorganizations built in MRLs that can exert additional kinetic and / or thermodynamic stability with metal complexes can be characterized by topological constraints, and superstructure It is thought that one or both of the improved hardness (loss of softness) as compared to the free parent macrocycle having no. MRLs, as described above, and their preferred crosslinked subfamily, referred to as "ultra-hard," combine two fixed pre-structure sources. Preferred MRL
Wherein the linking moiety and the parent macrocycle ring are typically of a significant, significant degree more than in the case of many known superstructure-bearing ligands where the superstructure is bonded to a mostly planar and often unsaturated macrocycle. Combined to form a ligand having a "fold". For example, DHBusch, Chemical Reviews, (1993), 93, 8
See 47-880. Furthermore, the preferred MRLs are (1) they are characterized by very high proton affinities, as in the case of so-called "proton sponges"; (2)
They tend to react slowly with polyvalent transition metals, which, when combined with (1) above, make the synthesis of their complexes with certain hydrolyzable metal ions difficult in hydroxylic solvents; (3) When coordinated to a transition metal atom as described above, the MRL becomes a complex with exceptional kinetic stability, such that the metal ion alone breaks the complex with the normal ligand. And (4) these complexes have some special properties, such as having exceptional thermodynamic stability, however, the unusual nature of MRL dissociation from transition metals Kinetics does not allow the use of conventional equilibrium assays that can quantify this property.

In one aspect of the invention, the MRL comprises: (i) having four or more donor atoms separated from each other by a covalent chain of at least one, preferably two or three, non-donor atoms (these Of the donor atoms are preferably N, more preferably at least 4 are N), and 2 to 5 (preferably 3 to 4, more preferably 4) of these donor atoms Is an organic macrocycle ring coordinated to the same transition metal in a complex; (ii) a linking moiety, preferably a bridged chain, that covalently links at least two (preferably non-adjacent) donor atoms of the organic macrocycle ring [The covalently bonded (preferably non-adjacent) donor atom is a bridgehead donor atom coordinated to the same transition metal in the complex, wherein the linking moiety (preferably a bridging chain) is from about 2 to about 10 atom Ranaru (preferably, the tether is selected from another donor atoms with three or four non-donor atoms, and 4-6 one non-donor atoms,) is those composed of].

Suitable MRLs are further non-limitingly exemplified by the following compounds:

Embedded image This is the MRL according to the invention, a highly preferred bridged methyl-substituted (all tertiary nitrogen atom) derivative of cyclam. Formally, this ligand is named 5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane using the extended von Baeyer system. "A Guide to IUPAC
Nomenclature of Organic Compounds: Recommendations 1993 ", R.Panico, WHPo
well and JC Richer (Eds.), Blackwell Scientific Publications, Boston, 1993
See especially section R-2.4.2.1. According to conventional usage, N1 and N8 are "bridgehead atoms"; more particularly, "bridgehead donor atoms" because, as mentioned above, they have a lone pair of electrons that can donate to a metal. N1 is attached to two non-bridgehead donor atoms N5 and N12 in separate saturated carbon chains 2, 3, 4, and 14, 13, and a "linking moiety" a, which is here a saturated carbon chain of two carbon atoms.
b is attached to the bridgehead donor atom N8. N8 has separate chains 6, 7 and 9,
At 10, 11 it is bonded to two non-bridgehead donor atoms N5 and N12. The chains a, b are of the "linking moiety" as described above and of a special preferred type referred to as a "bridge" moiety. The "macrocycle ring" or "main ring" (I
UPAC) includes all four donor atoms and chains 2, 3, 4; 6, 7; 9, 10
, 11; and 13, 14, but not a, b. The ligand is conventional bicyclic. The short bridges or "connecting portions" a, b are "bridges" as described above, and a, b bisect the macrocycle ring. MRLs are, of course, not limited to being synthesized from preformed macrocycles + preformed "hardening" or "conformational modification" elements, but rather various synthetic means such as template synthesis are useful. . For example, Busch et.al., "Heterocyclic com
pounds: Aza-crown macrocycles ", JSBradshaw et.al.

The transition metal bleach catalysts useful in the compositions of the present invention generally include known compounds that meet the definition of the present invention, and more preferably, are specifically designed for the present laundry or cleaning use. There are a number of new compounds, exemplified by, but not limited to: dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6
. 6.2] Hexadecanemanganese (II) dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5
. 5.2] Tetradecanemanganese (II) diako-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.
6.2] Hexadecanemanganese (II) hexafluorophosphate aco-hydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecanemanganese (III) hexafluorophosphate 4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.
5.2] Tetradecanemanganese (II) hexafluorophosphate diako-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.
6.2] Hexadecanemanganese (II) tetrafluoroborate diako-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5.
5.2] Tetradecanemanganese (II) tetrafluoroborate dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6
. 6.2] Hexadecanemanganese (III) hexafluorophosphate dichloro-5,12-di-n-butyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-5 , 12-Dibenzyl-1,5,8,12-tetraazabicyclo
[6.6.2] hexadecanemanganese (II) dichloro-5-n-butyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-5 -N-octyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-5-n-butyl-12-methyl-1,5,8, 12-tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6
. 6.2] Hexadecaneiron (II) dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5
. 5.2] Tetradecaneiron (II) dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6
. 6.2] Hexadecanecopper (II) dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5
. 5.2] Tetradecane copper (II) dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6
. 6.2] Hexadecanecobalt (II) dichloro-4,10-dimethyl-1,4,7,10-tetraazabicyclo [5
. 5.2] Tetradecanecobalt (II) dichloro-5,12-dimethyl-4-phenyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-4,10- Dimethyl-3-phenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecanemanganese (II) dichloro-5,12-dimethyl-4,9-diphenyl-1,5,8,12 -Tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-4,10-dimethyl-3,8-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecanemanganese (II) dichloro-5,12-dimethyl-2,11-diphenyl-1,5,8,12-
Tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-4,10-dimethyl-4,9-diphenyl-1,4,7,10-tetraazabicyclo [5.5.2] tetradecanemanganese (II) II) Dichloro-2,4,5,9,11,12-hexamethyl-1,5,8,12-
Tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-2,3,5,9,10,12-hexamethyl-1,5,8,12-
Tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-2,2,4,5,9,9,11,12-octamethyl-1,5,8
, 12-Tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-2,2,4,5,9,11,11,12-octamethyl-1,5
8,12-tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-3,3,5,10,10,12-hexamethyl-1,5,8,12
-Tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-3,5,10,12-tetramethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecanemanganese II) dichloro-3-butyl-5,10,12-trimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-1,5,8,12-tetra Azabicyclo [6.6.2] hexadecanemanganese (II) dichloro-1,4,7,10-tetraazabicyclo [5.5.2] tetradecanemanganese (II) dichloro-1,5,8,12-tetra Azabicyclo [6.6.2] hexadecaneiron (II) dichloro-1,4,7,10-tetraazabicyclo [5.5.2] tetradecaneiron (II) aco-chloro-2- (2-hydroxyphenyl )- , 12-dimethyl-1,
5,8,12-Tetraazabicyclo [6.6.2] hexadecanemanganese (II) aco-chloro-10- (2-hydroxybenzyl) -4,10-dimethyl-1
, 4,7,10-Tetraazabicyclo [5.5.2] tetradecanemanganese (II)
Chloro-2- (2-hydroxybenzyl) -5-methyl-1,5,8,12-
Tetraazabicyclo [6.6.2] hexadecanemanganese (II) chloro-10- (2-hydroxybenzyl) -4-methyl-1,4,7,10
-Tetraazabicyclo [5.5.2] tetradecanemanganese (II) chloro-5-methyl-12- (2-picolyl) -1,5,8,12-tetraazabicyclo [6.6.2] hexadecanemanganese (II) chloride chloro-4-methyl-10- (2-picolyl) -1,4,7,10-tetraazabicyclo [5.5.2] tetradecanemanganese (II) chloride dichloro-5- (2-sulfato ) Dodecyl-12-methyl-1,5,8,1
2-tetraazabicyclo [6.6.2] hexadecanemanganese (III) aco-chloro-5- (2-sulfato) dodecyl-12-methyl-1,5,8
, 12-Tetraazabicyclo [6.6.2] hexadecanemanganese (II) aco-chloro-5- (3-sulfonopropyl) -12-methyl-1,5,8,
12-tetraazabicyclo [6.6.2] hexadecanemanganese (II) dichloro-5- (trimethylammoniopropyl) dodecyl-12-methyl-
1,5,8,12-Tetraazabicyclo [6.6.2] hexadecanemanganese (I
II) Chloride Dichloro-5,12-dimethyl-1,4,7,10,13-pentaazabicyclo [8.5.2] heptadecanemanganese (II) dichloro-14,20-dimethyl-1,10,14 , 20-Tetraazatricyclo [8.6.6] docosa-3 (8), 4,6-trienemanganese (II) dichloro-4,11-dimethyl-1,4,7,11-tetraazabicyclo [ 6
. 5.2] Pentadecanemanganese (II) dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [7
. 6.2] Heptadecanemanganese (II) dichloro-5,13-dimethyl-1,5,9,13-tetraazabicyclo [7
. 7.2] Heptadecanemanganese (II) dichloro-3,10-bis (butylcarbonyl) -5,12-dimethyl-1,
5,8,12-Tetraazabicyclo [6.6.2] hexadecanemanganese (II) diaco-3,10-dicarboxy-5,12-dimethyl-1,5,8,12-
Tetraazabicyclo [6.6.2] hexadecanemanganese (II) chloro-20-methyl-1,9,20,24,25-pentaaza-tetracyclo [7.7.7.1 ^3,7 . 1 ^11,15 ] pentacosa-3,5,7 (24),
11, 13, 15 (25) - hexa ene manganese (II) hexafluorophosphate trifluoromethanesulfonyl Roh-20-methyl -1,9,20,24,25- pentaaza - tetracyclo [7.7.7.1 ^{3, 7} . 1 ^11,15 ] pentacosa-
3,5,7 (24), 11,13,15 (25) -hexaene manganese (II) trifluoromethanesulfonate trifluoromethanesulfono-20-methyl-1,9,20,24,25-pentaaza-tetracyclo [ 7.7.7.1 ^3,7 . 1 ^11,15 ] pentacosa-
3,5,7 (24), 11,13,15 (25) -hexaeneiron (II) trifluoromethanesulfonate chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo [ 6.6.5] nonadecanemanganese (II) hexafluorophosphate chloro-4,10,15-trimethyl-1,4,7,10,15-pentaazabicyclo [5.5.5] heptadecanemanganese (II) ) Hexafluorophosphate chloro-5,12,17-trimethyl-1,5,8,12,17-pentaazabicyclo [6.6.5] nonadecanemanganese (II) chloride chloro-4,10,15-trimethyl -1,4,7,10,15-pentaazabicyclo [5.5.5] heptadecanemanganese (II) chloride

Implementers may be more informative if certain terms have additional definitions and explanations. As used herein, a "macrocycle ring" refers to four or more donor atoms
(Ie, a heteroatom such as nitrogen or oxygen) and a covalently bonded ring formed from the carbon chains connecting them, and any macrocycle ring described herein has at least 10 , Preferably at least 12 atoms in the macrocycle ring. The MRL may have more than one type of ring per ligand, but at least one macrocycle ring must be identifiable. Further, in a preferred embodiment, the two heteroatoms are not directly bonded. Preferred transition metal bleach catalysts have an MRL of at least 10
It consists of an organic macrocycle ring (main ring) having 20 atoms, preferably 12 to 18 atoms, more preferably about 12 to about 20 atoms, most preferably 12 to 16 atoms.

A “donor atom” is a heteroatom such as nitrogen, oxygen, phosphorus or sulfur that, when incorporated into a ligand, is used to form a donor-acceptor bond with a metal. It still has at least one lone pair of electrons. Preferred transition metal bleach catalysts are those wherein the donor atom in the organic macrocycle ring of the bridged MRL is selected from the group consisting of N, O, S and P, preferably N and O, most preferably all N. All coordinated to the same transition metal,
Preference is also given to bridged MRLs having 4 or 5 donor atoms. The most preferred transition metal bleach catalysts are those in which the bridged MRL has four nitrogen donor atoms all coordinated to the same transition metal, and five nitrogens in which the bridged MRL is all coordinated to the same transition metal. It has atoms. The "non-donor atom" of the MRL is most commonly carbon, and some atom types are particularly useful for any exocyclic substituent of the macrocycle (eg, the "side group" moiety described below). Although they may be included, they are not only donor atoms for the purposes essential in forming metal catalysts, but they are also not carbon. Thus, in the broadest sense, the term "non-donor atom" relates to an atom that is not essential for forming a donor bond with the metal of the catalyst. Examples of such atoms include sulfur incorporated into non-coordinating sulfonate groups, phosphorus incorporated into phosphonium salt moieties, phosphorus incorporated into P (V) oxide, non-transition metals, and the like. There are heteroatoms. In certain preferred embodiments, all non-donor atoms are carbon.

Synthesis of [Mn (Biciclem) Cl ₂ ]

Embedded image (A) Method I "Biciclem" (5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane) was prepared according to GRWeisman et al., J. Amer. Chem. Soc. , (1
990), 112, 8604. Bicyclam (1.00 g,
The 3.93 mmol) dry _CH 3 CN (35ml, dissolved in distilled) from CaH _2.
The solution is then degassed at 15 mm until the CH ₃ CN starts to boil. The flask is then returned to atmospheric pressure with Ar. This deaeration operation is repeated four times. HTWitteveen et
Mn (pyridine) ₂ Cl ₂ (1.12 g, 3.93 mmol), synthesized according to the literature procedure of al., J. Inorg. Nucl. Chem., (1974), 36, 1535, is added under Ar. The cloudy reaction slowly darkens. After stirring overnight at room temperature, the reaction begins to turn dark brown with suspended particulates. Filter the reaction through a 0.2μ filter. The liquid is pale yellow-brown. The filtrate is evaporated to dryness using a funnel evaporator. 0.05 at room temperature
After drying in mm overnight, 1.35 g of an off-white solid product is collected in 90% yield. Elemental analysis:% Mn, 14.45;% C , 44.22;% H, 7.95; [Mn (bicyclam) Cl _{2], MnC 14 H 30 N 4 Cl} 2, the theoretical value of MW = 380.26 Found:% Mn, 14.98;% C, 44.48;% H, 7.86; ion spray mass spectrometry, one major at 354 mu corresponding to [Mn (bicicram) (formate)] ^+. Indicates a peak.

[0042](B) Method II Freshly distilled bicyclam (25.00 g) produced in the same manner as above
, 0.0984 mol) in dry CH₃CN (900ml, CaH₂Dissolved from)
Understand. Then CH₃Degas solution at 15 mm until CN begins to boil
. The flask is then returned to atmospheric pressure with Ar. This deaeration operation is repeated four times. MnCl ₂ (11.25 g, 0.0894 mol) is added under Ar. The cloudy reaction solution is immediately
Begins to darken. After stirring under reflux for 4 hours, the reaction solution becomes dark brown with suspended fine particles.
Start. The reaction solution is filtered with a 0.2 μ filter under dry conditions. The liquid is pale yellow-brown
is there. The filtrate is evaporated to dryness using a funnel evaporator. The resulting tan solid
The material is dried overnight at room temperature at 0.05 mm. The solid substance was dissolved in toluene (100 m
l) and heat to reflux. Decant the toluene and repeat the operation with another toluene
Repeat with 100 ml. Residual toluene is removed with a funnel evaporator. Room
After drying overnight at 0.05 mm at room temperature, 31.75 g of a pale blue solid product was obtained in a yield of 9
Collect at 3.5%. Elemental analysis:% Mn, 14.45;% C, 44.22;% H,
7.95;% N, 14.73;% Cl, 18.65; [Mn (bicicrum) Cl ₂ ], MnC₁₄H₃₀N₄Cl₂, MW = 380.26, theoretical value; measured value:% Mn
% C, 44.69;% H, 7.99;% N, 14.78;% Cl, 14.69;
, 18.90 (Karl Fischer water, 0.68%);
In the vector measurement, [Mn (bicyclam) (formate)]⁺354m equivalent to
u indicates one major peak.

Bleaches other than oxygen bleaches are known in the art and may be used in the present invention. One type of non-oxygen bleach that is of particular interest is a light activated bleach such as a sulfonated zinc and / or aluminum phthalocyanine. These substances can adhere to the substrate during the cleaning process. Like hanging clothes in the sun and drying
Upon irradiation with light in the presence of oxygen, the sulfonated zinc phthalocyanine is activated, thereby bleaching the substrate. A preferred zinc phthalocyanine and light activated bleaching process is described in U.S. Pat. No. 4,033,718. Typically, the detergent compositions contain from about 0.025 to about 1.25% by weight of the sulfonated zinc phthalocyanine.

Surfactant system The cleaning composition according to the invention is characterized in that the surfactant is selected from nonionic and / or anionic and / or cationic and / or amphoteric and / or zwitterionic and / or semipolar surfactants. And usually a surfactant system. Surfactants are typically present at a level of 0.1-60% by weight. Further preferred loading levels are 1 to 35% by weight, most preferably 1 to 30% by weight, for the cleaning composition according to the invention. The surfactant is preferably formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions, surfactants are most preferably formulated to promote the stability of, or at least degrade, the enzyme in these compositions. Preferred surfactant systems for use in accordance with the present invention include the ones described herein.
One or more nonionic and / or anionic surfactants are included as surfactants.

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of the surfactant system of the present invention, with polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols with alkyl phenols having an alkyl group of from about 6 to about 14, preferably from about 8 to about 14, carbon atoms in a linear or branched configuration. In a preferred embodiment, the ethylene oxide is present in an amount corresponding to about 2 to about 25 moles, more preferably about 3 to about 15 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include GAF Cor
Igepal ^™ CO-630 from poration, all Rohm & Haas Compan
Triton ^™ X-45, X-114, X-100 and X-1 sold by y
02. These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

The primary and secondary fatty alcohols are combined with about 1 to about 25 moles of ethylene oxide.
The condensation product is used as a nonionic surfactant in the nonionic surfactant system of the present invention.
Suitable for The alkyl chain of the aliphatic alcohol is linear or branched, primary or
It is secondary and usually has about 8 to about 22 carbon atoms. About 8 to about 20 carbon atoms
More preferably an alcohol having an alkyl group of about 10 to about 18 carbon atoms;
Condensation products with about 2 to about 10 moles of ethylene oxide per mole of alcohol are preferred.
Good. About 2 to about 7 moles of ethylene oxide per mole of alcohol, most preferably
Alternatively, 2 to 5 moles of ethylene oxide are present in the above condensation product. This Thailand
Examples of commercially available nonionic surfactants include Union Carbide Corporation
Sold by Tergitol^TM15-S-9 (C₁₁-C_FifteenStraight-chain alcohols and ethi
Condensation product with 9 mol of lenoxide), Tergitol^TM24-L-6NMW (C₁₂-C ₁₄ Condensation product of primary alcohol and 6 moles of ethylene oxide with narrow molecular weight distribution)
; Neodol sold by Shell Chemical Company^TM45-9 (C₁₄-C_Fifteenstraight
Condensation product of a chain alcohol and 9 moles of ethylene oxide), Neodol^TM23-3 (C ₁₂ -C₁₃Condensation product of linear alcohol and 3.0 moles of ethylene oxide), Neodol ^TM 45-7 (C₁₄-C_FifteenCondensation product of linear alcohol with 7 mol of ethylene oxide
), Neodol^TM45-5 (C₁₄-C_FifteenLinear alcohol and 5 moles of ethylene oxide
Kyro sold by The Procter & Gamble Company^TMEOB
(C₁₃-C_FifteenCondensation product of alcohol and 9 moles of ethylene oxide);
LA O3O or O5O (C₁₂-C₁₄With alcohol
Condensation products with 3 or 5 moles of ethylene oxide). In these products
The preferred range of HLB is 8-11, most preferably 8-10.

The nonionic surfactants of the surfactant system of the present invention include hydrophobic groups having about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and about 1.3 to about 10 carbon atoms. ,
Llenado, published January 21, 1986, having a polysaccharide having preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units, such as a polyglycoside hydrophilic group. Also useful are the alkyl polysaccharides disclosed in U.S. Patent No. 4,565,647. Reducing sugars having 5 or 6 carbon atoms can also be used, for example, glucose, galactose and galactosyl moieties can be used in place of the glucosyl moiety (optionally a hydrophobic group is attached to the 2, 3, 4 position, etc. to form a glucoside or Give glucose or galactose instead of galactoside). For example, an intersugar linkage may be present between one position of the additional saccharide unit and positions 2, 3, 4, and / or 6 of the preceding saccharide unit.

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _{x where} R ² is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and (Alkyl groups have about 10 to about 18, preferably about 12 to about 14 carbon atoms); n is 2 or 3, preferably 2; t is 0 to about 10, preferably 0; x is about 1
. 3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7.
It is. Glycosyl is preferably derived from glucose. To make these compounds, an alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose or a source of glucose to form glucoside (1).
Bond). Additional glycosyl units may also be linked between their 1-position and the preceding glycosyl unit at positions 2, 3, 4, and / or 6, preferably predominantly at position 2.

[0049] 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 the additional nonionic surfactant system of the present invention. The hydrophobic portion of these compounds is preferably about 1500
It has a molecular weight of ~ 1800 and is water-insoluble. The addition of a polyoxyethylene moiety to this hydrophobic moiety tends to increase the overall water solubility of the molecule, and the liquidity of the product is such that the polyoxyethylene content is up to about 50% of the total weight of the condensation product. Again, this corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain commercially available Plurafac ^™ LF sold by BASF
There are 404 and Pluronic ^™ surfactants.

As the nonionic surfactant of the nonionic surfactant system of the present invention, a product obtained from the reaction of propylene oxide with ethylenediamine and a condensation product of ethylene oxide are also suitable for use. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, usually from about 2500 to about 300
It has a molecular weight of 0. The hydrophobic moiety is condensed with ethylene oxide to an extent that the condensation product contains about 40 to about 80% by weight polyoxyethylene and has a molecular weight of about 5000 to about 11,000. Examples of nonionic surfactants of this type include certain commercial Tetronic ^™ compounds sold by BASF.

The nonionic surfactants of the surfactant system of the present invention include polyethylene oxide condensates of alkylphenols, primary and secondary aliphatic alcohols and about 1 to about 25
Condensation products with moles of ethylene oxide, alkyl polysaccharides, and mixtures thereof are preferred for use. _C 8 -C ₁₄ alkyl phenol ethoxylates having from 3 to 15 ethoxy groups, _C 8 -C ₁₈ alcohol ethoxylates having from 2 to 10 ethoxy groups (preferably C ₁₀ average), and mixtures thereof are most preferred.

A highly preferred nonionic surfactant is a polyhydroxy fatty acid amide surfactant of the formula:

Embedded image Or the formula ^{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, Z is A polyhydroxyhydrocarbyl having a linear hydrocarbyl chain and at least three hydroxyls directly attached to the chain, or an alkoxylated derivative thereof. Preferably, R ¹ is methyl, R ² is a linear C _11-15 alkyl or C _16-18 alkyl or alkenyl chain, such as coconut alkyl, or a mixture thereof, and Z is glucose, It is derived from reducing sugars such as fructose, maltose and lactose.

Suitable anionic surfactants used are “The Journal of the American O.
il Chemists Society ", 52 (1975 ), C 8 -C 20 carboxylic acids which are sulfonated with gaseous SO ₃ according Pp.323-329 (i.e., fatty acids), including straight-chain esters of, linear alkylbenzene sulfonates, alkyl It is an ester sulfonate surfactant.
Suitable starting materials include natural fatty substances such as those derived from tallow, palm oil and the like.

Particularly preferred alkyl ester sulfonate surfactants for laundry applications include:
There are alkyl ester sulfonate surfactants of the following structural formula:

Embedded image Wherein R ³ is C ₈ -C ₂₀ hydrocarbyl, preferably alkyl, or a combination thereof, R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl, or a combination thereof, and M is an alkyl ester sulfonate. Is a cation that forms a water-soluble salt with the cation. Suitable salt-forming cations include metals such as sodium, potassium and lithium, substituted or unsubstituted ammonium cations, for example, monoethanolamine, diethanolamine and triethanolamine. Preferably, R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Methyl ester sulfonates wherein R ³ is C ₁₀ -C ₁₆ alkyl are particularly preferred.

Other suitable anionic surfactants include alkyl sulfate surfactants, which are water-soluble salts or acids of the formula ROSO ₃ M, wherein R is preferably C ₁₀ -C ₂₄ hydrocarbyl, preferably alkyl or hydroxyalkyl having a C ₁₀ -C ₂₀ alkyl moiety, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), ammonium or Substituted ammonium (eg,
Quaternary ammonium cations such as methyl-, dimethyl- and trimethyl-ammonium cations, and tetramethylammonium and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and And mixtures thereof). Typically, C ₁₂ -C ₁₆ alkyl chains are preferred at low wash temperatures (eg, below about 50 ° C.) and C ₁₆ -C ₁₈ alkyl chains are preferred at high wash temperatures (eg, above about 50 ° C.).

[0056] Other anionic surfactants useful for cleaning purposes can also be included in the cleaning compositions of the present invention. These include salts of soaps, including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as the mono, di and triethanolamine salts, C ₈ -C ₂₂ primary or secondary alkane sulfonates,
C ₈ -C ₂₄ olefin sulfonates, for example British Patent Specification 1,082,17
As described in US Pat. No. 9, sulphonated polycarboxylic acid, C ₈ -C ₂₄ alkyl polyglycol ether sulphate produced by the sulphonation of the pyrolysis products of alkaline earth metal citrates (within 10 mol of ethylene oxide Including);
Alkyl glycerol sulfonate, fatty acyl glycerol sulfonate, fatty oleyl glycerol sulfate, alkyl phenol ethylene oxide ether sulfate, paraffin sulfonate, alkyl phosphate, isethionate such as acyl isethionate, N-acyl taurate, alkyl succinamate and sulfosuccinate, sulfo monoesters of succinate (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and sulfosuccinate diesters (especially saturated and unsaturated C ₆ -C ₁₂ diesters), acyl sarcosinates, sulfates of alkylpolyglucoside Sulfates of such alkyl polysaccharides (nonionic non-sulfate compounds are described below), branched primary alkyl sulfates, And the formula RO (CH ₂ CH ₂ O) _k —CH ₂ COO ⁻ M ⁺ (
R is C ₈ -C ₂₂ alkyl, k is an integer from 1 to 10 and M is a soluble salt-forming cation). Resin acids and hydrogenated resin acids, such as rosin, hydrogenated rosin, resin acids and hydrogenated resin acids, which are present in or derived from tall oil, are also suitable. Another example is "Surface Active Agents and Detergents" (Vol.I and II, Schwart
z, Perry and Berch). Various such surfactants include 197
Laughlin et al., U.S. Pat. No. 3,929,678, issued Dec. 30, 5th, is also generally disclosed in column 23, line 58 to column 29, line 23 (for reference). Incorporated herein). When included in the present compositions, the laundry detergent compositions of the present invention typically contain from about 1 to about 40% by weight, preferably from about 3 to about 20%, of such anionic surfactant. I have.

Highly preferred anionic surfactants include those of the formula RO (A)_mSO₃Water solubility of M
There are alkylalkoxylated sulfate surfactants that are salts or acids,
And R is unsubstituted C_Ten-C_{twenty four}Alkyl or C_Ten-C_{twenty four}Hydro with alkyl moiety
A xyalkyl group, preferably C₁₂-C₂₀Alkyl or hydroxyalkyl, further
Preferably C₁₂-C₁₈Alkyl or hydroxyalkyl, wherein A is ethoxy
M is greater than zero, typically from about 0.5 to about
6, more preferably from about 0.5 to about 3, wherein M is H or a cation, such as a metal
Cations (eg sodium, potassium, lithium, calcium, magnesium
Etc.), ammonium or substituted ammonium cations. Alkyl ethoxy
Sulfated and alkylpropoxylated sulfates are contemplated in the present invention.
Can be Specific examples of the substituted ammonium cation include methyl, dimethyl, and trimethyl.
Ammonium cation, and tetramethylammonium and dimethylpi
Quaternary ammonium cations such as peridinium cations, and ethylamine
, Derived from alkylamines such as diethylamine, triethylamine
And mixtures thereof. Exemplary surfactants include C₁₂-C₁₈Alkyl
Polyethoxylate (1.0) sulfate (C₁₂-C₁₈E (1.0) M), C ₁₂ -C₁₈Alkyl polyethoxylate (2.25) sulfate (C₁₂-C₁₈E
(2.25) M), C₁₂-C₁₈Alkyl polyethoxylate (3.0) sulfate
(C₁₂-C₁₈E (3.0) M) and C₁₂-C₁₈Alkyl polyethoxyle
(4.0) sulfate (C₁₂-C₁₈E (4.0) M), where M is a convenience
It is selected from sodium and potassium.

The cleaning compositions of the present invention include cationic, amphoteric, bipolar and semipolar interfaces.
Activators, and nonionic and / or anionic other than those already mentioned above
Surfactants may also be included. Cationic detersive surfactants suitable for use in the cleaning compositions of the present invention include:
Having two long-chain hydrocarbyl groups. Such cationic surface activity
Examples of agents include ammonium surfactants such as alkyltrimethylammonium
There are halogenides, and surfactants having the formula: [R²(OR³)_y] [R⁴(OR³)_y]₂R⁵N⁺X⁻ R in the above formula²Is an alkyl having about 8 to about 18 carbon atoms in the alkyl chain or
An alkylbenzyl group; each R³Is -CH₂CH₂-, -CH₂CH (CH₃ )-, -CH₂CH (CH₂OH)-, -CH₂CH₂CH₂-And their
Selected from the group consisting of mixtures; each R⁴Is C₁-C₄Alkyl, C₁-C₄Hi
Droxyalkyl, two R⁴Benzyl ring structure formed by linking groups, -CH ₂ CHOH-CHOHCOR⁶CHOHCH₂OH (R⁶Is about 1000 or less
Hexose or hexose polymer having a molecular weight), and y is 0.
R is selected from the group consisting of hydrogen; R⁵Is R⁴Is the same as R² + R⁵Is an alkyl chain having a total number of carbon atoms of about 18 or less;
0 and the sum of y values is from 0 to about 15; X is any suitable anion
It is.

A quaternary ammonium surfactant suitable for the present invention has the following formula (I):

Embedded image Wherein R ₁ is short chain length alkyl (C ₆ -C ₁₀ ) or alkylamidoalkyl of formula (II):

Embedded image Wherein y is 2-4, preferably 3 .; wherein R ₂ is H or C ₁ -C ₃ alkyl; x is 0-4, preferably 0-2, most preferably 0. Wherein R ₃ , R ₄ and R ₅ are the same or different and are a short-chain alkyl (C ₁ -C ₃ ) or an alkoxylated alkyl of the following formula III:

Embedded image (R ⁶ is C ₁ -C ₄ and z is 1 or 2) wherein X ⁻ is a counter ion, preferably a halide such as chloride or methyl sulfate.

Preferred quaternary ammonium surfactants are those of the formula wherein R ₁ is C ₈ , C ₁₀ or mixtures thereof, x = 0, R ₃ , R ₄ ＝ CH ₃ and R ₅ ＣＨCH ₂ CH ₂ OH. I
As defined in

Highly preferred cationic surfactants are water-soluble quaternary ammonium compounds useful in the present composition, having the formula: R ₁ R ₂ R ₃ R ₄ N ⁺ X ⁻ (i) Wherein R ₁ is C ₈ -C ₁₆ alkyl, and each of R ₂ , R ₃ and R ₄ is independently C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl and-(
C ₂ H ₄₀₎ are _x H (x has a value of 2 to 5), X is an anion. No more than one of R ₂ , R ₃ or R ₄ must be benzyl.

The preferred alkyl chain length for R ₁ is C ₁₂ -C ₁₅ , especially where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat, or synthesized by olefin build-up or oxo alcohol synthesis. Induced by. R ₂ ,
Preferred groups for R ₃ and R ₄ are methyl and hydroxyethyl groups, and the anion X is selected from halide, methosulfate, acetate and phosphate ions. Examples of quaternary ammonium compounds of formula (i) suitable for use in the present invention are: coconut trimethylammonium chloride or bromide coconut methyldihydroxyethylammonium chloride or bromide decyltriethylammonium chloride decyldimethylhydroxyethylammonium chloride or bromide C _12-15 dimethyl hydroxyethyl ammonium chloride or bromide coconut dimethyl hydroxyethyl ammonium chloride or bromide myristyl trimethyl ammonium methyl sulphate lauryl dimethyl benzyl ammonium chloride or bromide lauryl dimethyl (ethenoxy) ₄ ammonium chloride or bromide choline esters (R ₁ is CH ₂ -CH _2- OC (= O) _-C12-14Al A compound of formula (i) wherein R ₂ , R ₃ , R ₄ are methyl. Dialkylimidazoline (compound of formula (i)) Other cationic surfactants useful in the present invention are described in 1980. U.S. Patent No. 4,228,044 to Cambre and European Patent Application No.
No. 00,224.

Typical cationic fabric softening components include water-insoluble quaternary ammonium fabric softening activators or their corresponding amine precursors, with dilong chain alkyl ammonium chloride or methyl sulfate being the most commonly used. I have.

Among these preferred cationic softeners are: 1) ditallow dimethyl ammonium chloride (DTDMAC) 2) dihydrogenated tallow dimethyl ammonium chloride 3) dihydrogenated tallow dimethyl ammonium methyl sulfate 4) dihydrogenated tallow dimethyl ammonium methyl sulfate Stearyl dimethyl ammonium chloride 5) Dioleyl dimethyl ammonium chloride 6) Dipalmityl hydroxyethyl methyl ammonium chloride 7) Stearyl benzyl dimethyl ammonium chloride 8) Tallow trimethyl ammonium chloride 9) Hydrogenated tallow trimethyl ammonium chloride 10) _C12-14 alkyl hydroxy _{Ethyldimethylammonium} chloride 11) _{C12-18 alkyldihydroxyethylmethylammonium} chloride 12) Di (stearoyl) (Oxyethyl) dimethylammonium chloride (DSOEDMAC) 13) di (tallowoxyethyl) dimethylammonium chloride 14) ditallow imidazolinium methyl sulfate 15) 1- (2-tallowylamidoethyl) -2-tallowyl imidazolinium methyl sulfate Biodegradable quaternary ammonium compounds have been provided as an alternative to the traditionally used dilong chain alkyl ammonium chloride and methyl sulfate. Such a quaternary ammonium compound has a long-chain alkyl (alkenyl) group in which a functional group such as a carboxy group is interposed. The above substances and fabric softening compositions containing them are described in EP-A-0,040,562 and EP-A-0,
It has been disclosed in numerous documents such as 239,910.

The quaternary ammonium compound and its amine precursor are represented by the following formula (I) or (II)
)have:

Embedded image The formula Q is -O-C (O) -, - C (O) -O -, - O-C (O) -O-, -NR 4 -C (O) -, - C (O) - NR ⁴ - is selected from; ^{R 1} is _{(CH 2)} is n ^{-Q-T 2} or ^{T 3;} is ^{R 2} is _{(CH 2)} m ^{-Q-T 4} or ^{T 5} or ^{R 3,;} R ³ is C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl or H; R ⁴ is H, C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl; T ¹ , T ² , T ³ , T ⁴ , T ⁵ are independently C ₁₁ -C ₂₂ alkyl or alkenyl; n and m are integers from 1 to 4; and X ⁻ is a softener compatible anion. Non-limiting examples of softener compatible anions include chloride or methyl sulfate. The alkyl or alkenyl chains T ¹ , T ² , T ³ , T ⁴ , T ⁵ are at least 11
And preferably at least 16 carbon atoms.
The chain may be straight or branched. Tallow is a convenient and inexpensive source of long-chain alkyl and alkenyl materials. Compounds in which T ¹ , T ² , T ³ , T ⁴ , T ⁵ represent a mixture of long chain substances typical of tallow are particularly preferred.

Specific examples of quaternary ammonium compounds suitable for use in the present aqueous fabric softening composition include: 1) N, N-di (tallowyloxyethyl) -N, N-dimethylammonium chloride 2) N, N N-di (tallowyloxyethyl) -N-methyl, N- (2-hydroxyethyl) ammonium methyl sulfate 3) N, N-di (2-tallowyloxy-2-oxoethyl) -N, N-dimethylammonium Chloride 4) N, N-di (2-tallowyloxyethylcarbonyloxyethyl) -N, N-dimethylammonium chloride 5) N- (2-tallowyloxy-2-ethyl) -N- (2-tallowyl) Oxy-2-oxoethyl) -N, N-dimethylammonium chloride 6) N, N, N-tri (tallowyloxyethyl) -N-methyl Ammonium chloride 7) N- (2-Tallowyloxy-2-oxoethyl) -N- (tallowyl-N, N-dimethylammonium chloride) 8) 1,2-Ditaloyloxy-3-trimethylammoniopropane chloride and There are mixtures of the above substances.

When included in the present compositions, the cleaning compositions of the present invention typically have a pH of 0.5.
It contains from 2 to about 25% by weight, preferably from about 1 to about 8%, of such cationic surfactants. Amphoteric surfactants are also suitable for use in the cleaning compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic group is linear or It may be a branched chain. One of the aliphatic substituents is at least about 8
It has two carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one has an anionic water-soluble group, such as a carboxy, sulfonic acid, sulfate group. For examples of amphoteric surfactants, see Laughlin et al., U.S. Pat. No. 3,929,678, issued Dec. 30, 1975, column 19, lines 18-35. When included in the present compositions, the cleaning compositions of the present invention typically have a pH of 0.5.
It contains from 2 to about 15% by weight, preferably from about 1 to about 10%, of such amphoteric surfactants. Zwitterionic surfactants are also suitable for use in the cleaning composition. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. . For examples of zwitterionic surfactants, see Laughlin et al., US Pat. No. 3,929, issued Dec. 30, 1975.
, 678, column 19, line 38 to column 22, line 48. When included in the present compositions, the cleaning compositions of the present invention typically have a pH of 0.5.
It contains from 2 to about 15% by weight, preferably from about 1 to about 10%, of such a zwitterionic surfactant.

The semi-polar nonionic surfactant comprises one alkyl moiety of about 10 to about 18 carbon atoms and two moieties selected from the group consisting of alkyl and hydroxyalkyl groups of about 1 to about 3 carbon atoms. Water-soluble amine oxide having a carbon atom of about 10
A water-soluble phosphine oxide having from about 1 to about 18 alkyl moieties and two moieties selected from the group consisting of alkyl and hydroxyalkyl groups of from about 1 to about 3 carbon atoms; A specific category of nonionic surfactants, including water-soluble sulfoxides, having one alkyl moiety and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of about 1 to about 3 carbon atoms. Semi-polar nonionic detergent surfactants include amine oxide surfactants having the formula:

Embedded imageR in the above formula³Is an alkyl, hydroxyalkyl having from about 8 to about 22 carbon atoms
, An alkylphenyl group or a mixture thereof;⁴Is about 2-3 carbon sources
An alkylene, hydroxyalkylene group having a substituent or a mixture thereof;
x is 0 to about 3; each R⁵Is an alkyl or arsenic having from about 1 to about 3 carbon atoms.
Polyether having a hydroxyalkyl group or about 1 to about 3 ethylene oxide groups
It is a tylene oxide group. R⁵The groups are mutually linked, for example, via an oxygen or nitrogen atom.
It may combine to form a ring structure. These amine oxide surfactants include, in particular, C_Ten-C₁₈Alkyl dimethyla
Minoxide and C₈-C₁₂Alkoxyethyl dihydroxyethylamine oxy
There is Sid. When included in the present compositions, the cleaning compositions of the present invention typically have a pH of 0.5.
2 to about 15% by weight, preferably about 1 to about 10%, of such a semipolar nonionic field
Contains surfactant. The cleaning composition of the present invention comprises a co-selected from the group of primary or tertiary amines.
It may further contain a cosurfactant. Primary amines suitable for use in the present invention include those of formula R₁NH₂Amine
Where R₁Is C₆-C₁₂, Preferably C₆-C_TenAlkyl chain, or R₄X (CH ₂ )_nAnd X is -O-, -C (O) NH- or -NH-, and R is₄Is C ₆ -C₁₂An alkyl chain, and n is 1 to 5, preferably 3. R₁Alkyl chain
May be linear or branched and may have an ethylene oxide of 12 or less, preferably less than 5.
A sid moiety may be interposed. Preferred amines according to the above formula are n-alkylamido
It is. Amines suitable for use in the present invention are 1-hexylamine, 1-octyl
Selected from amines, 1-decylamine and laurylamine. Other preferred
Primary amines include C₈-C_TenOxypropylamine, octyloxypropyla
Min, 2-ethylhexyloxypropylamine, laurylamidopropylami
And amidopropylamine.

Tertiary amines suitable for use in the present invention include tertiary amines having the formula R ₁ R ₂ R ₃ N, wherein R ₁ and R ₂ are a C ₁ -C ₈ alkyl chain or

Embedded image And R ₃ is a C ₆ -C ₁₂ , preferably a C ₆ -C ₁₀ alkyl chain, or R ₃ is R ₄ X (CH ₂ ) _n (X is —O—, —C (O) NH -Or -NH-), R ₄ is C ₄ -C ₁₂ and n is 1-5, preferably 2-3.
R ₅ is H or C ₁ -C ₂ alkyl, and x is 1-6. R ₃ and R ₄ may be linear or branched, and the R ₃ alkyl chain may have no more than 12, preferably no more than 5, ethylene oxide moieties.

A preferred tertiary amine is R₁Is C₆-C₁₂In the alkyl chain, R₂And R₃Is C ₁ -C₃Alkyl or

Embedded image (Wherein R ₅ is H or CH ₃ and x = 1 to 2), and is R ₁ R ₂ R ₃ N.

Amidoamines of the following formula are also preferred:

Embedded image Wherein R ₁ is C ₆ -C ₁₂ alkyl, n is 2 to 4, preferably n is 3, and R ₂ and R ₃ are C ₁ -C ₄ .

The most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C _8-10 oxypropylamine, N-
Coco-1,3-diaminopropane, coconut alkyldimethylamine, lauryldimethylamine, laurylbis (hydroxyethyl) amine, cocobis (hydroxyethyl) amine, 2 mol propoxylated laurylamine, 2 mol propoxylated octylamine, laurylamide dimethylamine, there is C _8-10 dimethylamine and C ₁₀ amidopropyl dimethylamine. The most preferred amines for use in the composition are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Particularly desirable is n
-Dodecyl dimethylamine, bishydroxyethyl coconut alkylamine, 7
Ethoxylated oleylamine, laurylamidopropylamine and cocoamidopropylamine.

[0073]Color care and fabric care effects Technologies that exert a type of color care effect can also be included. this
Examples of these technologies are metal catalysts for color maintenance. Such metal touch
The medium is described in co-pending European Patent Application No. 92870181.2.
. Dye fixing agent, polyolefin dispersant for preventing wrinkles and improving water absorption, fragrance,
Amino-functional polymers for color care treatments and perfume persistence are available in color care / fabric
Another example of textile care technology is the simultaneous application filed on November 7, 1996.
It is described in pending patent application 96870140.9. Fabric softeners can also be incorporated into the cleaning compositions according to the present invention. These agents are
The type may be inorganic or organic. The inorganic softener is GB-A-1,400,8
98 and the smectite clay disclosed in US Pat. No. 5,019,292.
Is shown. Organic fabric softeners include GB-A-1,514,276 and EP-B
Water-insoluble tertiary amines as disclosed in EP-0,011,340, EP-B-0,
Mono-C as disclosed in EP-B-0,527 and EP-B-0,026,528₁₂-C ₁₄ Quaternary ammonium salts and combinations thereof, and EP-B-0,242,91
There are dilong chain amides as disclosed in No. 9. Other useful organic components in fabric softening systems
Are disclosed in EP-A-0,299,575 and 0,313,146.
There are such high molecular weight polyethylene oxide materials. The level of smectite clay is usually 2-20% by weight, more preferably 5-15%.
%, The substance is added as a dry mix ingredient to the rest of the formulation
You. Organic fabric softeners, such as water-insoluble tertiary amines or di-long chain amide materials, may be used in aqueous solutions.
It is blended at a level of 5 to 5% by weight, usually 1 to 3% by weight.
Oxide substances and water-soluble cationic substances are 0.1 to 2% by weight, usually 0.15 to 1%.
. Added at the 5% level. These substances pass through the spray-dried part of the composition.
Usually added, but in some cases they are added as dry mix particles
Or spray them as a molten liquid on the other solid components of the composition
It is profitable.

Builder System The composition according to the invention may further comprise a builder system. Aluminosilicate materials, silicates, polycarboxylates, alkyl or alkenyl succinic acids, and fatty acids, materials such as ethylenediaminetetraacetic acid, diethylenetriaminepentamethyleneacetic acid, sequestering agents such as aminopolyphosphonates,
Any conventional builder system is suitable for use in the present invention, including especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Phosphate builders may also be used in the present invention. Suitable builders include inorganic ion exchange materials, usually inorganic hydrated aluminosilicate materials, and more specifically hydrated synthetic zeolites, such as hydrated zeolites A, X
, B, HS or MAP. Another suitable inorganic builder material is a laminated silicate, such as SKS-6
(Hoechst). SKS-6 is a crystal laminated silicate made of sodium silicate (Na ₂ Si ₂ O ₅ ).

Suitable polycarboxylates having one carboxy group include lactic acid, glycolic acid and lactic acid, as disclosed in Belgian patents 831,368, 821,369 and 821,370. There are those ether derivatives. 2
Polycarboxylates having two carboxy groups include succinic acid, malonic acid,
Water-soluble salts of (ethylenedioxy) diacetate, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, and German Patent Publication Nos. 2,446,686, 2,446,687 and U.S. Pat. There are the ether carboxylate described in 3,935,257 and the sulfinyl carboxylate described in Belgian Patent 840,623. Polycarboxylates having three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates, as well as carboxymethyloxysuccinates described in GB 1,379,241, Netherlands application 72050873. And oxypolycarboxy such as 2-oxa-1,1,3-propanetricarboxylate described in GB 1,387,447. There are rate substances.

The polycarboxylates having four carboxy groups are described in GB 1,26
Oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,1,2,3-propane disclosed in 1,829 There are tetracarboxylates. Polycarboxylates having sulfo substituents include those described in GB 1,398,421,
398,422 and U.S. Pat. No. 3,936,448, and the sulfonated pyrolytic citrate described in GB 1,082,179; Polycarboxylates having substituents are disclosed in GB 1,439,000. Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,
Cis, cis-tetracarboxylate, cyclopentadienidepentacarboxylate, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,
2,5,5-tetrahydrofuran-tetracarboxylate, 1,2,3,4
There are 5,6-hexane-hexacarboxylate and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include melitic acid, pyromellitic acid, and the phthalic acid derivatives disclosed in GB 1,425,343. Among the above preferred polycarboxylates are hydroxycarboxylates having up to 3 carboxy groups per molecule, more particularly citrates.
Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder or laminated silicate (SKS-6) such as zeolite A and a water-soluble carboxylate chelating agent such as citric acid. . Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder such as zeolite A and a water-soluble carboxylate chelating agent such as citric acid. Preferred builder systems for use in the liquid detergent compositions of the present invention are soaps and polycarboxylates. Other builder substances that can form part of the builder system on use in the granular composition include carbonates, bicarbonates, inorganic substances such as alkali metal silicates, and organic phosphonates,
There are organic substances such as aminopolyalkylene phosphonates and aminopolycarboxylates. Other suitable water-soluble organic salts are homo- or copolymeric acids or salts thereof, wherein the polycarboxylic acids have at least two carboxyl groups separated from one another by no more than two carbon atoms. This type of polymer is GB-A-1,596
, 756. Examples of such salts are polyacrylates with a MW of 2000 to 5000 and copolymers thereof with maleic anhydride, such copolymers having a molecular weight of 20,000 to 70,000, in particular of about 40,000. The washing builder salt is usually contained in an amount of 5 to 80%, preferably 10 to 70%, most usually 30 to 60% by weight of the composition.

Chelating Agents The cleaning compositions may also optionally include one or more iron and / or manganese chelating agents. Such chelators can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelators and mixtures thereof, all as described below. Without being bound by theory, it is believed that the effects of these materials are due in part to their exceptional ability to remove iron and manganese ions from the wash liquor by the formation of soluble chelates. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid,
There are ethylene diamine tetrapropionic acid, triethylene tetraamine hexaacetic acid, diethylene triamine pentaacetic acid and ethanol diglycine, their alkali metal, ammonium and substituted ammonium salts, and mixtures thereof. Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are acceptable in the detergent composition, and include ethylenediaminetetrakis (methylene phosphonate) such as DEQUEST. Preferably,
These aminophosphonates do not contain alkyl or alkenyl groups of about 7 or more carbon atoms. Polyfunctionally substituted aromatic chelators are also useful in the present compositions. May 2, 1974
See U.S. Pat. No. 3,812,044 issued to Connor et al. A preferred compound of this type is a dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene, in the acid form. A preferred biodegradable chelator for use in the present invention is Har
Ethylenediaminedisuccinic acid ("EDDS"), particularly the [S, S] isomer, as described in US Pat. No. 4,704,233 to tman and Perkins. The composition may also contain a water-soluble methylglycine diacetate (MGDA) salt (or acid form) as a cobuilder useful as an insoluble builder, such as zeolites, laminated silicates, and the like, or as a chelant. If utilized, these chelating agents will usually be from about 0.1 to about 15% by weight of the detergent composition. More preferably, if utilized, the chelating agent will be from about 0.1 to about 3.0% by weight of such a composition.

[0078] Another optional component foam control agents, silicone and silica - a foam control agent which is exemplified by silicone mixture. Silicones are typically represented by alkylated polysiloxane materials, and silica is commonly used in finely divided form, exemplified by silica airgel, xerogels and various types of hydrophobic silica. These materials can be formulated as particles, and the suds suppressor is advantageously formulated to be released in a water-soluble or water-dispersible, substantially non-surfactant, detergent-impermeable carrier. . Alternatively, the foam control agent may be applied by dissolving or dispersing in a liquid carrier and spraying on one or more other components. Preferred silicone suds suppressors are described in Bartollota et al., US Pat.
No. 72. Another particularly useful suds suppressor is a self-emulsifying silicone suds suppressor, which is disclosed in German Patent Application DT published April 28, 1977.
OS 2,646,126. Examples of such compounds are
DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Particularly preferred suds suppressors are silicone oils and 2-
A foam suppressant system consisting of a mixture of alkyl-alkanols. A suitable 2-alkyl-alkanol is 2-butyloctanol, sold under the trade name Isofol 12R. Such a suds suppressor system is described in co-pending European Patent Application No. N9298704.77, filed Nov. 10, 1992. Particularly preferred silicone suds suppressors are co-pending European Patent Application No. N # 9220.
1649.8. The compositions may comprise silicone / silica mixture in combination with a molten non-porous silica such as Aerosil ^R.
The above-mentioned foaming inhibitor is usually 0.001 to 2% by weight of the composition, preferably 0.02% by weight.
Used at levels of 1 to 1% by weight.

Other ingredients used in cleaning compositions, such as soil suspending agents, soil releasing agents,
Optical brighteners, abrasives, bactericides, haze inhibitors, colorants and / or encapsulated or unencapsulated fragrances may also be used. A particularly suitable encapsulating material is a water-soluble capsule consisting of a matrix of a polysaccharide and a polyhydroxy compound as described in GB 1,464,616. Other suitable water-soluble encapsulating materials are as described in US 3,455,838,
It consists of a dextrin derived from a non-gelatinized starch ester of a substituted dicarboxylic acid. These acid ester dextrins are preferably made from starches such as waxy maize, waxy sorghum, sago, tapioca and potato. A suitable example of the encapsulating material is N-Lok from National Starch.
The N-Lok encapsulant consists of modified maize starch and glucose. Starch is modified by adding a monofunctional substituent such as octenyl succinic anhydride. Antiredeposition and soil suspending agents suitable for the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymer polycarboxylic acids or salts thereof. Polymers of this type include polyacrylates and maleic anhydride-acrylic acid copolymers already described as builders, and maleic anhydride and ethylene,
There are copolymers with methyl vinyl ether or methacrylic acid, with maleic anhydride accounting for at least 20 mol% of the copolymer. These materials are generally used at levels of 0.5 to 10%, more preferably 0.75 to 8%, most preferably 1 to 6% by weight of the composition.

Preferred optical brighteners are anionic in nature, examples of which are 4,4′-bis (2
-Diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonate disodium, 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino ) Stilbene-2,2'-
Disodium disulfonate, disodium 4,4'-bis (2,4-dianilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonate,
', 4 "-bis (2,4-dianilino-s-triazin-6-ylamino) stilbene-2-sulfonic acid monosodium salt, 4,4'-bis [2-anilino-4-
(N-methyl-N-2-hydroxyethylamino) -s-triazin-6-ylamino] stilbene-2,2'-disulfonate disodium salt, 4,4'-bis
(4-phenyl-2,1,3-triazol-2-yl) stilbene-2,2 '
Disodium disulfonate, disodium 4,4'-bis [2-anilino-4- (1-methyl-2-hydroxyethylamino) -s-triazin-6-ylamino] stilbene-2,2'-disulfonate Sodium 2,2-stilbyl-4 "-(naphth-1 ', 2', 4,5) -1,2,3-triazole-2" -sulfonate and 4,4'-bis (2-sulfostyryl) biphenyl It is. Highly preferred brighteners are the specific brighteners of co-pending European Patent Application 952020943.8.

Other useful polymeric substances are polyethylene glycols, especially molecular weights between 1000 and 1
0000, more specifically 2000-8000, most preferably about 4000. These are used at a level of from 0.20 to 5% by weight, more preferably from 0.25 to 2.5%. These polymers, and the previously described homo or copolymer polycarboxylate salts, provide whiteness maintenance, fabric ash adhesion (fabric ash).
deposition) and in the presence of transition metal impurities to improve cleaning performance on soil, proteins and oxidative soils. Soil release agents useful in the compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid and ethylene glycol and / or propylene glycol units in various configurations. Examples of such polymers are disclosed in commonly assigned U.S. Patent Nos. 4,116,885 and 4,711,730 and European Patent Application 0,272,033. EP-A-0,272,
A particularly preferred polymer according to 033 has the formula: (CH ₃ (PEG) ₄₃ ) _0.75 (POH) _0.25 (T-PO) _2.8 (T-PEG) _0.4 T (POH) _0.25 ((PEG) ₄₃ CH ₃ ) _{0.75 In the} above formula, PEG is-(OC ₂ H ₄ ) O-, PO is (OC ₃ H ₆ O), and T is (pcOC ₆ H ₄ CO). Modified polyesters are also very useful as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1,2-propanediol, with the end groups being mainly sulfobenzoate and, secondarily, ethylene glycol and / or propanediol Consisting of a monoester of The purpose is to obtain a polymer capped at both ends by sulfobenzoate groups, in the present context most of the copolymers being "mainly" end-capped with sulfobenzoate groups. However, some copolymers are not completely capped, so their end groups may consist of monoesters of ethylene glycol and / or propane-1,2-diol,
"Secondary" consists of such species.

The polyester selected in the present invention comprises about 46% by weight dimethyl terephthalic acid, about 16% by weight propane-1,2-diol, about 10% by weight ethylene glycol, about 13% by weight dimethyl sulfobenzoic acid And about 15% by weight of sulfoisophthalic acid and has a molecular weight of about 3000. Polyesters and their methods of manufacture are described in detail in EPA 311,342. It is well known in the art that free chlorine in tap water rapidly inactivates enzymes contained in detergent compositions. Thus, when a chlorine scavenger such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine is used in a formulation at a level of 0.1% by weight or more of the total composition, an improved through-the-wash of detergent enzymes ( throuth the wash) Demonstrate stability. Compositions comprising chlorine scavengers are described in European Patent Application No. 92/01, filed January 31, 1992.
No. 8700018. Alkoxylated polycarboxylates, such as those made from polyacrylates, are useful in the present invention to provide additional fat removal performance. Such materials are described in WO 91/08281 and PCT9, which are incorporated herein by reference.
0/01815 on page 4 et seq. Chemically, these substances are 7-
Consists of a polyacrylate with one ethoxy side chain for every eight acrylate units. Side chain of the formula _- consists _{(CH 2 CH 2 O) m} (CH 2) n CH 3, wherein m
Is 2-3 and n is 6-12. The side chains are esterified to the polyacrylate “backbone” to form a “comb” polymer type structure. Molecular weights vary, but typically range from about 2000 to about 50,000. Such alkoxylated polycarboxylates comprise from about 0.05% to about 10% by weight of the composition.
It is.

[0083]Dispersant The cleaning composition of the present invention may also contain a dispersant: suitable water solubility
Organic salts are homo- or copolymeric acids or their salts, their polycarboxylic acids
Acids contain at least two carboxyl groups separated from each other by no more than two carbon atoms
I have. This type of polymer is disclosed in GB-A-1,596,756
. Examples of such salts are polyacrylates of MW 2000-5000, and
And maleic anhydride, such copolymers being 1000-
It has a molecular weight of 100,000. In particular, acrylates and methyls such as 480N having a molecular weight of 4000
The copolymers of acrylates are present at levels of from 0.5 to 20% by weight of the composition according to the invention.
In the cleaning composition. The composition of the present invention may contain a lime soap peptizer compound, which comprises
A lime soap of below 8, preferably below 7, most preferably below 6
It preferably has a dispersing force (LSDP). Lime soap peptizer
The compound is preferably present at a level of 0-20% by weight. The numerical measure of the effectiveness of a lime soap peptizer is the lime soap dispersion force (LSD).
P), H.C.Borghetty and C.A.Bergman, J.Am.Oil.Chem.Soc., Volum
e 27, pages 88-90 (1950) using lime soap dispersion test as described in the paper.
Measured. This lime soap dispersion test method is widely used by those skilled in the art,
For example, the following review literature: W.N.Linfield, Surfactant Science Series, Volume 7,
p.3; W.N.Linfield, Tenside Surf.Det., Volume 27, pages 159-161 (1990);
K.Nagarajan, W.F.Masler, Cosmetics and Toiletries, Volume 104, pages 71-73 (
1989). LSDP is 333 ppm CaCo₃(Ca: M
g = 3: 2) 0.025 g of sodium oleate in 30 ml of water of equivalent hardness
Dispersant vs. oleic acid required to disperse the formed lime soap sediment
It is the percentage by weight of sodium. Surfactants with good lime soap peptizer capacity include certain amines.
Oxide, betaine, sulfobetaine, alkyl ethoxy sulfate and eth
There is a xylated alcohol. Exemplary surfactants having an LSDP of 8 or less for use according to the invention include C ₁₆ -C₁₈Dimethylamine oxide, C having an average ethoxylation degree of 1 to 5₁₂-C₁₈Al
Kill ethoxy sulphate, especially C with ethoxylation degree 3₁₂-C_FifteenAlkyl ethoxy
Cisulfate surfactant (LSDP = 4), and trade name from BASF GmbH
Average ethoxylation sold in Lutensol A012 and Lutensol A030 respectively
Degree 12 (LSDP = 6) or 30 C₁₄-C_FifteenThere is ethoxylated alcohol
. Polymer lime soap peptizers suitable for use in the present invention include Cosmetics and
M.K.Nagarajan, W.F.Ma found in Toiletries, Volume 104, pages 71-73 (1989)
It is described in a paper by sler. 4- (N-octanoyl-6-aminohexanoyl) benzenesulfonate,
4- (N-nonanoyl-6-aminohexanoyl) benzenesulfonate, 4-
(N-decanoyl-6-aminohexanoyl) benzenesulfonate and it
Hydrophobic bleach, such as a mixture of these; combined with a hydrophilic / hydrophobic bleach formulation
Nonanoyloxybenzenesulfonate is also a lime soap peptizer compound
Can be used as

Discoloration Inhibition The cleaning composition of the present invention is encountered during a fabric washing operation with a colored fabric,
Compounds for inhibiting the transfer of dye from one fabric to another with dissolved and suspended dyes can also be included.

Polymer Transfer Inhibitor The cleaning composition according to the present invention comprises from 0.001 to 10% by weight, preferably from 0 to 10% by weight.
. It also contains from 01 to 2%, more preferably from 0.05 to 1% of a polymeric dye transfer inhibitor. The polymeric transfer dye inhibitor is usually incorporated into the cleaning composition to prevent dye transfer from the colored fabric onto the washed fabric. These polymers have the ability to complex with or adsorb free dye washed off from the colored fabric before the dye has a chance to adhere to other objects in the wash liquor. Particularly suitable polymeric dye transfer inhibitors are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidone and polyvinylimidazole, or mixtures thereof.

The addition of such polymers also enhances the performance of the enzymes according to the invention.

A) Polyamine N-Oxide Polymers Suitable for use with polyamine N-oxide polymers comprise units having the following structural formula:

Embedded image In the above formula, P is a polymerizable unit, to which an R—N—O group can be bound, or the R—N—O group forms part of the polymerizable unit, or a combination of both A is NC (= O), C (= O) O, C = O, -O-, -S-, -N-;
x is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic, alicyclic group or a combination thereof, to which the nitrogen of the NO group can be attached, or The nitrogen of the NO group is part of these groups.

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

Embedded image Wherein R1, R2 and R3 are an aliphatic group, an aromatic, a heterocyclic, an alicyclic group or a combination thereof, x or / and y or / and z are 0 or 1; The nitrogens of the groups are attached, or the nitrogen of the NO group forms part of these groups. The NO group may be part of the polymerizable unit (P), attached to the polymer backbone, or a combination of both. Suitable polyamine N-oxides in which the NO group forms part of the polymerizable unit include those polyamine N-oxides in which R is selected from aliphatic, aromatic, cycloaliphatic or heterocyclic groups. is there. One class of the above polyamine N-oxides comprises a group of polyamine N-oxides in which the nitrogen of the NO group forms part of the R group. Preferred polyamine N
An oxide is where R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Another class of the above polyamine N-oxides consists of a group of polyamine N-oxides in which the nitrogen of the NO group is attached to the R group. Other suitable polyamine N-oxides are those in which the NO groups are attached to polymerizable units.

A preferred class of these polyamine N-oxides is the general formula (R) wherein R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the NO functional group is part of the R group. It is a polyamine N-oxide having I). Examples of these classes are polyamine oxides, where R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof. Another preferred class of polyamine N-oxides is the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the NO function is attached to the R group. ). Examples of these classes are polyamine oxides, where the R groups are aromatic, such as phenyl. Any polymer backbone may be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymer backbones are polyvinyl, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate and mixtures thereof. The amine N-oxide polymers of the present invention typically comprise 10: 1 to 1: 1000
It has a ratio of amine to amine N-oxide of 000. However, the amount of amine oxide groups present in the polyamine oxide polymer can be varied by suitable copolymerization or by moderate N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2: 3 to 1: 1,000,000, more preferably from 1: 4 to 1: 1,000,000, and most preferably from 1: 7 to 1: 100,000.
0. The polymers of the present invention actually include random or block copolymers in which one monomer type is an amine N-oxide and the other monomer type is or is not an amine N-oxide. The amine oxide units of the polyamine N-oxide have a pKa <10, preferably a pKa <7, more preferably a pKa <6. Polyamine oxides can be obtained at almost any degree of polymerization. The degree of polymerization is not critical as long as the material has the desired water solubility and dye suspending power. Typically, the average molecular weight is between 500 and 1,000,000, preferably 1000
~ 50,000, more preferably 2000 to 30,000, most preferably 30
It is in the range of 00 to 20,000.

B) Copolymer of N-vinylpyrrolidone and N-vinylimidazole The N-vinylimidazole N-vinylpyrrolidone polymer used in the present invention has an average molecular weight of 5000 to 1,000,000, preferably 5000 to 200,000. Having a range. Highly preferred polymers for use in the detergent compositions according to the present invention are those selected from N-vinylimidazole N-vinylpyrrolidone copolymers, the polymers being 5000 to 50,000, more preferably 8000 to 30,000.
And most preferably has an average molecular weight range of 10,000 to 20,000. The average molecular weight range is based on Barth HGand Mays JW, Chemical Analysis, Vol. 113, "M
odern Methods of Polymer Characterization ". Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers are 5,000-50,000, more preferably 8,000-30,000, most preferably It has an average molecular weight range of 10,000 to 20,000 N-vinylimidazole N-vinylpyrrolidone copolymer, characterized by having the above average molecular weight range, is formulated with it while exhibiting excellent dye transfer inhibition properties. The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention does not adversely affect the cleaning performance of the detergent composition.
0.2, more preferably 0.8: 0.3, most preferably 0.6: 0.4 N-
It has a molar ratio of vinylimidazole to N-vinylpyrrolidone.

C) Polyvinylpyrrolidone In the detergent compositions of the present invention, from about 2500 to about 400,000, preferably about 50
Polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 00 to about 200,000, more preferably from about 5000 to about 50,000, and most preferably from about 5000 to about 15,000 may also be utilized. Suitable polyvinylpyrrolidone is available under the product name PV
PK-15 (viscosity molecular weight of 10,000), PVP K-30 (40,000
Average molecular weight), PVP K-60 (average molecular weight of 160,000) and PV
As PK-90 (average molecular weight of 360,000), ISP Corporation, New
Commercially available from York, NY and Montreal, Canada. Other suitable polyvinylpyrrolidones commercially available from the BASF Cooperation include Sokalan HP165 and Sokalan HP12; polyvinylpyrrolidone known to the detergent industry (eg, E
Nos. PA-262,897 and EP-A-256,696).

D) Polyvinyl oxazolidone In the detergent composition of the present invention, polyvinyl oxazolidone may also be used as a polymer transfer inhibitor. The above polyvinyl oxazolidone is used in an amount of about 2500 to about 400.
000, preferably from about 5000 to about 200,000, more preferably about 500
It has an average molecular weight of from about 0 to about 50,000, most preferably from about 5000 to about 15,000.

E) Polyvinylimidazole In the detergent composition of the present invention, polyvinylimidazole may also be used as a polymer transfer inhibitor. The above polyvinyl imidazole is used in an amount of about 2500 to about 400,0.
00, preferably about 5000 to about 200,000, more preferably about 5000 to about 200,000.
It has an average molecular weight of about 50,000, most preferably from about 5000 to about 15,000.

F) Crosslinked Polymers Crosslinked polymers are polymers in which the backbone is linked to some extent, these links may be of chemical or physical nature, with the possibility that the active groups may be on the backbone or It may be on the side chain, and the crosslinked polymer can be found in Journal of Polymer Science, volum
e 22, pages 1035-1039. In one embodiment, the cross-linked polymer is made to form a three-dimensional rigid structure, allowing the pores formed by the three-dimensional structure to trap the dye. In another aspect, the crosslinked polymer captures the dye by swelling. Such crosslinked polymers are described in co-pending patent application 94870213.9.

Cleaning Methods The compositions of the present invention may be used in essentially any cleaning or cleaning method, including dipping, pre-treatment, and methods involving a rinsing step in which another rinse aid composition is added. . The process described herein consists of contacting a fabric with a wash liquor in a conventional manner, and is exemplified below. The process of the present invention is conveniently performed during the cleaning process. The cleaning method is preferably performed at 5 to 95 ° C, particularly 10 to 60 ° C. The pH of the treatment solution is preferably 7-12. A preferred machine dishwashing method consists of treating the soiled object with an aqueous liquid dissolved or formulated with an effective amount of a machine dishwashing or rinsing composition. A conventional effective amount of a machine dishwashing composition is a product 8 to 8 dissolved or dispersed in a wash volume of 3 to 10 L.
Means 60 g. According to the manual dishwashing method, the soiled dish is contacted with an effective amount of the dishwashing composition, typically from 0.5 to 20 g (per 25 dishes). Preferred manual dishwashing methods include applying a concentrate to the surface of the dish or dipping the detergent composition into a large volume of diluent. The following examples are meant to illustrate the compositions of the present invention and do not necessarily limit or limit the scope of the present invention.

In detergent compositions, enzyme levels are expressed as pure enzyme by weight of total composition, and unless otherwise specified, detergent components are expressed by weight of total composition.
Abbreviated ingredients displayed have the following meanings: LAS: Sodium linear C _11-13 alkyl benzene sulphonate TAS: Sodium tallow alkyl sulfate CxyAS: Sodium C _1X -C _1Y alkyl sulfate CxySAS: Sodium C _1X -C _1Y two grade (2,3) alkyl sulfates CxyEz: mean z moles of ethylene oxide condensed with C _1X -C _1Y primarily straight chain primary alcohol CxyEzS: mean z moles of ethylene oxide condensed with C _1X -C _1Y sodium alkyl Sulfate QAS: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) (R ₂ = C ₁₂ -C ₁₄ ) QAS 1: R ₂ N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) (R _{2 = C 8 -C 11) APA:} C 8-10 amido propyl dimethyl amine soap: tallow Contact Sodium linear alkyl carboxylate nonionic derived from 80/20 mixture of fine coconut fatty acids: C ₁₃ -C ₁₅ mixed ethoxylated with an average ethoxylation degree 3.8 and the average propoxylation degree 4.5 / propoxylated fatty alcohols _{Neodol 45-13: Shell Chemical CO C 14} -C 15 linear primary alcohol ethoxylate, sold by STS: sodium toluene sulphonate CFAA: C ₁₂ -C ₁₄ alkyl N- methyl glucamide TFAA: C ₁₆ -C ₁₈ alkyl N-methylglucamide TPKFA: C ₁₂ -C ₁₄ topped whole cut fatty acid DEQA: di (tallowoxyethyl) dimethylammonium chloride DEQA (2): di (soft tallowyloxyethyl) hydroxyethylmethyl ammonium Methyl sulfate D TDMAMS: ditallow dimethyl ammonium methyl sulfate SDASA: stearyl dimethylamine in a 1: 2 ratio: triple-pressed stearic acid silicate: amorphous sodium silicate (ratio of SiO ₂ : Na ₂ O = 1.6-) 3.2) metasilicate: sodium metasilicate _{(SiO 2:} Na 2 O ratio = 1.0) zeolite a: formula Na _{12 (AlO} 2 _SiO 2 having a main particle size of 0.1~10μm _range) 12 · 27H Hydrated sodium aluminosilicate of ₂ O (weight on an anhydrous basis) NaSKS-6: Crystal-laminated silicate citrate of formula δ-Na ₂ Si ₂ O ₅ : activity 86.4 with a particle size distribution in the range of 425-850 μm % Trisodium citrate dihydrate Citric acid: anhydrous citric acid Borate: sodium borate Carbonate: anhydrous sodium carbonate having a particle size of 200 to 900 μm Bicarbonate: anhydrous sodium hydrogencarbonate having a particle size distribution of 400 to 1200 μm Sulfate: anhydrous sodium sulfate Mg: anhydrous magnesium sulfate STPP: sodium tripolyphosphate TSPP: tetrasodium pyrophosphate MA / AA: random copolymer of 4: 1 acrylate / maleate Average molecular weight of about 70,000 to 80,000 MA / AA 1: 6: 4 random copolymer of acrylate / maleate Average molecular weight of about 10,000 AA: polyacryl of average molecular weight of 4500 Sodium acid polymer PA30: polyacrylic acid 480N having an average molecular weight of about 4500 to 8000: random copolymer of 7: 3 acrylate / methacrylate average molecular weight of about 3500 polygel / carbopol: High molecular weight cross-linked polyacrylate PB1: empirical formula NaBO ₂ · _{H 2 O 2} in anhydrous sodium perborate monohydrate PB4: Sodium perborate of empirical formula _{NaBO 2 · 3H 2 O · H} 2 O 2 tetrahydrate percarbonate: empirical formula _{2Na 2 CO 3 · 3H 2 O} 2 in anhydrous sodium percarbonate NaDCC: sodium dichloroisocyanurate TAED: tetraacetylethylenediamine NOBS: nonanoyl sodium salt form oxybenzene sulphonate NACA-OBS: (6- Nonamidokapuro Yl) oxybenzenesulfonate DTPA: diethylenetriaminepentaacetic acid HEDP: 1,1-hydroxyethanediphosphonic acid DETPMP: diethyltriaminepenta (methylene) phosphonate ED sold under the trade name Dequest 2060 by Monsanto S: ethylenediamine-N, N'-disuccinic acid (S, S) isomer of its sodium salt form MnTACN: manganese 1,4,7-trimethyl-1,4,7-triazacyclononane Photoactivated bleach: dextrin soluble Sulfonated Zinc Phthalocyanine Encapsulated in Polymer Photoactivated Bleach 1: Sulfonated Aluminophthalocyanine Encapsulated in Dextrin Soluble Polymer PAAC: Pentamine Cobalt (III) Acetate Salt Paraffin: Sold by Wintershall under the trade name Winog 70 Paraffin oil NaBz: Sodium benzoate BzP: Benzoyl peroxide cytochrome I: Recombinant cytochrome P450bm3 cytochrome II from E. coli according to Wen and Fulco, J. Biol. Chem., 262, 6676, 1987: Peterson et al., Methods in Enzymology, Academic Press New York, 1978, Vol. 52, pp. 151-157 Cytochrome P450cam electron donor I: NADPH, nicotinamide adenine dinucleotide phosphate reduced form, isolated from Pseudomonas putida grown on camphor, Sigma product number N1630 electron donor II: sodium sulfite Na ₂ SO ₃ Photo grade (pfs) 97%,
Sigma product S6778 Ferredoxin: 25% from partially purified spinach, Sigma product F3013 Ferredoxin reductase: Ferredoxin-NADP from spinach
Blend of reductase (EC 1.18.1.2) and ferredoxin-NADP, Sigma product F0628 dehydrogenase I: alcohol dehydrogenase E. from Thermoanaerobium brockii. C. 1.1.1.2, Sigma Product No. A9287 Dehydrogenase I: alcohol dehydrogenase from Thermoanaerobium brockii immobilized on agarose beads. C. 1.1. 1.2, Sigma product number A2809 dehydrogenase III: aromatic alcohol dehydrogenase from Lactobacillus kefir C. 1.1.1.2, Sigma product number A9560 dehydrogenase IV: formate dehydrogenase from Candida boidinii C. 1.2.1.2, Sigma product number F5632 Isopropanol: 2-propanol 99%, Sigma product number 27,049-0 Benzyl alcohol: 99%, Sigma product number B2263 Protease: Trade name Savinase, Alcalase from Novo Nordisk A / S, Proteolytic enzymes sold by Durazym; Maxacal, Maxapem sold by Gist-Brocades; and patent WO 91/06637.
And / or WO 95/10591 and / or EP 251
Protease amylase described under 446: an amylolytic enzyme sold by Genencor under the trade name Purafact Ox Am ^R , described in WO 94/18314, WO 96/05295; all commercially available from Novo Nordisk A / S
Termamyl ^R , Fungamyl ^R and Duramyl ^R ; and those described in WO 95/26397 Lipase: Lipoase sold by Novo Nordisk A / S under the trade names Lipolase, Lipolase Ultra, and Lipomax by Gist-Brocades
Cellulase: Cellulolytic enzyme sold by Novo Nordisk A / S under the trade name Carezyme, Celluzyme and / or Endolase CMC: Sodium carboxymethylcellulose PVP: Polyvinyl polymer with an average molecular weight of 60,000 PVNO: Polyvinylpyridine with an average molecular weight of 50,000 -N-oxide PVPVI: copolymer of vinylimidazole and vinylpyrrolidone having an average molecular weight of 20,000 Brightener 1: Disodium 4,4'-bis (2-sulfostyryl) biphenyl brightener 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-
Triazin-2-yl) stilbene-2,2'-disulfonate disodium Silicone antifoam: siloxane-oxyalkylene copolymer as dispersant at a ratio of foam inhibitor to dispersant of 10: 1 to 100: 1 Compounded polydimethylsiloxane foam suppressant Foam suppressant: Granular, 12% silicone / silica, 18% stearyl alcohol, 70% starch Opaquer: water-based sold by BASF Aktiengesellschaft under the trade name Lytron 621 Monostyrene latex mixture SRP1: Anionic end-capped polyester SRP2: Diethoxylated poly (1,2-propylene terephthalate) short block polymer QEA: Bis [(C ₂ H ₅ O) (C ₂ H ₄ O) _n ] (CH ^{_{3) -N + - C 6 H}} 12 -N + - (CH 3 Bis _{[(C 2 H 5 O) (} C 2 H 4 O) n ] (n = 20~30) PEI: polyethyleneimine having an average degree of ethoxylation of average molecular weight 1800 and a nitrogen per seven ethyleneoxy residues SCS : Sodium cumene sulfonate HMWPEO: High molecular weight polyethylene oxide PEGx: Polyethylene glycol with molecular weight x PEO: Polyethylene oxide with average molecular weight of 5000 TEMPAE: Tetraethylenepentamine ethoxylate BTA: Benzotriazole Silica Dental abrasive: Specified as Zeodent 119 supplied by JMHuber Precipitated silica carboxyvinyl polymer: Carbopol carrageenan supplied by BFGoodrich Chemical Company: l-carrageenan supplied by Hercules Chemical Company pH: Measured as a 1% solution in distilled water at 20 ° C

Example 1 The following high-density laundry detergent composition was prepared according to the present invention: I II III IV V VI LAS 8.0 8.0 8.0 2.0 6.0 6.0 TAS -0.5-0.5 1.0 0.1 C46 (S) AS 2.0 2.5--- -C25AS---7.0 4.5 5.5 C68AS 2.0 5.0 7.0---C25E5--3.4 10.0 4.6 4.6 C25E7 3.4 3.4 1.0---C25E3S---2.0 5.0 4.5 QAS-0.8----QAS1---0.8 0.5 1.0 Zeolite A 18.1 18.0 14.1 18.1 20.0 18.1 Citric acid---2.5-2.5 Carbonate 13.0 13.0 27.0 10.0 10.0 13.0 NaSKS-6---10.0-10.0 Silicate 1.4 1.4 3.0 0.3 0.5 0.3 Citrate-1.0-3.0--Sulfate 26.1 26.1 26.1 6.0--Mg sulfate 0.3--0.2-0.2 MA / AA 0.3 0.3 0.3 4.0 1.0 1.0 CMC 0.2 0.2 0.2 0.2 0.4 0.4 PB4 9.0 9.0 5.0---Percarbonate----18.0 18.0 TAED 1.5 0.4 1.5-3.9 4.2 NACA-OBS-2.0 1.0---DETPM 0.25 0.25 0.25 0.25--SRP1---0.2-0.2 EDDS-0.25 0.4-0.5 0.5 CFAA-1.0-2.0--HEDP 0.3 0.3 0.3 0.3 0.4 0.4 QEA---0.2-0.5 Cytochrome I 0.005 0.005 0.1 0.1 0.2 0.5 electron Donor I 0.05 0.1 0.9 1.0 2.0 2.0 Protease 0.009 0.009 0.01 0.04 0.05 0.03 Amylase 0.002 0.002 0.002 0.006 0.008 0.008 Cellulase 0.0007--0.0007 0.0007 0.0007
Lipase 0.006--0.01 0.01 0.01 Light activated bleach (ppm) 15 15 15-20 20 PVNO / PVPVI---0.1--Brightener 1 0.09 0.09 0.09-0.09 0.09 Fragrance 0.3 0.3 0.3 0.4 0.4 0.4 Silicone defoamer 0.5 0.5 0.5-0.3 0.3 Density g / L 850 850 850 850 850 850 Others Up to 100%

Example 2 The following granular laundry detergent compositions which are particularly useful under European machine wash conditions were prepared according to the present invention: I II III IV V VI LAS 5.5 7.5 5.0 5.0 6.0 7.0 TAS 1.25 1.9-0.8 0.4 0.3 C24AS / C25AS-2.2 5.0 5.0 5.0 2.2 C25E3S-0.8 1.0 1.5 3.0 1.0 C45E7 3.25----3.0 TFAA--2.0---C25E5-5.5----QAS 0.8------QAS1-0.7 1.0 0.5 1.0 0.7 STPP 19.7-----Zeolite A-19.5 25.0 19.5 20.0 17.0 NaSKS-6 / citric acid (79:21)-10.6-10.6--NaSKS-6--9.0-10.0 10.0 Carbonate 6.1 21.4 9.0 10.0 10.0 18.0 weight Carbonate-2.0 7.0 5.0-2.0 Silicate 6.8--0.3 0.5-Citrate--4.0 4.0--Sulfate 39.8--5.0-12.0 Mg sulfate--0.1 0.2 0.2-MA / AA 0.5 1.6 3.0 4.0 1.0 1.0 CMC 0.2 0.4 1.0 1.0 0.4 0.4 PB4 5.0 12.7----Percarbonate----18.0 15.0 TAED 0.5 3.1--5.0-NACA-OBS 1.0 3.5---2.5 DETPMP 0.25 0.2 0.3 0.4-0.2 HEDP-0.3-0.3 0.3 0.3 QEA--1.0 1.0 1.0-Cytochrome I 0.07 0.1 0.2 0.07 0.1 0.2 Electron donor I 0.7 1.0 1.5 0.1 1.0 1.5 Protease 0.009 0.03 0.03 0.05 0.05 0.02 Lipase 0.003 0.003 0.006 0.006 0.006 0.004 Cellulase 0.0006 0.0006 0.0005 0.0005 0.0007 0.0007 Amylase 0.002 0.002 0.006 0.006 0.01 0.003 PVNO / PVPVI--0.2 0.2--PVP 0.9 1.3---0.9 SRP1- -0.2 0.2 0.2-Light activated bleach (ppm) 15 27--20 20 Light activated bleach (1) (ppm) 15-----Brightener 1 0.08 0.2--0.09 0.15 Brightener 2-0.04 ----Fragrance 0.3 0.5 0.4 0.3 0.4 0.3 Silicone defoamer 0.5 2.4 0.3 0.5 0.3 2.0 Density g / L 750 750 750 750 750 750 Others Up to 100%

Example 3 The following detergent compositions, which are particularly useful under European machine wash conditions, were prepared in accordance with the present invention: I II III IV Blown Powder: LAS 6.0 5.0 11.0 0 TAS 2.0--2.0 Zeolite A 24.0--20.0 STPP-27.0 24.0-Sulfate 4.0 6.0 13.0-MA / AA 1.0 4.0 6 2.0 2.0 silicate 1.0 7.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 Brightener 1 0.2 0.2 0.2 0.2 Silicone antifoam 1.0 1.0 1.0 0.3 DETPMP 0.4 0.4 0.2 0.4 Spray-on: whitening agent 0.02 --- 0.02
C45E7---5.0 C45E2 2.5 2.5 2.0-C45E3 2.6 2.5 2.0-Perfume 0.5 0.3 0.5 0.2 Silicone defoamer 0.30 0.3 0.3-Dry additive: QEA---1.0 EDDS 0.3---Sulfate 2.0 3.0 5.0 10.0 10.0 Carbonate 6.0 13.0 15.0 14. 0 Citric acid 2.5--2.0 QAS1 0.5--0.5 NaSKS-6 10.0---Percarbonate 18.5----PB4-18.0 10.0 21.5 TAED 2 2.0 2.0-2.0 NACA-OBS 3.0 2.0 4.0-Cytochrome I 0.007 0.05 0.1 0.05
Electron donor I 0.02 0.1 1.0 0.1 protease 0.03 0.03 0.03 0.03
Lipase 0.008 0.008 0.008 0.004 Amylase 0.003 0.003 0.003 0.006 Brightener 1 0.05--0.05
Others up to 100%

[0100] Example 4 below granular detergent compositions were prepared in accordance with the present invention: I II III IV V VI Blown Powder: LAS 23.0 8.0 7.0 9.0 7.0 7.0 TAS - - - - 1.0 - C45AS 6.0 6.0 5.0 8.0 - - C45AES - 1.0 1.0 1.0--C45E35----2.0 4.0 Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0 MA / AA-0.5---2.0 MA / AA1 7.0------AA-3.0 3.0 2.0 3.0 3.0 Sulfate 5.0 6.3 14.3 11.0 15.0 19.3 Silicate 10.0 1.0 1.0 1.0 1.0 1.0 Carbonate 15.0 20.0 10.0 20.7 8.0 6.0 PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0 DTPA-0.9 0.5--0.5 Brightener 2 0.3 0.2 0.3-0.1 0.3 Spray-on: C45E7-2.0--2.0 2.0 C25E9 3.0------C23E9--1.5 2.0-2.0 Fragrance 0.3 0.3 0.3 2.0 0.3 0.3 Aggregate: C45AS-5.0 5.0 2.0-5.0 LAS-2.0 2.0--2.0 Light A-7.5 7.5 8.0-7.5 Carbonate-4.0 4.0 5.0-4.0 PEG4000-0.5 0.5--0.5 Other (water, etc.)-2.0 2.0 2.0-2.0 Dry additive: QAS----1.0-Citric acid---- -2.0-PB4----12.0 1.0 PB1 4.0 1.0 3.0 2.0--Percarbonate-----2.0 10.0 Carbonate-5.3 1.8-4.0 4.0 NOBS 4.0-6.0--0.6 Methylcellulose 0.2------NaSKS-6 8.0------STS--2.0-1.0-Cumenesulfonic acid-1.0---2.0 Cytochrome I 0.05 0.1 2.0 0.005 0.1 2.0 Electron donor I 0.05 0.1 2.0 0.05 0.1 2.0 Protease 0.02 0.02 0.02 0.01 0.02 0.02 Lipase 0.004-0.004 -0.004 0.008 Amylase 0.003-0.002-0.003-Cellulase 0.0005 0.0005 0.0005 0.0007 0.0005 0.0005
PVPVI-----0.5 0.1 PVP-----0.5-PVNO--0.5 0.3--QEA-----1.0-SRP1 0.2 0.5 0.3-0.2-Silicone defoamer 0.2 0.4 0.2 0.4 0.1-Mg sulfate--0.2 -0.2-Others up to 100%

Example 5 The following bleach-free detergent compositions particularly useful in washing colored clothing were prepared in accordance with the present invention: I II III Blown Powder: Zeolite A 15.0 15.0-Sulfate-5.0-LAS 3 3.0 3.0-DETPMP 0.4 0.5-CMC 0.4 0.4-MA / AA 4.0 4.0-Aggregate: C45AS--11.0 LAS 6.0 5.0-TAS 3.0 2.0-silicate 4.0 4.0-zeolite A 10.0 15.0 13.0 CMC--0.5 MA / AA--2.0 carbonate 9.0 7.0 7.0. 0 Spray-on: Fragrance 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 2.0 Dry additive: MA / AA--3.0 NaSKS-6- -12.0 Citrate 1 0.0-8.0 Bicarbonate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI / PVNO 0.5 0.5 0.5 Cytochrome I 0.01 0.05 0 .1 electron donor I 0.05 0.15 0.1 protease 0.03 0.02 0.05 lipase 0.008 0.008 0.008
Amylase 0.01 0.01 0.01 Cellulase 0.001 0.001 0.001
Silicone defoamer 5.0 5.0 5.0 Sulfate-9.0-Density (g / L) 700 700 700 700 Others up to 100%

[0102] Example 6 The following detergent composition was prepared in accordance with the present invention: I II III IV Base granule Zeolite A 30.0 22.0 24.0 10.0 Sulfate 10.0 5.0 10.0 7.0 MA / AA 3.0 - - - AA - 1.6 2.0 - MA / AA1 -12.0-6.0 LAS 14.0 10.0 9.0 20.0 C45AS 8.0 7.0 9.0 7.0 C45AES-1.0 1.0-Silicate-1.0 0.5 10.0 Soap-2.0--Brightener 1 0.2 0.2 0.2 0.2 Carbonate 6.0 9.0 10.0 10.0 PEG4000-1.0 1.5-DTPA- 0.4--Spray-on: C25E9---5.0 C45E7 1.0 1.0--C23E9-1.0 2.5-Fragrance 0.2 0.3 0.3-Dry additive: Carbonate 5.0 10.0 18.0 8.0 PVPVI / PVNO 0.5-0.3-Cytochrome I 0.001 0.005 0.01 0.1 Electron Donor I 0.01 0.05 0.09 0.9 Protease 0.03 0.03 0.03 0.02 Lipase 0.008--0.008 Amylase 0.002--0.002 Cellulase 0.0002 0.00 05 0.0005 0.0002 NOBS-4.0-4.5 PB1 1.0 5.0 1.5 6.0 Sulfate 4.0 5.0-5.0 SRP1-0.4--Foaming inhibitor-0.5 0.5-Others up to 100%

Example 7 The following granular detergent composition was prepared in accordance with the present invention: I II III Blown powder: Zeolite A 20.0-15.0 STPP-20.0 Sulfate 5.0 Carbonate -5 1.0 TAS--1.0 LAS 6.0 6.0 6.0 C68AS 2.0 2.0-Silicate 3.0 8.0-MA / AA 4.0 2.0 2.0 CMC 0.6 0.6 0.2 Brightener 1 0.2 0.2 0.1 DETPMP 0.4 0.4 0.1 STS --- 1.0 Spray-on: C45E7 5.0 5.0 4.0 Silicone Foaming agent 0.3 0.3 0.1 Fragrance 0.2 0.2 0.3 Dry additive: QEA--1.0 Carbonate 14.0 9.0 10.0 10.0 PB1 1.5 2.0- PB4 18.5 13.0 13.0 TAED 2.0 2.0 2.0 QAS--1.0 Light-activated bleach 15 ppm 15 ppm 15 ppm NaSKS-6--3.0 Cytochrome I 0.005 0.005 0.005 Electron donor I 0.005 0.05 0.5 Dehydrogenase I 0.015--Dehydrogenase II- 0.015-dehydrogenase III--0.03
Isopropanol 0.004 0.004-benzyl alcohol--0.08
Protease 0.03 0.03 0.007 Lipase 0.004 0.004 0.004 Amylase 0.006 0.006 0.003 Cellulase 0.0002 0.0002 0.0005 Sulfate 10.0 20.0 5.0 Density (g / L) 700 700 700 Others up to 100%

Example 8 The following detergent composition was prepared according to the present invention: I II III Blown powder: Zeolite A 15.0 15.0 15.0 Sulfate-5.0-LAS 3.0 3.0 3.0 QAS-1.5 1.5 DETPMP 0.4 0.2 0.4 EDDS-0.4 0.2 CMC 0.4 0.4 0.4 MA / AA 4.0 2.0 2.0 Aggregate : LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray-on: Fragrance 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 2.0 C25E3 2.0 --- Dry additive: Citrate 5.0-2.0 Bicarbonate --3. 0-carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PB1 14.0 7.0 10.0 PEO--0.2 Bentonite clay--10.0 Cytochrome II 0.01 0.05 0.1 Electron donor I 0.09 0.2 0.1 Ferredoxin 0.003 0.01 0.1 Ferredoxin reductase 0.01 0.07 0.1 Protease 0.03 0.03 0.03 Lipase 0.008 0.008 0.008
Cellulase 0.001 0.001 0.001
Amylase 0.01 0.01 0.01 Silicone antifoaming agent 5.0 5.0 5.0 Sulfate-3.0-Density (g / L) 850 850 850 Others Up to 100%

Example 9 The following detergent composition was prepared according to the present invention: I II III IV LAS 18.0 14.0 24.0 20.0 QAS 0.7 1.0-0.7 TFAA-1.0 --C23E56.5--1.0-C45E7-1.0--C45E3S 1.0 2.5 1.0-STPP 32.0 18.0 30.0 22.0 Silicate 9.0 5.09 8.0 8.0 Carbonate 11.0 7.5 10.0 5.0 Bicarbonate-7.5--PB1 3.0 1.0--PB4-1.0--NOBS 2.0 1. 0--DETPMP-1.0--DTPA 0.5-0.2 0.3 SRP1 0.3 0.2-0.1 MA / AA 1.0 1.5 2.0 0.5 CMC 8 0.4 0.4 0.2 PEI--0.4-Sulfate 20 0 10.0 20.0 30.0 sulfate Mg 0.2 - 0.4 0.9 Cytochrome I 0.1 0.05 0.1 0.05
Electron donor I 0.5 0.1 0.5 0.1 protease 0.03 0.03 0.02 0.02
Amylase 0.008 0.007-0.004 Lipase 0.004-0.002-Cellulase 0.0003--0.0001
Light activated bleach 30 ppm 20 ppm -10 ppm
Perfume 0.3 0.3 0.1 0.2 Brightener 1/2 0.05 0.02 0.08 0.1 Others Up to 100%

Example 10 The following liquid detergent formulation was prepared according to the present invention (levels are given in parts / weight; enzymes are expressed as pure enzyme): I II III IV V LAS 11.58 2.8-3.9-C25E2.5S-3.0 18.0-16.0 C45E2.25S 11.5 3.0-15.7-C23E9-2.7 1.8 2.0 1.0 C23E7 3.2-----CFAA--5.2-3.1 TPKFA 1.6-2.0 0.5 2.0 2.0 Citric acid (50%) 6.5 1.2 2.5 4.4 2 0.5 Ca formate 0.1 0.06 0.1 --- Na formate 0.5 0.06 0.1 0.05 0.05
SCS 4.0 1.0 3.0 1.2 -borate 0.6-3.0 2.0 2.9 Na hydroxide 5.8 2.0 3.5 3.7 2.7 2.7 ethanol 1.75 1.0 3.6 4.2 2.9 1,2-propanediol 3.3 2.0 8.0 7.9 5.3 Monoethanolamine 3.0 1.5 1.3 2.5 2.5. 8 TEPAE 1.6-1.3 1.2 1.2 Cytochrome I 0.05 0.05 0.07 0.07 0.1 Electron donor I 0.07 0.15 0.1 0.2 0.8 Protease 0.03 0.01 0.03 0.02 0.02
Lipase--0.002--Amylase----0.002-Cellulase--0.0002 0.0005 0.0001
SRP1 0.2-0.1--DTPA--0.3--PVNO--0.3-0.2 Brightener 1 0.2 0.07 0.1--Silicone defoamer 0.04 0.02 0.1 0.1 0.1 Water and other

Example 11 The following liquid detergent formulation was prepared in accordance with the present invention (levels are given in parts / weight; enzymes are expressed as pure enzyme): I II III IV LAS 10.0 0 9.0-C25AS 4.0 1.0 2.0 10.0 10.0 C25E3S 1.0--3.0 C25E7 6.0 8.0 13.0 2.5 TFAA---4.5 APA-1 ---TPKFA 2.0-13.0 7.0 Citric acid 2.0 3.0 1.0 1.5 Dodecenyl / tetradecenyl succinic acid 12.0 10.0--Rapeseed fatty acid 4.0 2.0 1.0-ethanol 4.0 4.0 7.0 2.0 1,2-propanediol 4.0 4.0 2.0 7.0 monoethanolamine---5.0 triethanolamine ---8.0-TEPAE - 0.5 0.2 DETPMP 1.0 1.0 0.5 1.0 Cytochrome I 0.1 0.2 0.5 0.05
Electron donor I 1.2 1.5 2.0 0.07
Protease 0.02 0.02 0.01 0.008 Lipase-0.002- 0.002 Amylase 0.004 0.004 0.01 0.008 Cellulase---0.002 SRP2 0.3-0.3 0.1 Boric acid 0.1 0.2 1.0 2.0 Ca chloride -0.02-0.01
Brightener 1-0.4--Foaming inhibitor 0.1 0.3-0.1 Opacifier 0.5 0.4-0.3 NaOH (up to right pH) 8.0 8.07 6.6 7.7 Water and other

Example 12 The following liquid detergent composition was prepared in accordance with the present invention (levels are given in parts / weight; enzymes are expressed as pure enzyme): I II III IV LAS 25.0-- -C25AS-13.0 18.0 15.0 C25E3S-2.0 2.0 4.0 C25E7--4.0 4.0 TFAA-6.0 8.0 8.0 APA 3.0 1.0 2.0-TPKFA-15.0 11.0 11.0 Citric acid 1.0 1.0 1.0 1.0 Dodecenyl / tetradecenyl succinic acid 15.0---Rapeseed fatty acid 1.0-3 5.5-ethanol 7.0 2.0 3.0 2.0 1,2-propanediol 6.0 8.0 10.0 13.0 monoethanolamine--9.0 9.0 TEMPE--0. 4 0.3 DETPMP 2.0 1.2 1.0-cytochrome I 0.05 0.07 0.07 0.1 electron donor I 0.15 0.1 0.2 0.8 protease 0.08 0.02 0.01 0.02
Lipase--0.003 0.003 Amylase 0.004 0.01 0.01 0.01 0.01
Cellulase--0.004 0.003 SRP2--0.2 0.1 Boric acid 1.0 1.5 2.5 2.5 Bentonite clay 4.0 4.0--Brightener 1 0.1 0.2 0. 3-Foaming suppressant 0.4---Opaque agent 0.8 0.7--NaOH (up to right pH) 8.0 7.5 8.0 8.2 Water and other

Example 13 The following liquid detergent composition was prepared according to the present invention (levels are given in parts / weight; enzymes are listed as pure enzyme): I II LAS 27.6 18.9 C45AS 13.8 5.9 C13E8 3.0 3.1 Oleic acid 3.4 2.5 Citric acid 5.4 5.4 Na hydroxide 0.4 3.6 Ca formate 0.2 0.1 Na formate- 0.5 ethanol 7.0-monoethanolamine 16.5 8.0 1,2-propanediol 5.9 5.5 xylene sulfonic acid-2.4 TEMPE 1.5 0.8 protease 0.05 0.02 Cytochrome I 0.1 0.05 Electron donor I 1.2-Electron donor II-0.09 Dehydrogenase IV 0.1-PEG-0.7 Brightener 2 0.4 0.1 Fragrance 0.5 0.3 Water and water Other

[0110] Example 14 The following granular fabric detergent compositions which exhibit the capacity "softening by washing" was prepared in accordance with the present invention: I II C45AS - 10.0 LAS 7.6 - C68AS 1.3 - C45E7 4.0 -C25E3-5.0 Cocoalkyldimethylhydroxyethylammonium chloride 1.4 1.0 citrate 5.0 3.0 NaSKS-6-11.0 Zeolite A 15.0 15.0 MA / AA 4.0 4.0 DETPMP 0.4 0.4 PB1 15.0-Percarbonate-15.0 TAED 5.0 5.0 Smectite clay 10.0 10.0 HMWPEO-0.1 Cytochrome I 0.1 0.1 Electron donor I 0 0.9 1.5 Protease 0.02 0.01 Lipase 0.02 0.01 Amylase 0.03 0.005 Cellulase 0.001-Silicate 3.0 5.0 Carbonate 10.0 10.0 Foaming inhibitor 1.0 4.0 CMC 0.2 0.1 Water and other up to 100%

Example 15 The following fabric softener composition with a rinse was prepared according to the present invention: DEQA (2) 20.0 cytochrome I 0.05 electron donor I 0.5 cellulase 0.001 HCl 0.03 defoaming Agent 0.01 blue pigment 25 ppm CaCl ₂ 0.20 fragrance 0.90 water and other up to 100%

Example 16 The following fabric softener and dryer-added fabric conditioner composition was prepared in accordance with the present invention: I II III IV V DEQA 2.6 19.0---DEQA (2)----51.8 DTMAMS---26.0 -SDASA--70.0 42.0 40.2 Stearic acid with IV = 0 0.3----Neodol 45-13--13.0--Hydrochloric acid 0.02 0.02---Ethanol--1.0--Cytochrome I 0.05 0.07 0.1 0.05 0.07 Electron donor I 0.05 0.1 0.2 0.05 0.1 Fragrance 1.0 1.0 0.75 1.0 1.5 Glycoperse S-20----15.4 Glycerol monostearate---26.0-Digeranyl succinate--0.38--Silicone defoamer 0.01 0.01---Electrolyte-0.1-- -Clay---3.0-Dye 10ppm 25ppm 0.01--Water and other 100% 100%---

Example 17 The following solid laundry detergent composition was prepared in accordance with the present invention (levels are given in parts / weight; enzymes are expressed as pure enzyme): I II III IV V VI VII VIII LAS --19.0 15.0 21.0 6.75 8.8-C28AS 30.0 13.5----15.75 11.2 22.5
Na laurate 2.5 9.0-------Zeolite A 2.0 1.25----1.25 1.25 1.25
Carbonate 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0 Ca carbonate 27.5 39.0 35.0--40.0-40.0 Sulfate 5.0 5.0 3.0 5.0 3.0--5.0 TSPP 5.0----5.0 2.5-STPP 5.0 15.0 10.0--7.0 8.0 10.0 Bentonite clay- 10.0--5.0---DETPMP-0.7 0.6-0.6 0.7 0.7 0.7 CMC-1.0 1.0 1.0 1.0--1.0 Talc--10.0 15.0 10.0----Silicate--4.0 5.0 3.0----PVNO 0.02 0.03-0.01-0.02 --MA / AA 0.4 1.0--0.2 0.4 0.5 0.4 SRP1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 cytochrome I 0.01 0.05 0.1 0.1 0.5 0.01 0.05 0.1 electron donor I 0.1 0.2 0.9 0.9 2.0 0.1 0.2 0.9 amylase--0.01---- 0.002-Protease-0.004-0.003 0.003--0.003
Lipase-0.002-0.002-----Cellulase-.0003--.0003 .0002--PEO-0.2-0.2 0.3--0.3 Fragrance 1.0 0.5 0.3 0.2 0.4--0.4 Mg sulfate--3.0 3.0 3.0---- Whitening agent 0.15 0.1 0.15-----0.1 Light activated bleach (ppm)-15.0 15.0 15.0 15.0--15.0

Example 18 The following detergent additive composition was prepared in accordance with the present invention: I II III LAS-5.0 5.0 STPP 30.0-20.0 Zeolite A-35.0 20.0 PB1 20.0 15.0-TAED 10.0 8.0-Protease-0.3 0.3 Amylase-0.06 0.06 Cytochrome I 0.1 0.1 0.1 Electron donor I 0.01 0.01 0.01. 01 Water and other up to 100%

Example 19 The following compact high density (0.96 Kg / L) dishwashing detergent composition was prepared in accordance with the present invention: I II III IV V VI VII VIII STPP--54.3 51.4 51.4--50.9 citrate 35.0 17.0-- -46.1 40.2-Carbonate-17.5 14.0 14.0 14.0-8.0 32.1 Bicarbonate------25.4--Silicate 32.0 14.8 14.8 10.0 10.0 1.0 25.0 3.1 Metasilicate-2.5-9.0 9.0----PB1 1.9 9.7 7.8 7.8 7.8 7.8 ----PB4 8.6---------------------6.7 11.8 4.8 Nonionic 1.5 2.0 1.5 1.7 1.5 2.6 1.9 5.3 TAED 5.2 2.4---------------------------------------------------------------------------------- DETPMP -0.6--------MnTACN---------0.008-PAAC---0.008 0.01 0.007----BzP-----1.4----Paraffin 0.5 0.5 0.5 0.5 0.5 0.5 0.6 -Cytochrome I 0.05 0.005 0.08 0.1 0.004 0.009 0.05 0.005 Electron donor I 0.5 0.03 0.9 1.0 0.1 0.1 0.5 0.03 Protease 0.072 0.072 0.029 0.053 0.046 0.026 0.059 0.06 Amylase 0.012 0.012 0.006 0.012 0.013 0.009 0.017 0.03 Lipase-0.001-0.005-----BTA 0.3 0.3 0.3 0.3 0.3 -0.3 0.3 MA / AA------------------------------------------------------------------0.9 0.9 Perfume 0.2 0.2 0.2 0.2 0.2 0.2 0.1 0.1 11.3 11.3 9.6 10.8 10.9 Water and other up to 100%

[0116] The following granular dishwashing detergent compositions of Example 20 Bulk Density 1.02 kg / L were prepared according to the present invention: I II III IV V VI VII VIII STPP 30.0 30.0 33.0 34.2 29.6 31.1 26.6 17.6 Carbonate 30.5 30.5 31.0 30.0 23.0 39.4 4.2 45.0 Silicate 7.4 7.4 7.5 7.2 13.3 3.4 43.7 12.4 Metasilicate--4.5 5.1-----Percarbonate---------PB1 4.4 4.2 4.5 4.5------NADCC------2.0-1.6 1.0 Nonionic 1.2 1.0 0.7 0.8 1.9 0.7 0.6 0.3 TAED 1.0-----0.8--PAAC-0.004 0.004 0.004-----BzP---1.4-----Paraffin 0.25 0.25 0.25 0.25-----Cytochrome I 0.05 0.05 0.05 0.05 0.03 0.03 0.03 0.03 Electron Donor I 0.05 0.1 0.15 0.05 0.05 0.1 0.15 0.05 Protease 0.036 0.015 0.026 0.028-0.01--Amylase 0.003 0.003 0.006 0.006-0.006--Lipa ZE 0.005-0.001------BTA 0.15 0.15 0.15 0.15------Fragrance 0.2 0.2 0.2 0.2 0.1 0.2 0.2-Sulfate 23.4 25.0 22.0 18.5 30.1 19.3 23.1 23.6 pH 10.8 10.8 11.3 11.3 10.7 11.5 12.7 10.9 Water and other 100% Until

Example 21 The following tablet detergent composition was prepared using a standard 12 head rotary press at 13K
Prepared according to the invention by compressing the granule dishwashing detergent composition under a pressure of N / cm ² : I II III IV V VI STPP -48.8 49.2 38.0 -46.8 citrate 26.4 ----- 31.1-carbonate-5.0 14.0 15.4 14.4 23.0 silicate 26.4 14.8 15.0 12.6 17.7 2.4 cytochrome I 0.05 0.05 0.05 0.005 0.1 0.01 electron donor I 0.05 0.015 0.5 0.05 1.0 0.1 protease 0.058 0.072 0.041 0.033 0.052 0.013 amylase 0.01 0.012 0.012 0.007 0.016 0.002 lipase 0.005-------PB1 1.6 7.7 12.2 10.6 15.7-PB4 6.9----14.4 Nonionic 1.5 2.0 1.5 1.65 0.8 6.3 PAAC--0.02 0.009--MnTACN-----0.007-TAED 4.3 2.5--1.3 1.8 HEDP 0.7--0.7-0.4 DETPMP 0.65-- ----Paraffin 0.4 0.5 0.5 0.55--BTA 0.2 0.3 0.3 0.3--PA30 3.2-------MA / AA---- -4.5 0.55 Flavor--0.05 0.05 0.2 0.2 Sulfate 24.0 13.0 2.3-10.7 3.4 Tablet weight 25g 25g 20g 30g 18g 20g pH 10.6 10.6 10.7 10.7 10.9 11.2 Water and other up to 100%

Example 22 The following liquid dishwashing detergent composition having a density of 1.40 Kg / L was prepared according to the present invention:
I II III IV STPP 17.5 17.5 17.2 16.0 Carbonate 2.0-2.4-silicate 5.3 6.1 6.1 14.6 15.7 NaOCl 1.15 1.15 1.15 1.25
Polygen / Carbopol 1.1 1.0 1.1 1.25
Nonionic--0.1-NaBz 0.75 0.75--Cytochrome I 0.01 0.01 0.05 0.05 0.05
Electron Donor I 0.05 0.1--Electron Donor II--0.2 0.5 NaOH-1.9-3.5 KOH 2.8 3.5 3.5-pH 11.0 11.7 10 9.9 11.0 Sulfate, water and other up to 100%

Example 23 The following liquid rinse aid composition was prepared in accordance with the present invention: I II III Nonionic 12.0-14.5 Nonionic Blend-64.0-Citric Acid 3.2-6.5 HEDP 0.5--PEG-5.0-Cytochrome I 0.004 0.005 0.005 Electron donor I 0.002 0.002 0.002 SCS 4.8-7.0 Ethanol 6.0 8.0- PH of the liquid 2.0 7.5 /

Example 24 The following liquid dishwashing composition was prepared in accordance with the present invention: I II III IV V C17ES 28.5 27.4 19.2 34.1 34.1 Amine oxide 2.6 5.0 2.0 3.0 3.0 C12 glucose amide--6.0--Betaine 0.9--2.0 2.0 Xylene Sulfonate 2.0 4.0-2.0-Neodol C11E9--5.0--Polyhydroxy fatty acid amide---6.5 6.5 Sodium diethylenepentaacetic acid (40%)--0.03--TAED---0.06 0.06 Sucrose---1.5 1.5 Ethanol 4.0 5.5 5.5 9.1 9.1 Alkyl diphenyl oxide sulfonate----2.3 Ca formate---0.5 1.1 Ammonium citrate 0.06 0.1---Na chloride-1.0---Mg chloride 3.3-0.7--Ca chloride--0.4--Na sulfate --0.06--Mg sulfate 0.08----Mg hydroxide---2.2 2.2 Na hydroxide---1.1 1.1 Hydrogen peroxide 200 ppm 0.16 0.006--Cytochrome I 0.005 0.007 0.009 0.1 0.15 Electron donor I 0.0 5 0.05 0.05 0.07 0.1 Protease 0.017 0.005 .0035 0.003 0.002 Flavor 0.18 0.09 0.09 0.2 0.2 Water and other up to 100%

Example 25 The following liquid hard surface cleaning composition was prepared in accordance with the present invention: I II III cytochrome I 0.01 0.05 0.1 electron donor I 0.1 0.9 0.9 amylase 0.01 0.002 0.005
Protease 0.05 0.01 0.02 EDTA ^* 0.05 0.05 0.05 Citrate 2.9 2.9 2.9 LAS 0.5 0.5 0.5 C12AS 0.5 0.5 0. 5 C12 (E) S 0.5 0.5 0.5 C12,13E6.5 Nonionic 7.0 7.0 7.0 Fragrance 1.0 1.0 1.0 Hexyl carbitol ^** 1.0 1 1.0 1.0 SCS 1.3 1.3 1.3 Water To the remaining 100% ^* Na4 ethylenediamine diacetate ^** diethylene glycol monohexyl ether ^*** All formulations were adjusted to pH 7-12

Example 26 The following spray composition for cleaning hard surfaces and removing domestic mold was prepared according to the present invention: Cytochrome I 0.01 Electron Donor I 0.1 Amylase 0.01 Protease 0.01 Na Octyl Sulfate 2.0 Na dodecyl sulfate 4.0 NaOH 0.8 silicate 0.04 Butyl carbitol ^* 4.0 Fragrance 0.35 Water / Others Up to 100% ^* Diethylene glycol monobutyl ether

Example 27 The following Rabatrie cleansing block composition was prepared in accordance with the present invention: I II III C16-18 fatty alcohol / 50EO 80.0--LAS--80.0 Nonionic-1.0-Oleoamide surfactant-26.0-Vinyl methyl Partial esterified copolymer of ether and maleic anhydride, viscosity 0.1-0.5 5.0--polyethylene glycol MW 8000-39.0-water soluble K-polyacrylate MW 4000-8000-12.0-of acrylamide (70%) and acrylic acid (30%) Water-soluble Na copolymer Low MW-19.0-Na triphosphate 10.0--Cytochrome I 0.05 0.05 0.05
Electron donor I 0.02 0.02 0.02
Dye 2.5 1.0 1.0 Fragrance 3.0-7.0 KOH / HCl solution pH6-11

[0124] was prepared in accordance with the present invention Example 28 toilet cleaning compositions the following: I II C14-15 linear alcohol 7 EO 2.0 10.0 Citric acid 10.0 5.0 Cytochrome I 0.05 0.05 Electronic Donor I 0.03 0.05 DETPMP-1.0 Dye 2.0 1.0 Fragrance 3.0 3.0 NaOH pH 6-11 Water and others up to 100%

Example 29 The following monolayer effervescent denture cleansing tablet was prepared according to the present invention: I II cytochrome I 0.1 0.1 electron donor I 0.5 0.5 protease 0.05 2.0 2.0 sodium bicarbonate 39 3.0 39.0 Malic acid 14.0 14.0 Sulfamic acid 3.0 3.0 TAED 2.0 2.0 Dye / Flavor 2.0 2.0 PB1 16.0 16.0 EDTA 3.0 3.0. 0 PEG 10,000 6.0 6.0 K monopersulfate 13.0 13.0 Na carbonate 1.0 1.0 LAS 1.0 1.0 Pyrolyzed silica 2.0 2.0

Example 30 The following dentifrice composition was prepared according to the present invention: I II III IV Sorbitol (70% aqueous solution) 35.0 35.0 35.0 35.0 PEG-6 1.0 1.0 1.0 1.0 Silica dental abrasive 20.0 20.0 20.0 20.0 Sodium fluoride 0.2 0.2 0.2 0.2 Titanium dioxide 0.5 0.5 0.5 0.5 Sodium saccharin 0.3 0.3 0.3 0.3 Cytochrome I 0.05 0.1 0.03 0.03 Electron donor I 0.09 0.2 0.3 0.5 Protease 0.05 0.1 0.9 2.0 Sodium alkyl sulfate (27.9% aqueous solution) 4.0 4.0 4.0 4.0 Flavor 1.0 1.0 1.0 1.0 Carboxyvinyl polymer 0.3 0.3 0.3 0.3 Carrageenan 0.8 0.8 0.8 0.8 Water and other up to 100%

[0127] Example 31 Mouthwash compositions below were prepared in accordance with the present invention: I II III IV SDA40 alcohol 8.0 8.0 8.0 8.0 Flavor 0.08 0.08 0.08 0.08 Emulsifier 0.08 0.08 0.08 0.08 Sodium fluoride 0.05 0.05 0.05 0.05 Glycerin 10.0 10.0 10.0 10.0 Sweetener 0.02 0.02 0.02 0.02 cytochrome I 0.05 0.08 0.1 0.1 electron donor I 0.5 0.8 0.5 1.0 protease 0.01 0.09 0.2 2.0 benzoic acid 0.05 0.05 0.05 0.05 sodium hydroxide 0.2 0.2 0.2 0.2 pigment 0.04 0.04 0.04 0.04 water and other up to 100%

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, KE, LS, MW, SD, SZ, UG, ZW) , EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, HU, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS , LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventor Alfred, Bush, Belgium 1840, Ron, Belgium Seel, Handelsstraat, 210 F-term (reference) 4H003 AB19 AB27 AB28 AB31 AC05 AC08 AE06 DA01 DA02 DA05 DA17 DA19 EA12 EA15 EA16 EA20 EA28 EB08 EB12 EB13 EB22 EB24 EB28 EB32 EB34 EB37 FA05

Claims (26)

[Claims] 1. A cleaning composition comprising cytochrome, an electron carrier and an electron donor compound. 2. The composition according to claim 1, wherein said cytochrome is present in an amount of from 0.0001 to 2% by weight of the total composition, preferably from 0.001 to 0%.
. The cleaning composition according to claim 1, wherein the cleaning composition is present at a pure enzyme level of 5%, more preferably 0.005 to 0.1%. 3. The cleaning composition according to claim 1, wherein the cytochrome is cytochrome P450. 4. The cleaning composition according to claim 1, wherein the electron carrier is contained within a cytochrome structure. 5. The cleaning composition according to claim 4, wherein the cytochrome is cytochrome P450bm3. 6. An electron donor compound comprising from 10 ^-6 to 15% by weight of the total composition, preferably from 10 ^{-5 to} 5%.
Cleaning composition according to any one of the preceding claims, wherein the cleaning composition is contained at a level of more preferably 0.0001 to 1%. 7. The method according to claim 1, wherein the electron donor is selected from nicotinamide adenine dinucleotide (reduced), nicotinamide adenine dinucleotide phosphate (reduced) and / or sodium sulfite. Cleaning composition. 8. An electron carrier comprising 0.0001 to 2% by weight of the total composition, preferably 0.001 to 2%.
The cleaning composition according to any one of the preceding claims, wherein the cleaning composition is present at a level of 0.5%, more preferably 0.005 to 0.1%. 9. The cleaning composition according to claim 1, wherein the electron carrier is selected from flavin mononucleotide, flavin adenine dinucleotide, iron-sulfur protein and / or iron-sulfur protein reductase. object. 10. The weight ratio of pure cytochrome enzyme to electron donor compound or electron carrier is preferably from 10: 1 to 1: 1000, more preferably from 2: 1 to 1: 100, and most preferably from 1: 1 to 1: 1. : 10. The cleaning composition according to any one of claims 1 to 9, wherein 11. The cleaning composition according to claim 1, wherein the cytochrome is alkaline. 12. The cleaning composition according to claim 1, further comprising a detergent enzyme, preferably selected from cellulases, lipases, proteases, amylases and / or mixtures thereof. 13. The cleaning composition according to claim 1, further comprising another bleaching system. 14. The cleaning composition according to claim 13, wherein the bleaching system is a conventional activated bleaching system. 15. The bleaching agent is selected from perborates and / or percarbonates and the activator is selected from tetraacetylethylenediamine, nonanoyloxybenzenesulfonate and / or 3,5-trimethylhexanoloxybenzenesulfonate. A cleaning composition according to claim 1. 16. The cleaning composition according to claim 13, wherein the bleaching system is another enzyme bleaching system. 17. The cleaning composition according to claim 13, wherein the bleaching system is a metallocatalyst-based bleaching system. 18. The cleaning composition according to claim 17, wherein the metallocatalyst is a transition metal complex of a macropolycyclic hard ligand. 19. The cleaning composition according to claim 17, wherein the metallo catalyst is manganese. 20. The cleaning composition according to claim 1, which is in the form of an additive. 21. A fabric softening composition comprising cytochrome, an electron carrier, an electron donor compound, and a cationic surfactant having two long chain lengths. 22. A cleaning and / or softening composition for fabric cleaning and / or fabric stain removal and / or fabric whiteness maintenance and / or fabric softening and / or fabric color appearance and / or fabric transfer dyeing inhibition. Use of cytochromes, electron carriers and electron donor compounds in materials. 23. Use of a cytochrome, an electron carrier and an electron donor compound in a cleaning composition for cleaning hard surfaces such as floors, walls, bathroom tiles, and the like. 24. The use of cytochromes, electron carriers and electron donor compounds in a cleaning composition for hand and machine dishwashing. 25. Use of cytochromes, electron carriers and electron donor compounds in a cleaning composition for oral and / or dental. 26. Use of a cytochrome, an electron carrier and an electron donor compound in a cleaning or softening composition for sanitizing treated surfaces.