JP2003529623A - Detergent composition containing pectate lyase and bleach - Google Patents

Abstract

  (57) [Summary] The present invention relates to the use of a pectate lyase enzyme, and a source of peroxygen and a color safe bleach booster, to provide excellent cleaning performance, especially against plant soil based stains, highly colored food stains / stains and body soils. Combination, metal bleach catalyst and / or detergent compositions containing a bleach system selected from diacyl peroxides.

Description

Detailed Description of the Invention

[0001]

【Technical field】

The present invention relates to a pectate lyase and a color safe bleach booster.
A detergent composition containing a bleach system selected from a combination of (color safe bleach booster) and a peroxygen source, a metal bleach catalyst and / or a diacyl peroxide.

[0002]

BACKGROUND OF THE INVENTION

The performance of a detergent product is judged by several factors, including the ability to remove soil and the ability to prevent redeposition of soil or soil degradation products on objects during washing. Therefore, detergent compositions now contain complex combinations of active ingredients that meet certain special needs. In particular, current detergent formulations usually contain surfactants and detergent enzymes that exert cleaning and fabric care benefits.

The removal of stains due to plants, wood, mold-clay based soils, mud soils and fruits is one of today's most troublesome cleaning operations, especially in view of the trend towards lower wash temperatures. These stains typically contain a complex mixture of fibrous materials based mainly on carbohydrates and their derivatives: fiber and cell wall components. Plant-based soils are further associated with amylose, sugars and their derivatives. Food soils are often difficult to effectively remove from soiled substrates. Highly colored or "dry" soils due to fruit and / or vegetable juices are particularly difficult to remove. Examples of such stains are orange juice, tomato juice, banana, mango or broccoli stains.
In fact, pectin polymers are an important constituent of plant cell walls. Pectin
It is a heteropolysaccharide having a main chain composed of homogalacturonan (smooth region) and rhamnogalacturonan (hairy region) alternately. Smooth region is 1,4-bonded α-
It is a linear polymer of D-galacturonic acid. Galacturonic acid residues can be methyl-esterified to varying degrees on the carboxyl groups, usually non-randomly blocks of polygalacturonic acid being completely methyl-esterified. Common substrates for pectin-containing stains are fabrics, dishes or hard surfaces.

In addition, highly colored or'derived, for example, from fruits and / or vegetables
Dry'dirts are also particularly difficult to remove. These pigmented stains are based on α-, β- and γ-carotene, carotenoid compounds such as lycopene and xanthophylls (zeaxanthin or capsanthin), porphyrins such as chlorophyll, and flavonoid pigments and dye components. Contains a colored compound. This latter group of natural flavonoid-based dye components consists of highly pigmented anthocyanin dyes and pigments based on pelargonidin, cyanidin, delphidin and their methyl esters, and anthoxanthins. These compounds are the most chromogenic sources of orange, red, purple and blue in fruits, including all berries, cherries, red and black currants, grapefruit, passionfruit, oranges, lemons, apples, pears, pomegranates, red cabbage. Abundant in red turnips and even flowers. Carotenoid stains come from carrots and tomatoes, any processed products containing these ingredients, and certain tropical fruits and saffron. Particularly in the dishwashing context, these colored food stains can flow out of the dirt into the wash liquor and redeposit from the wash liquor into other items being washed or inside the dishwasher. The problem is especially noticeable when food items naturally containing significant levels of colored dye molecules, such as tomato sauce and curry-stained articles, are in the wash.

The inventor has found that the plastic product being washed, especially the interior area of the dishwasher made of plastic material, is particularly susceptible to stains / discoloration of dishes due to colored food stains. The stains described above can interact with the surface of such plastic substrates which are very hard to remove. Several of our co-pending European patent applications have proposed a method of eliminating the problem of colored food dye deposition by mechanical dishwashing. For example, EP692947 provides an effective dye transfer inhibiting composition for machine dishwashing processes. The composition contains an enzyme system capable of generating hydrogen peroxide with a metal catalyst. EP 740521 describes the use of diacyl and tetraacyl peroxide bleaching species in hindering the migration of bleachable food soils and enhancing their removability from plastic substrates.

In addition, the complex nature of daily “body” stains typically found on pillowcases, T-shirts, collars and socks has led to the difficulty of continuous and thorough cleaning with detergents. These stains are due, in part, to the interaction with the pectin component in the major cell walls of the cotton fibers that make up the cotton-containing fabrics, and often also in the residue that accumulates on such fabrics and turns dark and yellow. , Difficult to completely remove. Moreover, stains of bodily fluids such as blood and menstrual fluid are often difficult to effectively remove from dirt, especially when the stains are aged. Everyday body stains
Also found on sanitary and kitchen surfaces such as bathtubs, toilet bowls and dishes.

Bleaching compositions for the bleaching of such plant stain-based stains, highly pigmented stains and stains, and body stains are widely described in the art. Suitable bleaching agents are usually
Per compounds that release hydrogen peroxide in aqueous solution, such as peroxyhydrates, perborates, percarbonates, perpyrophosphates, persilicates, urea peroxides. The use of such per-compounds is known to be improved by the use of organic bleach activators or peroxy acid precursors. Such bleaching compositions are known to be effective in removing all types of stains.
More recently, products containing bleach catalysts, especially manganese bleach catalysts, have become of interest.

In addition, oxygen bleaches have become increasingly popular in household and personal care products in recent years to facilitate stain and stain removal. Bleaching is particularly desirable due to their stain removal, darkened fabric cleanup, whitening and sanitizing properties. Oxygen bleach has been found to be particularly acceptable in laundry products such as detergents, automatic dishwashing products and hard surface cleansers. However, oxygen bleaches have somewhat limited efficacy. Some frequently encountered drawbacks are color damage to fabrics and damage to laundry appliances, especially the rubber hoses that these appliances carry. In addition, oxygen bleaches tend to be extremely temperature ratio dependent. Therefore, the cooler the solution in which they are used, the less effective the bleaching action. Temperatures above 60 ° C are typically required for the efficacy of oxygen bleaches in solution.

Attempts have been made to develop bleach systems that are effective under cold water conditions. Madison et al. US Pat. No. 5,360,568, Madison et al. US Pat. No. 5,360,569 and Madison et al. US Pat. The quaternary imine salts are said to increase the activity of peroxygen compounds over a range of water temperatures, including low temperatures. However, these positively charged quaternary imine salts are not entirely satisfactory for laundry bleaching. In particular, the positively charged quaternary imine salts disclosed in these references, when combined with peroxygen compounds, result in unacceptable levels of color damage to the fabric.

Thus, there remains a need for detergent compositions capable of effective bleaching, especially plant soil based stains, highly pigmented stains and stains, and body stains. Such a need is more acute at low water temperatures, while at the same time providing an improved color safety profile and / or preventing stains / discoloration of dishes from highly colored components. These needs are met by a detergent composition of the invention containing a pectate lyase enzyme and a bleach system selected from a combination of bleach booster and peroxygen source, a metal bleach catalyst and / or diacyl peroxide.

It was surprisingly found that such a selected bleach system can maximize the pectate lyase enzyme cleaning efficacy. Further, a detergent composition containing a pectate lyase and such a selected bleach system provides a selected bleach system for cleaning, stain removal, and whiteness maintenance in the laundry context, and the pectin component of such stains, It has been surprisingly found that, in laundry and / or laundry relations, due to the synergistic effect with pectate lyase, which decomposes the pectin component of the fabric, which can bind to such stains, it exhibits excellent cleaning properties. These selected bleach-enzyme mixed systems exert a significant cleaning effect, especially against food coloring stains and body stains. Moreover, when formulated as a laundry and / or fabric care composition, the compositions of the present invention provide synergistic whiteness maintenance.

Without being bound by theory, it is believed that the natural pectin found in many common fruit and plant based stains and the main walls of cotton fibers attracts and embraces stain residues, especially highly pigmented stain components. Has been. Removal of the pectin component by pectate lyase exposes these color bodies to the bleach system.
The synergistic effect is that these bleaching systems decolorize color components that are difficult to remove food stains and body stains, and pectate lyases cause pectin components of such stains and / or, in the laundry context, such stains. It is believed to be due to the decomposition of the pectin component of the fabric which makes it difficult to remove the stains by binding or interacting with.

In particular, the detergent composition of the present invention containing a diacyl peroxide, especially in plastic products, provides particularly effective stain removal of stains and stains, as well as stains / discoloration of dishes due to the stain components. Surprisingly, I found that it hindered me. Furthermore, it has been surprisingly found that the combination of pectate lyase and bleach booster as the bleach system of choice enhances the cleaning properties by improving the overall efficacy of the bleach system, especially at low wash temperatures. The addition of the bleach booster allows the oxygen-based bleaching system to more completely bleach these exposed color bodies at low wash temperatures, thus providing both improved stain removal and enhanced whiteness.

Pectin-degrading enzymes stain / waste when used in cleaning and cleaning operations.
Exhibits a stain removal effect, especially in a wide range of plant and fruit-based stain removal,
It is known to enhance the body soil cleaning properties of detergent compositions. Pectin-degrading enzyme means an enzyme that acts to decompose a pectin substance and a pectin-related substance. Pectin-degrading enzymes are substrates they prefer, high- or low-methyl-esterified pectin and polygalacturonic acid (pectic acid).
, And their reaction mechanism, β-elimination or hydrolyzability. Pectin-degrading enzymes predominantly endo-act to cleave the polymer at random sites within the chain to give a mixture of oligomers, or they exo-act and attack from one end of the polymer to the monomer or dimer. Occurs. Some pectinase activities that act on the smooth region of pectin include pectate lyase (EC4.
2.2.2), pectin lyase (EC4.2.2.10), polygalacturonase (EC3.2
.1.15), exo-polygalacturonase (EC3.2.1.67), exo-polygalacturonic acid lyase (EC4.2.2.9) and exo-poly-α-galacturonosidase (EC3.2.1.82) , Enzyme Nomenclature (1992). Pectin degrading enzymes are natural mixtures of the above enzymatic activities.

Each type of pectin degrading enzyme has a unique profile of substrate specificity, activity and stability under different hardness, pH, temperature, detergent and other detergent component matrix conditions. Pectin-degrading enzymes have been identified to degrade pectin substances, especially plant cell walls. In particular, the pectate lyase enzyme is involved in the cleavage of the α-D- (1,4) glycosidic bond in poly-D-galacturonan by a mechanism of β-elimination. These pectate lyase enzymes also serve to remove mixed stains / soil containing pectin material and other ingredients. However, stains / stains that are not sensitive to pectate lyase, such as non-pectin carbohydrates, lipids, proteins and their derivatives, block the access of pectin substances to the enzyme and require another strong detergent component. Sometimes.

The use of pectin degrading enzymes in detergents is already known in the art. The use of pectin enzymes is also known for contact lens cleaning (US 4,710,3).
13-J60196724). Enzymes with pectinase activity do not damage fabrics, cause discoloration, remove inorganic dirt, such as mud, from laundry, enhance detergent capacity and disperse inorganic substances over phosphates. Can also allow the use of less efficient zeolites and polycarbonate builders, D
It is described in E3635427. Detergent formulations, especially designed for laundering, dishwashing and household cleaning operations, the effect of using pectin enzymes has been found in WO 95/25790. JP 60226599 describes detergent compositions containing conventional detergent activators and cellulases and hydrolases such as hemicellulases, pectinases, amylases or proteases. The combination of cellulase and hydrolase is said to exert a good cleaning effect on inorganic soils, along with enzymatic activity. WO 95/09909 describes enzyme preparations containing a modifying enzyme selected from the group of amylases, lipases, oxidoreductases, pectinases or hemicellulases, the modifying enzyme being an alkaline pI obtained by chemical modification or amino acid substitution and And / or have improved performance due to increased surface activity. Modified pectin and /
Alternatively, pectin degrading and / or hemicellulose degrading and / or lipolytic enzymes are beneficially utilized in the paper industry and modified amylase and / or lipase are beneficially utilized in laundry and dishwashing.

In particular, pectate lyases are Erwinia, Pseudomonas, Klebsiella, Streptom
It has been cloned from different bacterial genera such as yces, Penicillium, Bacteroides, Thermomonospora, Fusarium, Aspergillus and Xanthomonas. Bacillus
subtilis (Nasser et al. (1993) FEBS, 335: 319-326) and Bacillus sp. YA-
14 (Kim et al. (1994) Biosci. Biotech. Biochem. 58: 947-949) also describes the cloning of pectate lyase. Bacillus pumilus (Dave and Vau
ghn (1971) J. Bacteriol. 108: 166-174), B. polymyxa (Nagel and Vaughn (1961) Ar
ch.Biochem.Biophys.93: 344-352), B.stearothermophilus (Karbassi and Vaug
hn (1980) Can.J.Microbiol.26: 377-384), Bacillus sp. (Hasegawa and Nagel (1
966) J. Food Sci. 31: 838-845) and Bacillus sp. RK9 (Kelly and Fogarty (1
978) Can. J. Microbiol. 24: 1164-1172), which has been reported to purify a pectate lyase with maximum activity in the pH range of 8-10. WO98 / 4
5393 discloses a detergent composition containing a protopectinase having a remarkable detergency against mud stains.

Diacyl peroxide is widely used as a polymerization initiator, a curing agent and a bleaching agent. US Pat. No. 5,334,326 discloses a liquid or paste consisting of diaroyl peroxide, a liquid alkyl ester of benzoic acid (wherein the alkyl group of the ester has 8-12 carbon atoms) and 0-40% wt of water. The dispersion is described. The ratio of the diaroyl peroxide to the alkyl benzoate is 0.3:
1 to 7: 1. US Pat. No. 4,255,277 describes a non-separated catalyst paste consisting of diacyl peroxide, a small proportion of water, and an amount of finely divided calcium carbonate that does not physically separate the composition into its components. The US patent describes solid organic peroxide compositions containing 50-70% wt of solid organic peroxide, such as dibenzoyl peroxide, and a combination of liquid and solid desensitizers. US Pat. No. 3,723,336 discloses a non-separable composition of 20-60 parts of dibenzoyl peroxide. WO 96/27586 relates to solid diacyl organic peroxide formulations in liquid or paste form with improved thermal stability. WO95 / 33817 is selected from the group of organic peroxy acids, diacyl peroxides, inorganic peroxygen compounds, bleach catalysts, peroxygen bleach precursors and / or mixtures thereof, together with 0.01 to 5% wt of surfactant. Wax encapsulated particles having core particles or agglomerates of core particles are described. GB 1,538,477 relates to a bleaching composition containing a surfactant, a builder salt, and a bleaching agent consisting of a diacyl peroxide of the general formula ROOR ¹ where R is a phthaloyl group and R ¹ is an acyl group. EP
257700 relates to a bleaching composition consisting of a per-compound and a mixture of at least two selected peroxyacid bleach precursors.

Metal bleach catalysts are known in the detergent art. Recent techniques include: WO 98/36403 describes laundry compositions containing a transition metal bleach catalyst consisting of a complex of a transition metal and a bridged macropolycyclic ligand. WO9
8/39405 is a bleach activator and / or organic percarboxylic acid,
The present invention relates to a laundry composition containing a transition metal bleach catalyst composed of a complex of a transition metal and a bridged macropolycyclic ligand. WO 97/36991 is a metal-containing bleach catalyst,
It relates to a bleaching composition containing an oxygen-releasing bleach system and a specific formula of aminotricarboxylic acid. WO 97/34985 discloses bleaching compositions containing a metal-containing bleach catalyst, an oxygen-releasing bleach system and a cellulase. WO97 / 2
9174 describes bleach catalyst particles for detergent compositions. WO9
7/22681 relates to an automatic dishwashing composition containing a metal bleach catalyst, a hydrogen peroxide source, a phosphate builder and a dishwashing ingredient.

However, for excellent cleaning performance in detergent compositions, pectate lyase and synergism of a bleaching composition, a combination of a bleach booster and a peroxygen source, a selected bleach system selected from metal catalysts and / or diacyl peroxides. Target combinations were not previously recognized.

[0021]

[Summary of Invention]

The present invention relates to a laundry, dishwashing or hard surface cleaner detergent composition containing a pectate lyase and a bleach system selected from a combination of a bleach booster and a peroxygen source, a metal bleach catalyst and / or a diacyl peroxide. These compositions exhibit excellent cleaning performance, especially on plant soil based stains, highly pigmented food stains / stains and body stains. Such a laundry detergent composition,
It also maintains excellent whiteness. Furthermore, these compositions containing a color safe booster exhibit an improved color safety profile while exhibiting excellent cleaning performance at low water temperatures. In addition, these compositions containing diacyl peroxide provide effective highly pigmented stain and stain removal, especially in plastic products, and also prevent stain / discoloration of dishes by highly pigmented ingredients.

[0022]

[Detailed Description of the Invention]

The detergent composition of the present invention contains as essential elements a pectate lyase enzyme and a bleach system selected from a combination of a bleach booster and a peroxygen source, a metal bleach catalyst and / or a diacyl peroxide.

Each type of pectin-degrading enzyme has a unique profile of substrate specificity, activity and stability under different hardness, pH, temperature, detergent and other detergent component matrix conditions. Pectin-degrading enzymes have been identified to degrade pectin substances, especially plant cell walls. In particular, pectate lyase is a pectin degrading enzyme that cleaves the α-1,4-glucoside bond of polygalacturonic acid found in pectin substances, forming a double bond between C4 and C5. The pectate lyase enzyme also serves to remove mixed stains / soil containing pectin material and other ingredients. However, stains / stains that are not sensitive to pectate lyases, such as non-pectin carbohydrates, lipids, proteins and their derivatives or highly pigmented substances associated with pectin, prevent access of the pectin substance to its enzyme and cause May require strong detergent ingredients.

It was surprisingly found that selected bleaches of the invention can maximize pectate lyase cleaning efficacy. It is known that such selected bleach systems are capable of excellent cleaning and stain removal of highly pigmented stains, whiteness maintenance, especially fat / oil stain removal in the context of laundry and / or fabric care. Without being bound by theory, it is believed that pectate lyase degrades the pectin component of stains and stains that act to bind the color bodies and chromophores. Such enzymatic degradation of the pectin component exposes these color bodies and chromophores to the bleach system, allowing them to be effectively removed. It has been found that such a combination provides a performance synergistic on soil and stain cleaning, especially for pigmented food stains / stains and body stains.

In particular, it is well known in the art that cleaning performance decreases with decreasing temperature. This is especially true for pectin-based stain / soil removal and the performance of oxygen bleaching systems. Without being bound by theory, pectate lyase catalyzes the hydrolysis of pectin, which is found in many soils / stains, and in the wash relationship, the residual major wall of the cotton fiber that entraps and embraces the collar body on the surface. It is believed that this helps to improve overall cleanability at low temperatures. Hydrolysis of pectin may facilitate removal by residual detergent components. The pectin component of highly pigmented food stains and the improved removal of pectin from cotton fibers expose the soil chromophore to the oxygen bleaching system of detergent formulations. The bleach booster improves the performance of the oxygen bleach system at low temperatures. The combination of pectate lyase and bleach booster in a detergent formulation containing an oxygen bleaching system is an effective means of removing highly colored food stains from dishes and fabric surfaces, and in the context of laundry it is effective in removing body stains from the fabric surface. Provides removability.

Pectate lyase enzyme An essential element of the detergent composition of the present invention is the pectate lyase enzyme. Pectate lyase is classified within the class of enzymes presented in Enzyme Nomenclature (1992) as EC 4.2.2.2. It is known that the enzyme cleaves the α-1,4-glucosidic bond of galacturonic acid found in pectin substances to form a double bond between C4 and C5, and other pectin degrading activity is substantially eliminated. %, Preferably not more than 25% by weight, preferably not more than 15%, more preferably not more than 5%, and other enzyme compounds having pectin-degrading enzyme activity.

Pectic acid lyases include Erwinia, Pseudomonas, Klebsiella, Streptomyces,
Penicillium, Bacteroides, Thermomonospora, Fusarium, Aspergillus and Xa
It has been cleaned from different bacterial genera such as nthomonas. Bacillus subtil
is (Nasser et al. (1993) FEBS, 335: 319-326) and Bacillus sp. YA-14 (K
im et al. (1994) Biosci. Biotech. Biochem. 58: 947-949) also describes the cloning of pectate lyase. Bacillus pumilus (Dave and Vaughn (19
71) J. Bacteriol. 108: 166-174), B. polymyxa (Nagel and Vaughn (1961) Arch. Bio
chem.Biophys.93: 344-352), B. stearothermophilus (Karbassi and Vaughn (198
0) Can.J.Microbiol.26: 377-384), Bacillus sp. (Hasegawa and Nagel (1966) J.
Food Sci. 31: 838-845) and Bacillus sp. RK9 (Kelly and Fogarty (1978) Ca
nJMicrobiol.24: 1164-1172) has been reported for the purification of pectate lyase with maximal activity in the pH range of 8-10. WO98 / 45393
Discloses a detergent composition containing a protopectinase having a remarkable detergency against mud stains.

Another pectate lyase suitable for use in the present invention is polygalacturonic acid in WO
Protopectinase having an optimum reaction pH of 7.0 or higher when used as a substrate as described in 98/45393, as well as the amino acid sequence SEQ NO. A pectate lyase having such an amino acid sequence having 1, or having one or more amino acids deleted, added or substituted.

The following pectate lyase enzymes are preferred, as described in International Co-pending Application PCT / DK98 / 00515, filed internationally on Nov. 24, 1998 and published in WO 99/27084: Sequence: Asn Leu Asn Ser Arg Val Pro (NL
A pectate lyase comprising a first amino acid sequence consisting of 7 amino acid residues having NSRVP);-the following pectate lyase: i) a polypeptide produced by Bacillus agaradhaerens NCIMB40482 or DSM8721, or Bacillus agaradhaerens DSM8721
Produced by Bacillus sp. Having at least 99% 16S rDNA sequence homology with, or ii) 27-359 of PCT / DK98 / 00515 SEQ ID NO: 2
A polypeptide comprising an amino acid sequence as indicated at position iii), or iii) an analog of the polypeptide defined in i) or ii) that is at least 45% homologous to the above polypeptide, or iv) one or more Derived from the above-mentioned polypeptide by amino acid substitution, deletion or addition (provided that the arginine at position 240 and optionally arginine at position 245 are conserved, and the derived polypeptide is at least the above-mentioned polypeptide. 42% homologous), or v) immunoreactive with a polyclonal antibody against the above polypeptide in purified form; -the following pectate lyase: i) the polypeptide produced by Bacillus licheniformis ATCC 14580, or Bacillus licheniformis. ATCC 14580 and at least 9
A polypeptide produced by Bacillus sp. Having 9% 16S rDNA sequence homology, or ii) 28-341 of PCT / DK98 / 00515 SEQ ID NO: 4
A polypeptide comprising an amino acid sequence as indicated at position iii), or iii) an analog of the polypeptide defined in i) or ii) that is at least 45% homologous to the above polypeptide, or iv) one or more Derived from the above polypeptide by amino acid substitution, deletion or addition (provided that the arginine at the 233 position and optionally the arginine at the 238 position are conserved, and the derived polypeptide is at least the above polypeptide. 42% homology), or v) immunoreactive with a polyclonal antibody against the above polypeptides in purified form; -the following pectate lyases: i) PCT / DK98 / 00515 SEQ ID NO: 14 16S r
A polypeptide produced by a Bacillus species having a DNA sequence, or PCT /
DK98 / 00515 SEQ ID NO: 14 and 97.3% or more of 16S
a polypeptide produced by Bacillus sp. having rDNA sequence homology, or ii) 181-50 of PCT / DK98 / 00515 SEQ ID NO: 6
A polypeptide comprising an amino acid sequence as shown at position 9, or iii) an analogue of the polypeptide defined in i), which is at least 50% homologous to the above polypeptide, or iv) one or more amino acids Derived from the above polypeptide by substitution, deletion or addition of arginine (provided that the arginine at position 390 and optionally arginine at position 395 are conserved, and the derived polypeptide is at least 44% of the above polypeptide). Homologous), or v) immunoreactive with a polyclonal antibody against said polypeptide in purified form; -the following pectate lyase: i) a polypeptide produced by Bacillus halodurans species, or ii) PCT / DK98 / 00515 SEQ ID NO: 8 42-348
A polypeptide comprising an amino acid sequence as indicated at position iii), or iii) an analog of the polypeptide defined in i) or ii) that is at least 45% homologous to the above polypeptide, or iv) one or more Derived from the above-mentioned polypeptide by amino acid substitution, deletion or addition (provided that the arginine at position 240 and optionally arginine at position 245 are conserved, and the derived polypeptide is at least the above-mentioned polypeptide. 40% homology), or v) immunoreactive with a polyclonal antibody against the above polypeptide in purified form; -the following pectate lyase: i) 16T of PCT / DK98 / 00515 SEQ ID NO: 13 r
A polypeptide produced by a Bacillus species having a DNA sequence, or PCT /
DK98 / 00515 SEQ ID NO: 13 and 98.1% or more of 16S
a polypeptide produced by Bacillus sp. having rDNA sequence homology, or ii) 25-33 of PCT / DK98 / 00515 SEQ ID NO: 10
A polypeptide comprising an amino acid sequence as shown at position 5, or iii) an analog of the polypeptide defined in i), which is at least 45% homologous to the above polypeptide, or iv) one or more amino acids Derived from the above-mentioned polypeptide by the substitution, deletion or addition of arginine (provided that the arginine at position 227 and optionally arginine at position 232 are conserved, and the derived polypeptide is at least 41% of the above-mentioned polypeptide. Homologous), or v) immunoreactive with a polyclonal antibody against the above polypeptide in purified form.

Pectinate lyase enzymes such as the following, described in International Co-pending Application PCT / DK98 / 00514, filed internationally on Nov. 24, 1998 and published in WO 99/27083, are likewise preferred: i) a polypeptide produced by Bacillus licheniformis ATCC 14580, or ii) 28-221 of PCT / DK98 / 00514 SEQ ID NO: 4
A polypeptide comprising an amino acid sequence as indicated at position iii), or iii) an analog of the polypeptide defined in i) or ii) that is at least 60% homologous to the above polypeptide, or iv) one or more Derived from the above-mentioned polypeptide by the substitution, deletion or addition of amino acid of
At least 66% homologous to positions 60-158 of SEQ ID NO: 4 of 0514), or v) immunoreactive with a polyclonal antibody against the above polypeptides in purified form.

Further preferred pectate lyases for the purposes of the present invention are those which have an optimum activity at pH> 7.0, and include Streptomyces Fradiae and Streptomyces nitrosporeu.
s, Erwinia carotovora, Bacillus spheroides, Thermomonospora fusca, Pseud
omonas solanacearum, Bacteroides thetaiotaomicron, Fusarium solani, Xant
homonas campestris, Bacillus agaradhaerens and / or Bacillus licheni
derived from formis. The most preferred pectate lyase for the purposes of the present invention is Bacillus agaradhae
rens NCIMB40482 or DSM8721-derived pectate lyase. The pectate lyase is preferably present at a pure enzyme level of 0.0001 to 2% by weight of the composition, more preferably 0.0005 to 0.1%, most preferably 0.001 to 0.02%. It is incorporated into a detergent composition.

The pectate lyase of the present invention contains a cellulose-binding domain (CBD) in addition to the enzyme core containing the catalytic domain, and the cellulose-binding domain and the enzyme core (catalytically active domain) of the enzyme act. Connected as possible. The cellulose binding domain (CBD) may be present as an integral part of the encoded enzyme, or CBD of other origin may be introduced into the enzyme to form an enzyme hybrid. In this context, the term "cellulose binding domain" refers to Peter Tomme et al. "Cellulose-Binding Domains: Classification and Prope
rties "(cellulose binding domain: classification and properties) in" Enzymatic Degradatio
n of Insoluble Carbohydrates ", Enzymatic Degradation of Insoluble Carbohydrates, John N. Saddler
and Michael H. Penner (Eds.), ACS Symposium Series, No. 618, 1996. This rule specifies that 10 or more cellulose-binding domains should be 10
Classified into families (IX), it has been shown that CBD is found in various enzymes such as cellulases, xylanases, mannanases, arabinofuranosidases, acetylesterases and chitinases. CBD is also found in algae such as the red alga Porphyra purpurea as a non-hydrolyzable polysaccharide binding protein; T
See omme et al., supra. However, most CBDs are from cellulases and xylanases, which are found at or are internal to the N and C termini of proteins. Enzyme hybrids are known in the art (eg WO90
/ 00609 and EO95 / 16782), incorporating a DNA construct containing at least a fragment of DNA encoding for a cellulose binding domain linked with or without a linker to a DNA sequence encoding a pectate lyase enzyme into a host cell. Alternatively, it may be prepared by growing the host cell and expressing the fusion gene. The enzyme hybrid is described by the formula: CBD-MR-X where CBD is N of the amino acid sequence corresponding to at least the cellulose binding domain.
Is a terminal or C-terminal region; is MR an intermediate region (linker), a bond or a short linking group, preferably about 2 to about 100 carbon atoms, more preferably 2 to 40 carbon atoms? Alternatively, preferably about 2 to about 100 amino acids, more preferably 2 to 40 amino acids; X is the N-terminal or C-terminal region of the pectate lyase of the present invention.

The enzyme may be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. The origin may further be mesophilic or extreme (eg, psychrophilic, eutrophic, thermophilic, pressure-sensitive, alkalophilic, acidophilic, halophilic). Purified or unpurified forms of these enzymes may also be used. It is now customary to modify wild-type enzymes by protein / genetic engineering techniques to maximize performance efficacy with the detergent compositions of the present invention. For example, variants are designed to increase the compatibility of the enzyme with the conventional ingredients of such compositions. Alternatively, the variants may be designed such that the optimum pH, bleach or chelant stability, catalytic activity, etc. of the enzyme variant are adjusted to suit a particular cleaning application.

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 substituting some charged amino acids, for example increasing the isoelectric point helps improve compatibility with anionic surfactants. Enzyme stability can be further enhanced by, for example, forming additional salt bridges and reinforcing metal binding sites to increase cherant stability.

Bleach System The detergent composition of the present invention further contains, as a second essential element, a bleach system selected from a combination of a bleach booster and a peroxygen source, a metal bleach catalyst and / or a diacyl peroxide.

Diacyl peroxide bleach system The bleach system included in the composition of the present invention includes diacyl peroxide (or DA).
There is P). The diacyl peroxide may be liquid, preferably incorporated into the liquid detergent composition in this form, or it may be particulate, preferably contained in such form in the granular detergent composition.

DAP is selected from the group consisting of dialiphatic peroxides, diaromatic peroxides, aliphatic-aromatic peroxides or mixtures thereof and has the general formula: RC (O) -OO- ( O) C-R ₁ the above formula R and R ₁ may be the same or different, are selected from aliphatic or aromatic group having 6 to 20 carbon atoms. The DAP of the present invention comprises di-aliphatic peroxide, di-aromatic peroxide, and aliphatic-
It is selected from the group consisting of aromatic peroxides and mixtures thereof. When R and R ₁ are aliphatic groups, they may be branched but are preferably straight-chain. Preferred aliphatic groups are from 8 to 14 carbon atoms, most preferably 10
It has -12 carbon atoms. Particularly preferred dialiphatic peroxides are dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dimyristoyl peroxide or mixtures thereof. Dilauroyl peroxide is commercially available under the tradename Laurox ^R from Akzo Nobel. Didecanoyl peroxide is commercially available from Akzo Nobel under the trade name Perkadox SE10. Preferred DAPs are aliphatic-aromatic peroxides, where _one of R or R ₁ is aliphatic and the other is aromatic. In these species, the aromatic moiety is preferably benzoyl. In another embodiment, the aromatic species may be a substituted benzoyl, the substituent preferably being an alkyl group having 1 to 20 carbon atoms. The aliphatic portion preferably has from 8 to 14 carbon atoms, more preferably 10 to 12 carbon atoms, which may be branched, but are preferably straight chains. Examples of suitable diacyl peroxides are dibenzoyl peroxide, benzoyl glutaryl peroxide, benzoyl succinyl peroxide, di (2-methylbenzoyl) peroxide, diphthaloyl peroxide, dioctanoyl peroxide, didecanoyl peroxide, dilauroyl peroxide, dilauryl. Myristoyl peroxide, benzoyl lauroyl peroxide, substituted benzoyl lauroyl peroxide and mixtures thereof. Preferred diacyl peroxides are dibenzoyl peroxide, diphthaloyl peroxide and mixtures thereof, more preferred diacyl peroxide is dibenzoyl peroxide. Further preferred for the purposes of the present invention are dilauroyl peroxide, dibenzoyl peroxide and / or mixtures thereof.

In that case, DAP is contained in the detergent composition of the present invention in the form of microparticles, such microparticles being such that, by weight of the microparticles, 1 to 80% of the water-insoluble diacyl peroxide and diacyl peroxide are dissolved. Not stabilizing additive 0.01-95%. Examples of suitable additives are inorganic salts, transition metal chelants, antioxidants, binders, coatings and / or mixtures thereof. The term "diacyl peroxide does not dissolve" means here that the diacyl peroxide does not dissolve in the stabilizing additive under particulate processing conditions and / or detergent storage conditions. The term "water-insoluble" means here that only limited water solubility, ie less than 1%, preferably less than 0.5%, is soluble in water. The term "stabilizing additive" refers to a compound that is capable of reacting with other components, especially diacyl peroxide, when the diacyl peroxide is stored in the product and does not degrade the diacyl peroxide. Means here.

The particles provide storage stability and protect the diacyl peroxide from being able to interact and degrade with other components over time in the composition. The stabilizing additive in the particles is about 0.1 to about 95%, preferably about 10 to about 95% by weight of the particles.
, And more preferably about 40 to about 95%. Preferably, the stabilizing additive is 100 ° F, preferably 120 ° F.
It is immiscible with the other components of the composition at temperatures below (about 49 ° C). In a particularly preferred embodiment, the stabilizer is soluble in the wash liquor. Inorganic salts useful as stabilizing additives include, but are not limited to, alkali metal sulphates, citric acid, boric acid and their salts, carbonic acid, bicarbonates and alkali metal silicates, and mixtures thereof. Preferred inorganic salts are sodium sulfate and citric acid because they are non-alkaline and prevent alkaline hydrolysis in the product.

Binders and coatings include certain water-soluble polymers in which diacyl peroxide does not dissolve, (ethoxylated C ₁₆ -C ₂₀ alcohols with sufficient ethoxylate groups to prevent dissolution of diacyl peroxide, aliphatic fatty acids , Aliphatic fatty alcohol, maltodextrin, dextrin, starch, gelatin, melting point 1
Polyethylene glycols, polyvinyl alcohols and sorbitols at or above 00 ° F are included but not limited to. The polymer has an average molecular weight of about 100.
0 to about 10,000 polyacrylates, average molecular weight about 2000 to about 80,000
0 and acrylate to maleate or fumarate segment ratio of about 30: 1 to
There is about 1: 2 acrylate / maleate or acrylate / fumarate copolymer. Examples of such copolymers based on a mixture of unsaturated mono and dicarboxylate monomers are incorporated herein by reference, 1982 1
It is disclosed in European patent application 66,915, published on February 15. Other suitable copolymers are both described in US Pat. No. 4,530, both incorporated herein by reference.
, 766 and 5,084,535.

Transition metal chelants which can be used are polyacetate and polycarboxylate builders such as ethylenediaminetetraacetic acid, ethylenediaminedisuccinic acid (especially S
, S form), nitrilotriacetic acid, tartaric acid monosuccinic acid, tartaric acid disuccinic acid, oxydisuccinic acid, carboxymethyloxysuccinic acid, sodium, potassium, lithium, ammonium and substituted ammonium salts of melitic acid, sodium benzene polycarboxylate salt, Nitrilotris (methylenephosphonic acid) diethylenetrinitrilopentakis (methylenephosphonic acid), 1-hydroxyethylidene-1,1
-Diphosphonic acids, other phosphonate chelants (eg Dequ product from Monsanto
est), ethylene-N, N'-bis (o-hydroxyphenylglycine), dipicolinic acid and mixtures thereof.

Antioxidants (radical traps, radical scavengers or free radical inhibitors) are also suitable stabilizing additives. These compounds, even if present in small amounts, slow or stop the reaction. It is believed by the present invention that antioxidants may scavenge or scavenge radicals formed due to the thermal decomposition of peroxide bonds. This prevents the radical from further reacting or promoting the formation of another radical (self-promoted decomposition). Since this material is used in small amounts in the particles, it is unlikely to adversely affect the overall performance of the detergent composition.
Suitable antioxidants include, but are not limited to, citric acid, phosphoric acid, BHT, BHA, α-tocopherol, Irganox series C (Ciba Giegy), Tenox series (Kodax) and mixtures thereof.

It is noted that the above stabilizing additives not only act as stabilizing additives, but can also exert other effects (eg pH control, carbonate / silicate dispersion) in detergent products. Therefore, these components may be added separately from the fine particles. For example, in the agglomerated form of the invention, an aqueous solution of the above polyacrylate may be used as the liquid binder to make the agglomerates. The diacyl peroxide particles formed are preferably from about 400 to about 1000μ.
m, more preferably from about 600 to about 800 μm, less than 1% of the diacyl peroxide particles are greater than 1180 μm (Tyler 14 mesh) and less than 1% are less than 212 μm (Tyler 65 mesh). is there. Typically, the diacyl peroxide is added to the detergent composition of the present invention at a level of 0.01 to 20% by weight of the composition, preferably 0.5 to 10%, more preferably 0.2 to 3%. When the diacyl peroxide is incorporated into the microparticles, the composition of the present invention comprises 0.1 to 30%, preferably 1 to 15%, more preferably 1.5 to 10% diacyl peroxide particles by weight of the composition. contains. Preformed diacyl peroxides such as those described in EP257700 are also contemplated by the present invention. Also suitable are diaroyl peroxides having improved chemical stability as described in US Pat. No. 5,334,326, and solid diacyl organic peroxide dispersions disclosed in WO 96/27856.

Metal Bleach Catalyst The metal bleach catalyst contained in the detergent composition of the present composition includes a metal bleach catalyst. When the detergent compositions of the present composition contain a metal bleach catalyst, they preferably contain a peroxygen source (also referred to as an oxygen source or oxygen bleach source) as described below, together with a bleaching system. To form.

Suitable types of bleach catalysts include copper, heavy metal cations of a given bleach catalytic activity such as iron cations, auxiliary metal cations with little or no bleach catalytic activity such as zinc or aluminum cations, and catalysts and A catalyst comprising a sequestering agent having a predetermined stability constant for an auxiliary metal cation, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in US Pat. No. 4,430,243.

Preferred types of bleach catalysts include US Pat. No. 5,246,621 and US
There are manganese-based complexes disclosed in US Pat. No. 5,244,594. Preferred examples of these catalysts include Mn ^IV ₂ (u—O) ₃ (1,4,7-trimethyl-1,4,7
-Triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (u-O) ₁ (u-OA
c) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (C
10 ₄ ) ₂ , Mn ^IV ₄ (u-O) ₆ (1,4,7-triazacyclononane) ₄ (
ClO ₄ ) ₂ , Mn ^III Mn ^IV ₄ (u-O) ₁ (u-OAc) ₂ (1,4,7-
Trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₃ and mixtures thereof. Others are described in European Patent Application Publication No. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-
1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononane, 1,2,4,7-
There is tetramethyl-1,4,7-triazacyclononane and mixtures thereof. Bleach catalysts useful in the composition are also selected from suitable bleach catalysts. See US Patent 4,246,612 and US Patent 5,227,084. Mn (1, 4,
US Pat. No. 5,194,41 disclosing mononuclear manganese (IV) complexes such as 7-trimethyl-1,4,7-triazacyclononane) (OCH ₃ ) ₃ (PF ₆ ).
See also 6.

Yet another type of bleach catalyst, such as disclosed in US Pat. No. 5,114,606, comprises a ligand that is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups, It is a water-soluble complex with manganese (III) and / or (IV). Preferred ligands include sorbitol, iditol, dulcitol, mannitol, xylitol, arabitol, adonitol, mesoerythritol, mesoinositol, lactose or mixtures thereof.

US Pat. No. 5,114,611 describes other suitable bleach catalysts, which consist of complexes of transition metals including Mn, Co, Fe or Cu with non- (macro) cyclic ligands. The ligand is of the formula:

[Chemical 10] In the above formula, R ¹ , R ² , R ³ and R ⁴ are each R ¹ -N = C-R ² and R ³ -C
═N—R ⁴ may each be selected from H, substituted alkyl and aryl groups such that they form a 5- or 6-membered ring. The ring may be further substituted. B is O, S
, CR ⁵ R ⁶ , NR ⁷ and C═O, wherein R ⁵ , R ⁶ and R ⁷ are each H, an alkyl or aryl group, including a substituted or unsubstituted group. . Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, the ring is substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Particularly preferred is the ligand 2,2'-bispyridylamine. Preferred bleach catalysts include Co, Cu, Mn, Fe-bispyridylmethane and -bispyridylamine complexes. A highly preferred catalyst is Co
(2,2′-bispyridylamine) Cl ₂ , di (isothiocyanato) bispyridylamine-cobalt (II), trisdipyridylamine-cobalt (II) perchlorate, Co (2,2-bispyridylamine) ₂ O ₂ ClO ₄ , bis (2,2 '
-Bispyridylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate and mixtures thereof. Preferred examples include binuclear Mn complexes with tetra-N- and bidentate ligands such as N ₄ Mn ^III (uO) ₂ Mn ^IV N ₄ ⁺ and [Bipy ₂ Mn ^III (uO
) ₂ Mn ^IV bipy ₂ ]-(ClO ₄ ) ₃ .

Other bleach catalysts are, for example, EP 408,131 (cobalt complex catalyst), EP 384,503 and 306,089 (metallo-porphyrin catalysts), US 4,728,455 (manganese / Multidentate ligand catalyst),
US 4,711,748 and European Patent Application Publication 224,952 (manganese absorbed on aluminosilicate catalyst), US 4,601,845 (aluminosilicate carrier carrying manganese and zinc or magnesium salt), US 4,62
6,373 (manganese / ligand catalyst), US 4,119,557 (ferric complex catalyst), German Patent Specification 2,054,019 (cobalt chelant catalyst), Canada 866,191 (transition metal containing salt) and It is described in US Pat. No. 4,430,243 (chelant with manganese cations and non-catalytic metal cations). Highly preferred catalysts are described in US 4,728,455 (manganese gluconate catalyst).

Suitable examples of manganese-catalyzed organic ligands include US-A-4,728,455.
, US-A-5,114,606, US-A-5,153,161, US-A-
5,194,416, US-A-5,227,804, US-A-5,246,
612, US-A-5,246,621, US-A-5,256,779, US
-A-5,274,147, US-A-5,280,117 and EP-A-5
44,440, EP-A-544,490, EP-A-549,271, EP-
A-549,272. Preferred examples of these catalysts include Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ and Mn ^III ₂ (u- O) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ , Mn ^IV ₄ (u
-O) ₆ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₄ (
ClO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (u-O) ₁ (u-OAc) ₂ (1,4,7-
Trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₃ , Mn ^IV (
_{1,4,7-trimethyl-1,4,7-triazacyclononane) (OCH 3)} is 3 (PF _6), and mixtures thereof. Other metal-based bleach catalysts include U
There are those disclosed in S-A-4,430,243 and US-A-5,114,611.

Useful herein are iron and manganese salts of aminocarboxylic acids, including the iron and manganese aminocarboxylate salts disclosed for bleaching in photographic color processing techniques. A particularly useful transition metal salt is derived from ethylenediamine disuccinate and is a complex of this ligand with iron or manganese. Another type of bleach catalyst as disclosed in US-A-5,114,606 is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups, a ligand and a manganese (II ), (III) and / or (IV). Preferred ligands include sorbitol, iditol, dulcitol, mannitol, xylitol, arabitol, adonitol, mesoerythritol, mesoinositol, lactose and mixtures thereof. Other examples, Mn _{gluconate, Mn (CF 3 SO 3)} 2, binuclear Mn complexes with four -N- seat and secondary -N- seat ligand, for example ^{_{[bipy 2 Mn III (u-O}} )
₂ Mn ^IV bipy ₂ ]-(ClO ₄ ) ₃ .

Other bleach catalysts are, for example, EP-A-408,131 (cobalt complex),
EP-A-384,503 and EP-A-306,689 (metallo-porphyrin), US-A-4,728,455 (manganese / polydentate ligand), US-A
-4,711,748 (manganese absorbed in aluminosilicate), US-A
-4,601,845 (aluminosilicate carrier carrying manganese, zinc or magnesium salt), US-A-4,626,373 (manganese / ligand),
US-A-4,119,557 (ferric iron complex), US-A-4,430,243
(Chelant with manganese cation and non-catalytic metal cation) and US-A-
4,728,455 (manganese gluconate). Other metal-containing catalysts suitable for use in the present invention include cobalt-containing catalysts such as pentaamine cobalt (III) acetate salts, and manganese-containing catalysts such as EPA 549.
271, EPA 549272, EPA 458397, US 5,246,621,
There are those described in EPA 458398, US 5,194,416 and US 5,114,611. A bleaching composition including a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in patent application No. 94870206.3 published in EP-A-718398.

Preferred catalysts are cobalt based catalysts, WO 96/23859,
WO96 / 23860, WO96 / 23861 and US-A-5,559,2
61. WO96 / twenty-three thousand eight hundred and sixty types _[Co n _L m _{X p]} ^z y and describes cobalt catalysts of _z, where L is N, P, organic ligand containing two or more heteroatoms selected from O and S Is a molecule; X is a coordinating species; n is preferably 1 or 2; m is preferably 1-5; p is preferably 0-4; Y is a counterion. An example of such a catalyst is Nm N '
-Bis (salicylidene) ethylenediaminecobalt (II). Other cobalt catalysts described in these applications include ammonia and Co (III) complexes with mono-, di-, tri- and tetradentate ligands such as Cl ⁻ , Oac ⁻ , PF ₆ ⁻ , SO ₄ ²⁻ , BF.
₄ ^- is the anion [Co _{(NH 3)} 5 OAc] ²⁺ based. Preferred cobalt catalysts are those described in US 5,798,326 and US 5,703,030. US Pat. No. 5,798,326 describes the selection of cobalt (III) catalysts having the formula: Co [(NH ₃ ) _n M _m B _b T _t Q _q P _p ] Y _y , where cobalt is the +3 oxidized form. Is an integer of 0 to 5, preferably 4 to 5, more preferably 5; M is a monodentate ligand; m is an integer of 0 to 5, preferably 1 or 2, and more preferably 1. B is a bidentate ligand; b is an integer from 0 to 2; T is a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1 P is a pentadentate ligand; p is 0
Or 1; n + m + 2b + 3t + 4q + 5p = 6; Y is one or more appropriately selected counter anions present in the number y in order to obtain a charge balanced salt, where Y is a -1 valent anion When y is 1-3, preferably 2-3
, And more preferably an integer of 2. US 5,703,030 describes a cobalt catalyst having the formula [Co (NH ₃ ) ₅ M] T _y , where cobalt is +
3 is in the oxidation state; M is a carboxylate-containing ligand having the formula RC (O) O-; T is a number y (y is an integer) (where T is When it is a -1 valent anion, it is present in 1 to 3, more preferably 2).
It is the above counter anion.

Certain transition metal-containing bleach catalysts can be prepared in situ by reaction of the transition metal salt with a suitable chelating agent, eg, a mixture of manganese sulfate and ethylenediamine disuccinic acid. The highly colored transition metal-containing bleach catalyst may be co-treated with zeolites to reduce color impact. A preferred metal catalyst for the purposes of the present invention is the catalyst described in WO 98/39406, which comprises a complex of a transition metal and a bridged macropolycyclic ligand, (1) the metal is Mn (II), Mn (IV), Mn. (V), Fe (II), Fe (III), Fe (
IV), Co (I), Co (II), Co (III), Ni (I), Ni (II), Ni (III),
Cu (I), Cu (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); and (2) the macropolycyclic rigid ligand is selected from: (i) 4 or 5 A ligand of formula (I) having a conformation number of: (ii) a ligand of formula (II) having a conformation number of 5 or 6: (iii) a formula (III) having a conformation number of 6 or 7 ) Ligand: (E = moiety (CRn) a-X- (CRn) a '; X = O, S, NR, P or covalent bond (especially covalent bond); sum of a + a' for each E = 1-5 (Especially 2 and 3); G = (CR _n ) _b ; R = H, alkyl, alkenyl, alkynyl, aryl, alkylaryl or heteroaryl, or two or more covalently bonded,
Forming an aromatic, heteroaromatic, cycloalkyl or heterocycloalkyl ring; D = donor atom selected from N, O, S or P, at least two D
The atom is a bridgehead donor atom coordinated to the transition metal; b = C or D or a cycloalkyl or heterocyclic ring; n = one or two satisfying the valency of the C atom to which the R moiety is attached N '= 0 and 1 satisfying the valence of the D donor atom to which the R moiety is bonded; n ″ = 0 satisfying the valence of the B atom to which the R moiety is bonded,
1 or 2; a, a '= 0 to 5, preferably a, a' = 2 or 3, the sum of all a's in the formula (I) + the sum of all a's is 7 to 12, and the formula (II) A + a in
The sum of ′ is 6 (particularly 8) to 12 and the sum of all a + a ′ in the formula (III) is 8
(Especially 10) to 15 and the sum of all a + a ′ in the formula (IV) is 10 (especially 12
) -18; b = 0-9 (especially 0-5), or as long as at least two (CR _n ) _b covalently bond two of the D donor atoms to the B atom. One or more of the (CR _n ) _b moieties covalently bonded to the B atom are absent and the sum of all b is 1-5); and (iv) optionally and preferably H ₂ O, ROH, NR ₃ , RCN, OH-, O
_{OH-, RS-, RO-, OCN-,} SCN-, N 3 -, CN-, F-, Cl,
_{Br-, I-, O 2 -,} NO 3 -, NO 2 -, SO 4 2-, SO 3 2-, PO 4 3-,
Organic phosphates, organic phosphonates, organic sulphates, organic sulphonates and aromatic N donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles (R is H, optionally substituted) One or more non-macropolycyclic ligands selected from), and (b) at least 0.1% of additional components, preferably oxygen bleaches. Preferably, the donor atoms in the macropolycyclic ligand are N, S, O or P, especially N or O, and especially all are N. The ligand contains 4 or 5 donor atoms all bound to the same transition metal. The ligand contains an organic macrocycle ring having at least 12, especially 12 to 20 atoms. All a are 2 or 3, all X are covalent bonds, a'is 0 and B is 0, 1 or 2. The transition metal to ligand molar ratio is 1: 1 and the transition metal is Mn or Fe.

A more preferred catalyst consisting of such a complex of a transition metal and a bridged macropolycyclic ligand is [Mn (Biciclam) Cl ₂ ]:

[Chemical 11] "Bisicrum" (5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane) is prepared according to J. Amer. Chem. Soc., (1990), 112, 8604. . Bicyclam (1.00 g, 3.93 mmol) was added to dry CH ₃ CN (35 ml).
, CaH ₂ distilled). Add 1 solution until CH ₃ CN begins to boil.
Exhaust at 5 mm. The flask is then brought back to atmospheric pressure with Ar. This degassing operation is repeated 4 times. Mn synthesized according to the literature procedure of J. Inorg. Nucl. Chem., (1974), 36, 1535.
(Pyridine) ₂ Cl ₂ (1.12 g, 3.93 mmol) is added under Ar and the mixture is stirred at room temperature overnight. Filter the reaction through a 0.2μ filter. The filtrate is evaporated. 1.35 g of product are collected with a yield of 90%.

Bleach catalysts are typically used in the compositions and processes in catalytically effective amounts. By "catalytically effective amount" is meant a sufficient amount, regardless of any comparative test conditions used, to improve the bleachability and removability of the stain of interest from the target substrate. Test conditions will vary depending on the type of cleaning equipment used and user habits. Some users choose to use very hot water,
Others use warm water, or even cold water, for washing operations. Of course, the catalytic performance of the bleach catalyst is affected by such considerations, and the level of bleach catalyst used in the fully formulated detergent, the bleach composition can be adjusted accordingly. As a practical matter,
Without limitation, the present compositions and processes allow at least 0.1 p in aqueous cleaning solutions.
It is adjusted to provide about pm of active bleach catalyst species, preferably about 1 to about 200 ppm catalyst species in the wash liquor. To further explain this point,
With a manganese catalyst of the order of μM, it is effective at 40 ° C. and pH 10 under European conditions using perborate and peroxyacid bleach precursors. 3 in concentration
A ~ 5-fold increase may be required under US-style conditions to obtain similar results. Therefore, the metal bleach catalyst is present in the detergent composition of the present invention at a level of from 1 ppb to 10%, preferably from about 0.1 ppm to about 1%, most preferably from about 1 ppm to about 0.1% by weight of the composition. Normally contained in.

Further preferred metal bleach catalysts for the detergent compositions of the present invention are US Pat. No. 5,798.
Cobalt catalyst Co [(NH ₃ ) _n M _m B _b T _t Q _q P _p ].
Y _y (see above); Cobalt catalyst described in US 5,703,030 [Co (
NH _{3) 5} M] _{T y} (supra) which is a made of a transition metal and a cross-linking atmospheric polycyclic ligand catalyst [Mn (bicyclam) Cl _2] and / or mixtures thereof.

Bleach Booster A third bleach system that may be selected for the detergent compositions of the present invention comprises a dipolar imine, an anionic imine polyion having a net negative charge of about -1 to about -3, and mixtures thereof. It is a combination of a bleach booster and a source of peroxygen.

[0059]   Suitable imine bleach boosters of the present invention include those of the following general structure:

[Chemical 12] In the above formula, R ¹ -R ⁴ may be hydrogen, phenyl, aryl, heterocyclic ring,
It may be an unsubstituted or a substituent selected from the group consisting of alkyl and cycloalkyl groups, provided that at least ^{one of} R ¹ -R ⁴ contains a negatively charged moiety.

A preferred bleach booster of the present invention comprises a negatively charged moiety attached to the imine nitrogen and has the formula:

[Chemical 13] In the above formula: R ¹ -R ³ is a moiety having a total charge of about 0 to about -1; R ¹ -R ³ is also hydrogen, or from a phenyl, aryl, heterocyclic ring, alkyl and cycloalkyl group. It may be an unsubstituted or a substituent selected from the group consisting of: T is-(CH ₂ ) _b- (b is from about 1 to about 8),-(CH (R ⁵ ))-(R ⁵ is C ₁ -C ₈ alkyl), -CH ₂ (C ₆ H ₄ )-,

[Chemical 14] And _{- (CH 2) d (E} ) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is -C (O) O -, - C (O) NR 6 Or

[Chemical 15] R ⁶ is H or C ₁ -C ₄ alkyl); Z is covalently bonded to T and is —CO ₂ ^— , —SO ₃ ^— and —OSO ₃ ^— Is selected from the group consisting of and a is at least 1. Thus, when Z is covalently bonded to T (when the total charge of R ¹ -R ³ is zero), the imine is a dipolar ion when a is 1 or a net negative when a is greater than 1. It is a charged polyion. Preferably, a is 1 or 2 and the bleach booster is a zwitterion or polyion with a net charge of -1.

In a more preferred embodiment, the bleach booster of the present invention is an aryliminium zwitterion, an aryliminium polyion with a net negative charge of about -1 to about -3, or mixtures thereof. In this preferred embodiment, R ¹ and R ² together form part of a common ring. In particular, R ¹ and R ² may together form one or more 5-, 6- or 7-membered rings. The most preferred aryliminium is formed from the following uncharged moieties:

[Chemical 16]

Thus, in the preferred aryliminium zwitterion, R ¹ and R ² together form the uncharged moiety (III), and T is — (CH ₂ ) _b — (b is about 1). Is about 6),-(CH (R ⁵ ))-(R ⁵ is methyl) and -C
Selected from the group consisting of H ₂ (C ₆ H ₄ )-, a is 1 and Z is selected from —CO ₂ ^— and —SO ₃ ^— . More preferably, in the aryliminium zwitterion of the present invention, R ¹ and R ² together form an uncharged moiety (III) and T is — (CH ₂ ) _b — or —CH _{2 (C} 6 _{H 4)} - a and, a is 1, Z is -SO ₃ ^- is, b is 2-4. The most preferred aryliminium zwitterion according to the present invention has the formula:

[Chemical 17] 3- (3,4-dihydroisoquinolinium) propanesulfonate, 4- (
3,4-dihydroisoquinolinium) butane sulfonate.

In a preferred aryliminium polyion according to the invention, R ¹ and R ² together form an uncharged moiety (III) and T is:

[Chemical 18] And _{- (CH 2) d (E} ) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is

[Chemical 19] , A is at least 2 and Z is selected from —CO ₂ ^— and —SO ₃ ^— . More preferably, in the aryliminium polyion of the invention, R ¹ and R ² together form an uncharged moiety (III) and T is:

[Chemical 20] And _{- (CH 2) d (E} ) (CH 2) f - (d is 2 to 6, f is 1, E is

[Chemical 21] , A is 2, and Z is —SO ₃ ^— . The most preferred polyions according to the present invention have the formula:

[Chemical formula 22]

Another suitable imine bleach booster of the present invention consists of a quaternary imine zwitterion of the formula:

[Chemical formula 23] In the above formula: R ¹ -R ³ may be hydrogen or an unsubstituted or substituted group selected from the group consisting of phenyl, aryl, heterocyclic ring, alkyl and cycloalkyl groups; T is:

[Chemical formula 24] In the above formula, x is 0 or 1; J is -CR ¹¹ R ¹² , -C when present.
R ¹¹ R ¹² CR ¹³ R ¹⁴ and -CR ¹¹ R ¹² CR ¹³ R ¹⁴ CR ¹⁵ R ¹⁶ are selected from the group consisting of; R ⁷ -R ¹⁶ are independently H, straight chain or branched C ₁ -C ₁₈ Selected from the group consisting of substituted or unsubstituted alkyl, alkylene, oxyalkylene, aryl, substituted aryl, substituted arylcarbonyl groups, and amido groups; provided that at least one of R ⁷ -R ⁸ is H or methyl. And one of R ⁷ -R ⁸ must be H when neither R ⁹ nor R ¹⁰ is H. Preferably, at least one of R ⁹ and R ¹⁰ must also be H. C _b and C _d are carbon atoms; Z is covalently bonded to J _x when x is 1 and to C _b when x is 0, —CO ₂ ^— , —SO ₂ ^— , — _{^{PO 3 -, -OPO 3 -,}} -SO 3 - and -O
Although selected from the group consisting of SO ₃ ⁻ , —OSO ₃ ⁻ is preferable and a is 1. Therefore, (when the total charge of the R ¹ -R ³ is zero) if Z is a covalent bond, quaternary imine is zwitterionic.

In a further preferred embodiment, the bleach booster of the present invention is an aryliminium zwitterion. In this preferred embodiment, R ¹ and R ² together form part of a common ring. In particular, R ¹ and R ² may together form one or more 5-, 6- or 7-membered rings. The most preferred aryliminium is formed from the following uncharged moieties:

[Chemical 25]

Thus, in a preferred aryliminium zwitterion, R ¹ and R ² are taken together to form the uncharged moiety (III) and T is

[Chemical formula 26] , A is 1 and Z is selected from —OSO ₃ ^— and —SO ₃ ^— . More preferably, in the aryliminium zwitterion of the present invention, R ¹ and R ² together form an uncharged moiety (III) and T is

[Chemical 27] , A is 1 and Z is —OSO ₃ ^— . The most preferred aryliminium zwitterion according to the present invention has the formula:

[Chemical 28] In the above formula, R ¹⁷ is H, linear or branched C ₁ -C ₁₈ substituted or unsubstituted alkyl,
Preferably it is selected from the group consisting of C ₁ -C ₁₄ alkyl, more preferably C ₈ -C ₁₀ straight chain alkyl.

Such a bleach booster was released on August 30, 1996 by The Procter &
The method described in co-pending international application WO 97/10323 filed by Gamble company, in particular Example I-III, and / or co-pending international application WO 98 / filed by Procter & Gamble on August 28, 1997 It can be prepared according to the method described in 16614, in particular Examples I-VIII.

The bleach booster of the present invention is used in combination with a peroxygen source in a bleaching composition. The source of peroxygen is 0.1-60% by weight of the composition, preferably 1% of the composition.
Levels of -40% by weight are usually present in the detergent compositions of the present invention. The bleach booster is 0.01 to 10% by weight of the composition, more preferably 0.05 to 10% of the composition.
Levels of 5% by weight are usually present in the detergent compositions of the invention.

The imine bleach booster of the present invention works in concert with a peroxygen source in improving bleaching effectiveness. The bleach booster reacts with a source of peroxygen to form the more active bleaching species, the oxaziridinium compound. The oxaziridinium compound formed is a zwitterion or polyion with a net negative charge, as in the case of imine bleach boosters. Oxaziridinium compounds have improved activity at low temperatures compared to peroxygen compounds. Oxaziridinium compounds are represented by the formula:

[Chemical 29] The imine of the present invention is produced according to the following reaction:

[Chemical 30] Thus, a preferred bleach booster of the present invention of formula (IV) yields an active oxaziridinium bleaching species of formula:

[Chemical 31] Peroxygen Sources Peroxygen sources are well known in the art, and the peroxygen sources used in the present invention may be any of these well known sources, including peroxygen compounds, and effective amounts of peroxygen under consumer use conditions. There are compounds that generate in situ. Peroxygen sources include hydrogen peroxide sources, in situ formation of peracid anions from the reaction of hydrogen peroxide sources and bleach activators, preformed peracid compounds or mixtures of suitable peroxygen sources. Such peroxygen sources include, for example, inorganic perhydrate bleach or organic peroxy acids. In a preferred embodiment, the bleaching system contains a hydrogen peroxide source and a peroxyacid bleach precursor compound.
The production of peroxyacids occurs by the in situ reaction of the precursor with a source of hydrogen peroxide. A preferred source of hydrogen peroxide is inorganic perhydrate bleach. Of course, those skilled in the art will appreciate that other sources of peroxygen may be used without departing from the scope of the invention.

A preformed peracid compound as used herein is any convenient compound that provides an effective amount of peracid anion under consumer use conditions. Suitable non-limiting examples include percarboxylic acids and salts, percarbonates and salts, perimidic acids and salts, peroxymonosulfates and salts, and mixtures thereof. Suitable examples of percarboxylic acids and salts include magnesium monoperoxyphthalate hexahydrate, m-chloroperbenzoic acid,
There is a magnesium salt of 4-nonylamino-4-oxoperoxybutyric acid and diperoxidedecanedioic acid. Such bleaching agents are described in US Pat. No. 4,483,781 to Hartman, US Pat. No. 4,634 to Burns et al. Issued Nov. 20, 1984.
, 551, European patent application 0,1 of Banks et al., Published Feb. 20, 1985.
33,354, and Chung et al., US Pat. No. 4,412,934, issued Nov. 1, 1983. Its source also includes 6-nonylamino-6-oxoperoxycaproic acid as described in Burns et al., US Pat. No. 4,634,551 issued Jan. 6, 1987. EIDu Pont de Ne
Persulfate compounds such as OXONE available from mours of Wilmington, DE can also be used as a suitable source of peroxymonosulfate.

A hydrogen peroxide source as used herein is any convenient compound or mixture that provides an effective amount of hydrogen peroxide under conditions of consumer use. Levels will generally vary, typically from about 0.1 to about 60% by weight of the present bleaching composition, and more typically from about 1 to about 40%. The hydrogen peroxide source used herein can be any convenient source, including the hydrogen peroxide itself. For example, perborate,
Sodium perborate (any hydrate, preferably mono- or tetrahydrate),
Sodium carbonate peroxyhydrate or the corresponding percarbonate salt, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate or sodium peroxide may be used here. Mixtures of any convenient hydrogen peroxide sources may also be used.

Inorganic Perhydrate Bleach Inorganic perhydrate salts are the preferred source of hydrogen peroxide. These salts, in the form of sodium salts, are 1 to 95% by weight of the bleaching composition, more preferably 10 to 90% by weight.
, Most preferably at a level of 20-80% by weight. When incorporated into a bleaching composition for inclusion in a detergent composition according to the present invention, the inorganic perhydrate salt is preferably 1-40% by weight of the detergent composition, more preferably 2-30% by weight, most preferably 5-25% by weight. Exists at the% level. Examples of inorganic perhydrate salts are perborate, perphosphate, persulfate and persilicate salts. Preferred inorganic perhydrate salts are alkali or alkaline earth metal percarbonate salts. Sodium percarbonate is a preferred percarbonate salt for inclusion in the bleach composition according to the present invention, which is an addition compound having a formula corresponding to 2Na ₂ CO ₃ .3H ₂ O ₂ and is commercially available as a crystalline solid. ing. Most preferably, the percarbonate is incorporated into such compositions in a coated form which provides product stability. The preferred percarbonate bleach is from about 500 to about 1.
Consisting of dry particles having an average particle size in the range of 000 μm, wherein less than about 10% by weight of the particles are less than about 200 μm and less than about 10% by weight of the particles are about 12
Greater than 50 μm. Optionally, the percarbonate can be coated with silicates, borates or water-soluble surfactants. Percarbonate is FMC,
It is available from various commercial sources such as Solvay and Tokai Denka. Sodium perborate can take the form of monohydrate or tetrahydrate NaBO ₂ H ₂ O ₂ .3H ₂ O of formula NaBO ₂ H ₂ O ₂ . The inorganic perhydrate salt is usually an alkali metal salt. The inorganic perhydrate salt may be included as a crystalline solid without additional protection. However, for some perhydrate salts, the preferred practice of such a granular composition utilizes a coated form of the material that provides the granulated product with good storage stability of the perhydrate salt. Suitable coating materials which exhibit product stability include mixed salts of water soluble alkali metal sulfates and carbonates. Such a coating, along with the coating process, was approved by Interox on March 9, 1977 GB1,
466,799. The weight ratio of mixed salt coating material to percarbonate ranges from 1: 200 to 1: 4, more preferably 1:99 to 1: 9, most preferably 1:49 to 1:19. Preferably, the mixed salt has the general formula N
consists sodium sulfate and sodium carbonate having _{a 2 SO 4 · nNa 2 CO} 3, where n is 0.1 to 3, preferably n is from 0.3 to 1.0, and most preferably n is It is 0.2 to 0.5. Other coatings, including silicates (alone or with borate salts, boric acid or other inorganics), waxes, oils, fatty soaps may also be used to advantage within the invention. Potassium peroxymonopersulfate is another inorganic perhydrate salt useful in the present detergent composition.

Peroxy Acid Bleach Precursor Compound The peroxy acid bleach precursor is preferably incorporated at a level of from 1 to 50% by weight of the bleaching composition, more preferably from 2 to 30% by weight, most preferably from 5 to 20% by weight. It When incorporated into a bleaching composition for inclusion in a detergent composition according to the present invention, the peroxyacid bleach precursor is preferably 0.5-20% by weight of the detergent composition, more preferably 1-15% by weight, most preferably Is present at a level of 1.5 to 10% by weight. Suitable peroxyacid bleach precursors typically have one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides, and acylated derivatives of imidazoles and oximes. Examples of useful substances belonging to these classes are GB-
It is disclosed in A-1586789. Suitable esters are GB-A-83698
8, 864798, 1147871, 2143231 and EP-A-0170.
386.

N-Acylated Lactam Precursor Compounds A lactam class of N-acylated precursor compounds is generally disclosed in GB-A-855735. Although the broadest aspect of this invention contemplates the use of any lactam useful as a peroxyacid precursor, preferred materials include caprolactams and valerolactams. Suitable N-acylated lactam precursors have the formula:

[Chemical 32] Where n is 0 to about 8, preferably 0 to 2, R ⁶ is H, an alkyl, aryl, alkoxyaryl or alkaryl group having 1 to 12 carbons, or 6 to 18 carbon atoms. It is a substituted phenyl group. Suitable caprolactam bleach precursors are of the formula:

[Chemical 33] In the above formula, R ¹ is H or alkyl having 1 to 12 carbon atoms, aryl,
It is an alkoxyaryl or alkaryl group, most preferably R ¹ is phenyl. Suitable valerolactams have the formula:

[Chemical 34] In the above formula, R ¹ is H or an alkyl, aryl, alkoxyaryl or alkaryl group having 1 to 12 carbon atoms, preferably 6 to 12 carbon atoms. In a highly preferred embodiment R ¹ is selected from phenyl, heptyl, octyl, nonyl, 2,4,4-trimethylpentyl, decenyl and mixtures thereof. Most preferred materials are those that are normally solid at <30 ° C, especially phenyl derivatives,
Benzoyl valerolactam, benzoyl caprolactam and their substituted benzoyl analogues such as chloro, aminoalkyl, alkyl, aryl and alkoxy derivatives. Caprolactam and valerolactam precursor materials in which the R ¹ moiety has at least 6, preferably 6-12, carbon atoms provide a peroxyacid in a hydrophobic perhydrolysis that is capable of nucleophilic and soil cleanup. Precursor compounds where R ¹ has ¹ to 6 carbon atoms provide a hydrophilic bleaching species that is particularly effective in bleaching beverage stains. A mixture of'hydrophobic 'and'hydrophilic' caprolactams and valerolactams, typically in a weight ratio of 1: 5 to 5: 1, preferably 1: 1,
May be used here for mixed stain removal effect.

Highly preferred caprolactam and valerolactam precursors include benzoylcaprolactam, nonanoylcaprolactam, benzoylvalerolactam, nonanoylvalerolactam, 3,5,5-trimethylhexanoylcaprolactam,
3,5,5-Trimethylhexanoylvalerolactam, octanoylcaprolactam, octanoylvalerolactam, decanoylcaprolactam, decanoylvalerolactam, undecenoylcaprolactam, undecenoylvalerolactam, (6-octanamidecaproyl) oxy There are benzene sulfonates, (6-nonanamidocaproyl) oxybenzene sulfonates, (6-decanamidocaproyl) oxybenzene sulfonates and mixtures thereof. Examples of highly preferred substituted benzoyllactams are methylbenzoylcaprolactam, methylbenzoylvalerolactam, ethylbenzoylcaprolactam, ethylbenzoylvalerolactam, propylbenzoylcaprolactam, propylbenzoylvalerolactam, isopropylbenzoylcaprolactam, isopropylbenzoylvalerolactam, butylbenzoylcaprolactam. Butylbenzoylvalerolactam, tert-butylbenzoylcaprolactam, tert-butylbenzoylvalerolactam, pentylbenzoylcaprolactam, pentylbenzoylvalerolactam, hexylbenzoylcaprolactam, hexylbenzoylvalerolactam, ethoxybenzoylcaprolactam, ethoxybenzoylvalerolactam,
Propoxybenzoylcaprolactam, propoxybenzoylvalerolactam,
Isopropoxybenzoylcaprolactam, isopropoxybenzoylvalerolactam, butoxybenzoylcaprolactam, butoxybenzoylvalerolactam, tert-butoxybenzoylcaprolactam, tert-butoxybenzoylvalerolactam, pentoxybenzoylcaprolactam, pentoxybenzoylvalerolactam, hexoxybenzoyl Hexoxybenzoylvalerolactam, 2,4,6-trichlorobenzoylvalerolactam, pentafluorobenzoylcaprolactam, pentafluorobenzoylvalerolactam, dichlorobenzoylcaprolactam, dimethoxybenzoylcaprolactam, 4-chlorobenzoylcaprolactam, 2,4-dichlorobenzoylcaprolactam , Terephthaloyl dicaprola Cutam, pentafluorobenzoylcaprolactam, pentafluorobenzoylvalerolactam, dichlorobenzoylvalerolactam,
Dimethoxybenzoylvalerolactam, 4-chlorobenzoylvalerolactam,
There are 2,4-dichlorobenzoylvalerolactam, terephthaloyldivalerolactam, 4-nitrobenzoylcaprolactam, 4-nitrobenzoylvalerolactam and mixtures thereof.

Perbenzoic Acid Precursors Essentially any perbenzoic acid precursor is suitable here, including those of the preferred N-acylated lactam class. Suitable O-acylated perbenzoic acid precursor compounds include substituted and unsubstituted benzoyloxybenzene sulfonates, including, for example, benzoyloxybenzene sulfonate:

[Chemical 35] Benzoylation products of sorbitol, glucose and all sugars with benzoylating agents are also suitable, including, for example:

[Chemical 36] Preferred perbenzoic acid precursor compounds of the Ac = COCH ₃ ; Bz = benzoyl imide type include N-benzoylsuccinimide, tetrabenzoylethylenediamine and N-benzoyl substituted urea. Suitable imidazole-type perbenzoic acid precursors include N-benzoylimidazole and N-benzoylbenzimidazole, and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoylpyrrolidone, dibenzoyltaurine and benzoyl. There is pyroglutamic acid. Preferred perbenzoic acid precursors include benzoyl diacyl peroxide, benzoyl tetraacyl peroxide and compounds having the formula:

[Chemical 37] The following phthalic anhydrides are another suitable perbenzoic acid precursor compound here:

[Chemical 38]

Perbenzoic Acid Derivative Precursors Suitable perbenzoic acid derivative precursors include any of the perbenzoic acid precursors disclosed herein wherein the perbenzoyl group is substituted with essentially any functional group including alkyl groups. Including the body.

Cationic Peroxy Acid Precursor Cationic peroxy acid precursor compounds are also suitable here. Typically, such cationic peroxyacid precursors are formed by replacing the peroxyacid moieties with ammonium or alkylammonium groups, preferably ethyl or methylammonium groups. Cationic peroxy acid precursors are described in US Pat. No. 4,904,406, 4,751.
, 015, 4,988, 451, 4,397, 757, 5,269, 962, 5
, 127,852, 5,093,022, 5,106,528, UK1,382
, 594, EP 475, 512, 458, 396 and 284, 292, and JP 87-318, 332. Examples of preferred cationic peroxy acid precursors are described in UK patent application 9407944.
． 9 and US patent applications 08/298903, 08/298650, 08/29
8904 and 08/298906. Suitable cationic peroxyacid precursors include ammonium or alkylammonium substituted alkyl or benzoyloxybenzene sulfonates, N-acylated caprolactams, and monobenzoyl tetraacetyl glucose benzoyl peroxide. A preferred cationically substituted benzoyloxybenzene sulfonate is the 4- (trimethylammonium) methyl derivative of benzoyloxybenzene sulfonate:

[Chemical Formula 39] Preferred cationically substituted alkyloxybenzene sulfonates are 2,3,3
-A methyl ammonium derivative of trimethylhexanoyloxybenzene sulfonate. Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include trialkylammonium methylenebenzoylcaprolactams, especially the following trimethylammoniummethylenebenzoylcaprolactams:

[Chemical 40] Another preferred cationic peroxy acid precursor is 2- (N, N, N-trimethylammonium) ethyl sodium 4-sulfophenylcarbonate chloride.

Alkyl Fat Peroxy Acid Bleach Precursor The alkyl fatty peroxy acid bleach precursor forms an alkyl fatty peroxy acid by perhydrolysis. A preferred precursor of this type produces peracetic acid upon perhydrolysis. Preferred imide-type alkyl fatty peroxy acid precursor compounds include N, N, N ', N'-tetraacetylated alkylenediamines in which the alkylene group has 1 to 6 carbon atoms, especially 1,2 and There are compounds with 6 carbon atoms. Tetraacetylethylenediamine (TAED) is particularly preferred.

Amide-Substituted Peroxy Acid Bleach Activator Another preferred class of peroxy acid bleach activator compounds is:
Is an amide-substituted compound of the general formula:

[Chemical 41] Wherein R ¹ is an alkyl or aryl group having ¹ to 14 carbon atoms,
R ² is an alkylene, arylene and alkaryl group having 1 to 14 carbon atoms, R ⁵ is H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms and L is essentially any It may be a leaving group. R ¹ preferably has 6 to 12 carbon atoms. R ² preferably has 4 to 8 carbon atoms. R ¹ is linear or branched alkyl, substituted aryl, or branched,
Alkylaryl, substituted or both, may be derived from either synthetic or natural sources including, for example, tallow. Similar structural variations are also allowed for R ² . Substitutions include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituents or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ should not have a total of more than 18 carbon atoms. In the case of an analog having R ¹ as an aryl or alkaryl group, L is selected from any of the above leaving groups. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386. The L group must be sufficiently reactive that the reaction occurs within an optimal time frame (eg, wash cycle). However, if L is too reactive, this activator is difficult to stabilize for use in bleaching compositions. These features usually correspond to the pKa of the leaving group's conjugate acid, although exceptions to this convention are known. Usually, leaving groups exhibiting such behavior are those whose conjugate acid has a pKa in the range 4 to 13, preferably 6 to 11, most preferably 8 to 11. Preferred bleach precursors are those in which R ¹ , R ² and R ⁵ are as defined for the amide substituted compound and L is selected from the group consisting of:

[Chemical 42] In the above formula, R ¹ is an alkyl, aryl or alkaryl group having ¹ to 14 carbon atoms, R ³ is an alkyl chain having 1 to 8 carbon atoms, R ⁴ is H or R ³ , Y is H or a solubilizing group. Preferred dissolution groups _{^{-SO 3 - M +, -CO 2}} - M +, -SO 4 - M +, -N + (R 3) 4 X - and _{^{O ← N (R 3) 3}} , and most preferably -SO ₃ ^- M ⁺ and _-CO ² - a ^{M +,} where ^{R 3} is an alkyl chain having 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator, X is Bleach It is an anion that imparts solubility to the activator. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, sodium and potassium are most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion. It should be noted that bleach activators with leaving groups that do not contain solubilizing groups must be well dispersed in the bleaching solution to aid their dissolution.

Organic Peroxy Acids The composition is used as a bleaching component, typically 2 to 30% by weight of the bleaching composition,
More preferably, the organic peroxy acid may be contained at a level of 5 to 20% by weight.
When the bleaching composition is contained in the detergent composition according to the invention, the organic peroxyacid is preferably present at a level of 1 to 15% by weight of the detergent composition, more preferably 1 to 10% by weight. A preferred class of organic peroxyacid compounds are the amide-substituted compounds of the general formula:

[Chemical 43] In the above formula, R ¹ is an alkyl, aryl or alkaryl group having ¹ to 14 carbon atoms, R ² is an alkylene, arylene or alkaryl group having 1 to 14 carbon atoms, and R ⁵ is H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms. R ¹ preferably has 6 to 12 carbon atoms. R ² preferably has 4 to 8 carbon atoms. R ¹ may be linear or branched alkyl, substituted aryl or alkylaryl, including branched, substituted or both, and may be derived from synthetic or natural sources including, for example, tallow. Similar structural variations are also allowed for R ² . Substitutions include alkyl, aryl, halogen, nitrogen, sulfur and other typical substituents or organic compounds. R ⁵ is preferably H or methyl. R ¹ and R ⁵ should not have more than 18 carbon atoms in total. This type of amide substituted organic peroxyacid compound is described in EP-A-0170386. Other organic peroxyacids include diperoxide decanedioic acid, diperoxytetradecanedioic acid and diperoxyhexadecanedioic acid, mono and diperazelaic acid, mono and diperbrassic acid.

Nonanoyloxybenzene sulfonate (NOBS, US 4,412,934
Are also suitable). Useful bleaching agents, including bleaching systems consisting of bleach activators and peroxygen bleaching compounds, and peroxyacids for detergent compositions according to the invention are described in our co-pending application USSN 08 / 136,626, PC.
T / US95 / 07823, WO95 / 27772, WO95 / 27773, W
O95 / 27774 and WO95 / 27775. Hydrogen peroxide may also be present at the beginning or during the washing and / or rinsing process with the addition of an enzymatic system (ie enzyme and its substrate) capable of generating hydrogen peroxide. Such an enzyme system is disclosed in EP patent application 91202655.6, filed October 9, 1991.

Detergent Ingredients The detergent composition of the present invention preferably further comprises additional detergent ingredients. The nature of these additional components, and their level of incorporation, depends on the physical form of the composition and the nature of the cleaning operation in which it is used. Detergent compositions according to the invention include liquids, pastes, gels, bars, tablets, sprays, foams, powders or granules. The granular composition may be in "compact" form and the liquid composition may be in "concentrated" form. The tablet composition may be in single phase or multiphase form.

It was surprisingly found that the cleaning effect of the pectate lyase enzyme can be optimized and maximized with time-controlled release technology. In particular, the time-controlled technique is a tablet in which the pectate lyase is kept separate from other detergent ingredients that can inhibit / inactivate in different product phases with different solubilities in the wash liquor. It was surprisingly found that the best performance potency of the pectate lyase enzyme was obtained when the enzyme was incorporated into tablets and such a system exerted a significant stain and stain cleaning effect. It has further been found that such time-controlled release technology allows the use of a wide range of pectate lyases, including those that exhibit a high degree of instability in standard detergent matrices. In practice, the pectate lyase and the buffer substance are preferably incorporated into the immediate dissolution portion of the tablet. Without being bound by theory, pectate lyase is released faster than other detergent components that can inhibit / inactivate, and the best pectate lyase activity is obtained under buffer conditions at the start of washing and available pectin. It is believed that pectic acid lyase can be formulated into detergents over the entire range of acid lyases.

Suitable tablets are detergents that are not only robust enough to withstand handling and shipping, but at least some of them dissolve rapidly in the wash water, releasing the pectate lyase enzyme rapidly. It is a tablet. At least one phase of the tablet comprises 10 minutes, preferably 5 minutes, more preferably 4 minutes in the beginning of the automatic dishwashing or washing machine washing cycle.
It is preferably dissolved in the washing water within a minute. Preferably, the washer is an automatic dishwashing or washing machine. The multi-phase tablet, its one phase or the detergent active ingredient is allowed to dissolve at least 6 times or a sufficient number of times to ensure reproducibility and a Bosch dishwasher with a standard 65 ° C washing program with a water hardness of 18 ° H. With DIN 44990.

As a first aspect, the present invention relates to laundry detergent compositions containing a pectate lyase and a selected bleach system (Examples 1-16). In a second aspect, the present invention relates to dishwashing detergent compositions containing a pectate lyase, a source of peroxygen and a bleach booster (Examples 17-27). The bleaching composition of the present invention is for washing, hard surface cleaning, automatic dish washing,
And for cosmetics, for example on dentures, teeth, hair and skin. However, due to the unique advantages of both improved effectiveness in cold solutions and excellent color safety profiles, the bleach boosters of the present invention are suitable for laundry such as bleaching of fabrics by the use of bleach-containing detergents or laundry bleach additives. Ideally suited for. Further, the bleach boosters of the present invention find use in both granular and liquid compositions. The compositions of the present invention include, for example, hand dishwashing compositions, hand and machine laundry detergent compositions,
For example, it is formulated as a laundry additive composition, and a composition suitable for dipping and / or pretreatment of soiled fabrics, and for general household hard surface cleaning operations. When formulated as a composition for hand dish washing, the composition of the present invention preferably comprises a surfactant, preferably an organic polymeric compound, a foam booster, a Group II metal ion, a solvent, a hydrotrope and an additional enzyme. And other detergent compounds selected from. When formulated as a composition suitable for machine wash methods, the composition of the present invention comprises:
Preferably both surfactants and builder compounds, preferably organic polymer compounds, bleaches, additional enzymes, foam inhibitors, dispersants, lime soap dispersants, soil suspension and anti-redeposition agents, and corrosion inhibitors. It further contains one or more detergent ingredients selected from the agents. The laundry composition may also contain softeners as additional detergent ingredients. Such a composition containing a pectate lyase, a source of peroxygen and a bleach booster, when formulated as a laundry detergent composition, can provide fabric cleaning, stain removal and color appearance. When formulated as a composition suitable for machine dishwashing, the composition of the present invention comprises:
Preferably, a low foaming nonionic surfactant, a builder system, and preferably an organic polymer compound, a bleaching agent, an additional enzyme, a foaming inhibitor, a dispersant, a lime soap dispersant,
It contains one or more ingredients selected from soil suspension and anti-redeposition agents, and corrosion inhibitors. The composition of the present invention may be used as a detergent additive product in solid or liquid form.
Such additive products are present to enhance or enhance the performance of conventional detergent compositions and may be added at any stage of the cleaning process.

If required, the density of the present laundry detergent composition is 4 at the composition measured at 20 ° C.
It is from 00 to 1200 g / L, preferably from 500 to 950 g / L. The "compact" form of the composition is best reflected in terms of density, and compositionally, the amount of inorganic filler salt; the inorganic filler salt is a conventional component of detergent compositions in powder form; conventional detergent compositions. In the composition, the filler salt is present in substantial amounts, typically 17-35% by weight of the total composition. In compact compositions, the filler salt is present in an amount of not more than 15% by weight of the total composition, preferably not more than 10% of the composition, most preferably not more than 5%. The inorganic filler salt as meant in the present composition is selected from the alkali and alkaline earth metal salts of sulphates and chlorides. The 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%. Detergent compounds suitable for use herein are selected from the group consisting of the following compounds:

Surfactant System Preferably, the detergent composition of the present invention comprises a surfactant system wherein the surfactant can be selected from cationic, nonionic and / or conventional anionic and / or mixtures thereof. Contains. Amphoteric and / or dipolar and / or semipolar surfactants are also suitable. Surfactant systems are typically present at levels of 0.1-60% by weight. A more preferred compounding level is 1-35% by weight of the laundry detergent composition according to the present invention, most preferably 1-30% by weight. The surfactant is preferably formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions, the surfactant is most preferably formulated to promote or at least not degrade the stability of the enzyme in these compositions.

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 alkylene oxides with alkylphenols having an alkyl group of about 6 to about 14 carbon atoms, preferably about 8 to about 14 carbon atoms in a linear or branched configuration. In a preferred embodiment, ethylene oxide is present in an amount corresponding to about 2 to about 25 moles, and 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
There are Igepal ^™ CO-630 sold by poration, Triton ^™ X-45, X-114, X-100 and X-102 all sold by Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (eg alkylphenol ethoxylates).

Condensation products of primary and secondary aliphatic alcohols with about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant in the nonionic surfactant system of the present invention. The alkyl chains of the aliphatic alcohols are straight or branched, primary or secondary and usually have from about 8 to about 22 carbon atoms. About 8 to about 20 carbon atoms
And 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. About 2 to about 7 moles of ethylene oxide per mole of alcohol, most preferably 2 to 5 moles of ethylene oxide are present in the above condensation product. Examples of commercially available nonionic surfactants of this type are both Union Carbide Corporation
Tergitol ^TM 15-S-9 (condensation product of C ₁₁ -C ₁₅ straight chain alcohol and 9 moles of ethylene oxide), Tergitol ^TM 24-L-6 NMW (C ₁₂ -C ₁₄ primary alcohol and ethylene oxide 6 sold by Condensation product of narrow molecular weight distribution with mol); Shel
l Chemical Company Neodol sold by ^TM 45-9 _(C 14 _{-C 15} condensation product of linear alcohol with 9 moles ethylene _{^{oxide), Neodol TM 23-3 (C 12}} -C 1 3 linear alcohols with ethylene oxide 3 Condensation product with 0.0 mol), Neodol ^TM 45-7
(Condensation product of C ₁₄ -C ₁₅ straight chain alcohol and 7 mol of ethylene oxide), Ne
odol ^TM 45-5 _(C 14 _{-C 15} linear alcohol with condensation product of 5 moles of ethylene oxide); The Procter & Gamble Company, sold by _{^{Kyro TM EOB (C 1 3 -C}} 15 alcohol with 9 moles ethylene oxide and Condensation product of Genapol LA O3O or O50 (condensation product of C ₁₂ -C ₁₄ alcohol and 3 or 5 mol of ethylene oxide) sold by Hoechst. HLB in these products
Is preferably 8 to 11, and most preferably 8 to 10.

As the nonionic surfactant of the surfactant system of the present invention, a hydrophobic group having about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and about 1.3 to about 10 are included. ,
Llenado, issued Jan. 21, 1986, preferably with a polysaccharide having a sugar unit of about 1.3 to about 3, most preferably about 1.3 to about 2.7, eg a hydrophilic group of a polyglycoside. The alkyl polysaccharides disclosed in U.S. Pat. No. 4,565,647 are also useful. Reducing sugars having 5 or 6 carbon atoms may also be used, eg glucose, galactose and galactosyl moieties may be used in place of the glucosyl moiety (optionally a hydrophobic group attached at the 2, 3, 4 position etc.). , Yields glucose or galactose rather than glucoside or galactoside). For example, there may be an intersugar linkage between one position of the additional sugar unit and the 2, 3, 4 and / or 6 position of the preceding sugar 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 Selected from the group consisting of mixtures of (alkyl groups having 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.
Is. Glycosyl is preferably derived from glucose. To produce these compounds, an alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose or a glucose source to give the glucoside (1
Bond to position) is formed. Additional glycosyl units may also be attached between their 1-position and the preceding glycosyl units at the 2, 3, 4 and / or 6-positions, preferably predominantly the 2-position.

Condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide and 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 about 1800 and is water insoluble. The addition of polyoxyethylene moieties to this hydrophobic moiety tends to increase the overall water solubility of the molecule and the product humor is such that the polyoxyethylene content is up to about 50% of the total weight of the condensation product. Retained, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type are certain commercial Plurafac ^™ LF404 and Pluronic ^™ surfactants sold by BASF.

Also suitable as nonionic surfactants of the nonionic surfactant system according to the invention are the condensation products of ethylene oxide with the products obtained from the reaction of propylene oxide with ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide and usually has a molecular weight of about 2500 to about 3000. The hydrophobic portion is condensed with ethylene oxide to the extent that the condensation product contains from about 40 to about 80 weight percent polyoxyethylene and has a molecular weight of from about 5000 to about 11,000. Examples of this type of nonionic surfactant include B
There are certain commercially available Tetronic ^™ compounds sold by ASF.

The surfactant-based nonionic surfactants of the present invention include polyethylene oxide condensates of alkylphenols, primary and secondary aliphatic alcohols and from 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.

Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula:

[Chemical 44] 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 3 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 mixtures thereof, Z is glucose in a reductive amination reaction,
It is derived from reducing sugars such as fructose, maltose and lactose.

Suitable anionic surfactants used are those described in "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 Ester sulfonate surfactants Suitable starting materials include natural fatty materials 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 structural formula:

[Chemical formula 45] Where 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. It is a cation that forms a water-soluble salt with. Suitable salt forming cations include metals such as sodium, potassium and lithium, substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. Preferably R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Methyl ester sulfonates in which R ³ is C ₁₀ -C ₁₆ alkyl are particularly preferred.

Other suitable anionic surfactants are alkylsulfate surfactants, which are water-soluble salts or acids of formula ROSO ₃ M, where 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, eg an alkali metal cation (
Eg sodium, potassium, lithium), ammonium or substituted ammonium (eg methyl-, dimethyl- and trimethyl-ammonium cations,
And quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof). Typically, C ₁₂ -C ₁₆ alkyl chains are preferred at low wash temperatures (eg, about 50 ° C. or below), and C ₁₆ -C ₁₈ alkyl chains are preferred at high wash temperatures (eg, about 50 ° C. or above).

Other anionic surfactants useful for cleaning purposes can also be included in the detergent compositions of the present invention. These include soap salts (eg sodium, potassium,
Ammonium and substituted ammonium salts, for example including mono-, di- and triethanolamine _salts), C 8 _{-C 22} primary or secondary alkane sulfonates, _{C 8} -
C ₂₄ olefin sulfonates, for example sulfonated polycarboxylic acids prepared by sulfonation of the pyrolysis products of alkaline earth metal citrates, C ₈ -C, as described in British Patent Specification No. 1,082,179. ₂₄ alkyl polyglycol ether sulphates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, fatty oleyl glycerol sulphates, alkylphenol ethylene oxide ether sulphates, paraffin sulphonates, alkyl phosphates, isethionates such as acyl isethionates, N- acyl taurates, alkyl succinate cinnamate and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁ -C ₁₈ monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated _C 6 _{-C 12} diesters), acyl sarcosinates,
Alkyl polysaccharide sulphate (such as alkyl polyglucoside sulphate
Nonionic non sulfate compound are described below), branched primary alkyl sulfates, and the formula _{RO (CH 2 CH 2 O)} k -CH 2 COO - M + (R is a _C 8 _{-C 22} alkyl, k Is an integer from 1 to 10 and M is a soluble salt forming cation). Also suitable are resin acids and hydrogenated resin acids, such as rosins, hydrogenated rosins, resin acids and hydrogenated resin acids present in or derived from tall oil.

Another example is “Surface Active Agents and Detergents” (Vol. I and II, Schwar.
tz, Perry and Berch). A variety of such surfactants are available in 19
It is also generally disclosed at column 23, line 58 to column 29, line 23 of US Patent 3,929,678, issued December 30, 1975, to Laughlin et al. (Incorporated herein by reference). ).

When included herein, 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 surfactants. There is.

Highly preferred anionic surfactants are alkylalkoxylated sulphate surfactants which are water-soluble salts or acids of the formula RO (A) _m SO ₃ M, where R is an unsubstituted C _10- A hydroxyalkyl group having a C ₂₄ alkyl or C ₁₀ -C ₂₄ alkyl moiety, preferably a C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably a C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A being an ethoxy or propoxy unit And m is greater than zero, typically about 0.5 to about 6, more preferably about 0.5 to about 3, and M is H or a cation, such as a metal cation (eg, sodium, potassium, lithium). , Calcium, magnesium, etc.), ammonium or substituted ammonium cations .
Alkyl ethoxylated sulphates and alkyl propoxylated sulphates are considered here. Specific examples of substituted ammonium cations are derived from methyl, dimethyl, trimethyl-ammonium cations, and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and alkylamines such as ethylamine, diethylamine, triethylamine. Things, their mixtures, and so on. Exemplary surfactants are C _12-
C ₁₈ alkyl polyethoxylate (1.0) sulfate (C ₁₂ -C ₁₈ E
_{(1.0) M), C 12} -C 18 alkyl polyethoxylate (2.25) sulfate _{(C 12 -C 18 E (2.25} ) M), C 12 -C 18 alkyl polyethoxylate (3. 0) sulfate _{(C 12 -C 18 E (3.0} ) M) , and _C 12 _{-C 18} alkyl polyethoxylate (4.0) sulfate _{(C 12} -
C ₁₈ E (4.0) M), where M is conveniently selected from sodium and potassium.

The detergent compositions of the present invention may also contain cationic, amphoteric and semipolar surfactants, and nonionic and / or anionic surfactants other than those already described herein.

Cationic detersive surfactants suitable for use in the detergent compositions of the present invention are those that have one long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants, such as alkyl trimethyl ammonium halogenides, and surfactants having the formula: [R ² (OR ³ ) _y ] [R ⁴ ( oR ³⁾ _{y] 2} R ⁵ N ⁺ X ^- the formula ^{R 2} is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain; each ^{R 3} is _-CH 2 CH ₂ - , -CH ₂ CH (CH ₃ )-, -CH ₂ CH (CH ₂ OH)-, -CH ₂ CH ₂ CH _2-, and mixtures thereof; each R ⁴ is C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, a benzyl ring structure formed by linking two R ⁴ groups, -C
H ₂ CHOH-CHOHCOR ⁶ CHOHCH ₂ OH (R ⁶ is a hexose or hexose polymer having a molecular weight of about 1000 or less), and when y is not 0, is selected from the group consisting of hydrogen; R ⁵ is the same as R ^4. Or an alkyl chain having a total number of carbon atoms of R ² + R ⁵ of about 18 or less; each y is 0 to about 10 and the sum of y values is 0 to about 15; X is Any compatible anion.

[0107]   Quaternary ammonium surfactants suitable for the present invention have the formula (I):

[Chemical formula 46] Where R ₁ is short chain length alkyl (C ₆ -C ₁₀ ) or alkylamidoalkyl of formula (II):

[Chemical 47] (Y is 2 to 4, preferably 3); In the above formula, R ₂ is H or C ₁ -C ₃ alkyl; x in the above formula is 0 to 4, preferably 0 to 2, most preferably 0. in it, the formula _R 3, _{R 4} and _{R 5} are identical or different, is a short chain alkyl _(C 1 -C ₃₎ or alkoxylated alkyl of the formula III; in the above formulas X ^- Is a counterion, preferably a halide such as chloride or methylsulfate;

[Chemical 48] (R ⁶ is C ₁ -C ₄ and z is 1 or 2)

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

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) above. 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
A _{(C 2 H 40) x H} (x has a value of 2 to 5), X is an anion.
No more than 1 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 synthetically derived by olefin build-up or oxoalcohol synthesis. To be done. Preferred groups for R ₂ , R ₃ and R ₄ are methyl and hydroxyethyl groups and the anion X is selected from halide, methosulfate, acetic acid and phosphate ions.

Examples of quaternary ammonium compounds of formula (i) suitable for use herein are: coconut trimethylammonium chloride or bromide coconut methyldihydroxyethylammonium chloride or bromidedecyltriethylammonium chloride decyldimethylhydroxyethylammonium chloride or Bromide C _12-15 dimethylhydroxyethylammonium chloride or bromide Coconut dimethylhydroxyethylammonium chloride or bromide Myristyl trimethylammonium methylsulfate lauryl dimethylbenzylammonium chloride or bromidolauryl dimethyl (ethenoxy) ₄ ammonium chloride or bromide choline ester (R ₁ is CH ₂ -CH ₂ -OC (= O) -C _{12-1 4} alkyl and R ₂ , R ₃ and R ₄ are methyl compounds of formula (i) Dialkyl imidazolines (compounds of formula (i))

Other cationic surfactants useful herein are Cambre's US Pat. No. 4,228,044, issued October 14, 1980, and European Patent Application EP000,2.
24 is also described.

Typical cationic fabric softening ingredients 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. There is. Among these preferred cationic softeners are: 1) ditallowdimethylammonium chloride (DTDMAC) 2) dihydrogenated tallowdimethylammonium chloride 3) dihydrogenated tallowdimethylammonium methylsulfate 4) distearyldimethylammonium Chloride 5) Dioleyldimethylammonium chloride 6) Dipalmitylhydroxyethylmethylammonium chloride 7) Stearylbenzyldimethylammonium chloride 8) Tallowtrimethylammonium chloride 9) Hydrogenated tallowtrimethylammonium chloride 10) C _12-14 alkylhydroxyethyldimethylammonium chloride chloride 11) C _12-18 alkyl dihydroxyethyl methyl ammonium chloride 12) di (stearoyl oxyethyl) dimethacrylate Le chloride (DSOEDMAC) 13) di (tallow oxyethyl) dimethyl ammonium chloride 14) ditallow imidazolinium methylsulfate 15) 1- (2-tallow-ylamide ethyl) -2-tallow-yl-imidazo Riniu arm methylsulfate

Biodegradable quaternary ammonium compounds have been provided as an alternative to the traditionally used di-long chain alkyl ammonium chlorides and methyl sulphates. Such a quaternary ammonium compound has a long-chain alkyl (alkenyl) group with a functional group such as a carboxy group interposed. The above substances and the fabric softening composition containing them are EP-A-0,040,562 and EP-A-0,
It is 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:

[Chemical 49] 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 methylsulfate.

The alkyl or alkenyl chain T ¹ , T ² , T ³ , T ⁴ , T ⁵ is at least 11
Must have at least 16 carbon atoms, preferably at least 16 carbon atoms.
The chain may be linear or branched. Tallow is a convenient and inexpensive source of long chain alkyl and alkenyl materials. Particularly preferred are compounds in which T ¹ , T ² , T ³ , T ⁴ , T ⁵ represent a mixture of long chain substances typical of tallow.

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-di (tallowyloxyethyl) -N-methyl, N- (2-hydroxyethyl) ammonium methylsulfate 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-tallowyloxy-2-oxoethyl) -N, N-dimethylammonium chloride 6) N, N, N -Tri (tallowyloxyethyl) -N-methylammonium chloride 7) N- (2-tallowyloxy-2-oxoethyl) -N- (tallowyl-
N, N-dimethylammonium chloride) 8) 1,2-ditaroyloxy-3-trimethylammoniopropane chloride and mixtures of the above substances.

When included herein, the detergent compositions of the present invention will typically contain from 0.2 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 detergent composition 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, where the aliphatic groups may be straight chain or It may be a branched chain. One of the aliphatic substituents has at least about 8 carbon atoms, typically about 8 to about 18 carbon atoms, and at least one is an anionic water-soluble group such as carboxy, sulfonic acid, sulfuric acid. Has a group. For examples of amphoteric surfactants, see Laughlin et al., US Pat. No. 3,929,678, column 19, lines 18-35, issued Dec. 30, 1975. When included herein, the detergent compositions of the present invention typically contain from 0.2 to about 15% by weight, preferably from about 1 to about 10% of such amphoteric surfactants.

Dipolar surfactants are also suitable for use in the detergent composition. These surfactants are
It can be broadly described as a derivative of a secondary or tertiary amine, a derivative of a heterocyclic secondary or tertiary amine, or a derivative of a quaternary ammonium, quaternary phosphonium or tertiary sulfonium compound. For examples of zwitterionic surfactants, see 19
See Laughlin et al., US Pat. No. 3,929,678, December 19, 1975, column 19, line 38 to column 22, line 48. When included herein, the detergent compositions of the present invention typically contain from 0.2 to about 15% by weight, preferably from about 1 to about 10% of such a dipolar surfactant.

Semi-polar nonionic surfactants contain two moieties selected from the group consisting of one alkyl moiety of about 10 to about 18 carbon atoms, an alkyl group of about 1 to about 3 carbon atoms and a hydroxyalkyl group. Having water-soluble amine oxide; about 10 to about 1 carbon atom
A water-soluble phosphine oxide having one alkyl moiety of eight, two moieties selected from the group consisting of an alkyl group of about 1 to about 3 carbon atoms and a hydroxyalkyl group; one alkyl of about 10 to about 18 carbon atoms A special category of nonionic surfactants, including water soluble sulfoxides having moieties, moieties 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:

[Chemical 50] Wherein R ³ is an alkyl, hydroxyalkyl, alkylphenyl group having from about 8 to about 22 carbon atoms or a mixture thereof; R ⁴ is an alkylene having from about 2 to about 3 carbon atoms, a hydroxyalkylene group or X is 0 to about 3; each R ⁵ is an alkyl or hydroxyalkyl group having from about 1 to about 3 carbon atoms, or a polyethylene oxide group having from about 1 to about 3 ethylene oxide groups. is there. The R ⁵ groups may be joined together, for example via an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants include, in particular, C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₈ -C ₁₂ alkoxyethyldihydroxyethylamine oxides.

When included herein, the cleaning composition of the present invention typically comprises from 0.2 to
It contains from about 15% by weight, preferably from about 0.1 to about 10% of such semipolar nonionic surfactants.

The detergent composition of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines. Primary amines suitable for use herein include amines according to the formula R ₁ NH ₂ , where R ₁ is a C ₆ -C ₁₂ , preferably a C ₆ -C ₁₀ alkyl chain, or R ₄ X (C
H ₂ ) _n , X is —O—, —C (O) NH— or —NH—, R ₄ is a C ₆ -C ₁₂ alkyl chain, n is 1-5, preferably 3 is there. The R ₁ alkyl chain may be straight or branched and may be intervened with up to 12 ethylene oxide moieties, preferably less than 5. The preferred amine according to the above formula is an n-alkylamine. Amines suitable for use herein are selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines are C ₈ -C ₁₀ oxypropylamine, octyloxypropylamine, 2-ethylhexyloxypropylamine, laurylamidopropylamine and amidopropylamine.

Tertiary amines suitable for use herein include tertiary amines having the formula R ₁ R ₂ R ₃ N, wherein R ₁ and R ₂ are C ₁ -C ₈ alkyl chains or

[Chemical 51] And R ₃ is a C ₆ -C ₁₂ , preferably 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 straight or branched and the R ₃ alkyl chain may be mediated by up to 12 and preferably less than 5 ethylene oxide moieties.

Preferred tertiary amines are those wherein R ₁ is a C ₆ -C ₁₂ alkyl chain and R ₂ and R ₃ are C ₁ -C ₃ alkyl or

[Chemical 52] Wherein R ₅ is H or CH ₃ and x = 1 to 2 and R ₁ R ₂ R ₃ N. Also preferred are amidoamines of the formula:

[Chemical 53] In the above formula, R ₁ is C ₆ -C ₁₂ alkyl, n is 2-4, preferably n is 3, and R ₂ and R ₃ are C ₁ -C ₄ .

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 mole propoxylated laurylamine, 2 mole propoxylated octylamine, laurylamide There are propyldimethylamine, C _8-10 amidopropyldimethylamine and C ₁₀ amidopropyldimethylamine. The most preferred amines for use in the composition are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especially desirable is
n-dodecyldimethylamine, bishydroxyethyl coconut alkylamine,
7-ethoxylated oleylamine, laurylamidopropylamine and cocoamidopropylamine.

Bleach The detergent composition of the present invention may further contain another bleach in addition to the selected bleach system of the present invention. Bleaching agents that can be used include halogen bleaching agents. Examples of hypohalous acid bleach include:
Examples are trichloroisocyanuric acid, sodium and potassium dichloroisocyanurate, N-chloro and N-bromoalkanesulfonamide. Such materials are usually added at 0.5-10% by weight of the final product, preferably 1-5%.

Bleaching agents other than oxygen bleaching agents are known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest is a light activated bleaching agent such as sulfonated zinc and / or aluminum phthalocyanines. These materials can adhere to the substrate during the cleaning process. Light exposure in the presence of oxygen, such as hanging clothes to dry in the sun, activates the sulfonated zinc phthalocyanine, resulting in bleaching of the substrate. Preferred zinc phthalocyanines and photoactivated bleaching processes are described in US Pat. No. 4,033,718. Typically,
The detergent composition contains from about 0.025 to about 1.25% by weight of sulfonated zinc phthalocyanine.

Builder System The detergent composition of the present invention may further comprise a builder. Aluminosilicate materials, silicates, polycarboxylates, alkyl or alkenyl succinic acids, and fatty acids, materials such as ethylenediaminetetraacetic acid, diethylenetriaminepentamethyleneacetic acid, sequestering agents such as aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriamine. Any conventional builder system is suitable for use herein, including pentamethylenephosphonic acid. Phosphate builders may also be used here.

Suitable builders include inorganic ion exchange materials, usually inorganic hydrated aluminosilicate materials, more specifically hydrated synthetic zeolites such as hydrated zeolites A, X, B,
There is 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 their ether derivatives, as disclosed in Belgian patents 831,368, 821,369 and 821,370. Polycarboxylates with two carboxy groups include succinic acid, malonic acid, (ethylenedioxy)
Water-soluble salts of diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, and the ethers described in German Patent Publication 2,446,686, 2,446,687 and US Pat. No. 3,935,257. There are carboxylates and the sulfinyl carboxylates described in Belgian Patent 840,623. Polycarboxylates having three carboxy groups include, among others, water-soluble citrates, aconitrates and citraconates, and British Patent 1,379,241.
Carboxymethyl oxysuccinate described in US application 720587
Succinate derivatives such as lactoxysuccinate described in 3, and oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylate described in British Patent 1,387,447. is there.

Polycarboxylates with four carboxy groups are described in British Patent 1,261
, 829, oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,
There is 1,2,3-propane tetracarboxylate. Polycarboxylates having sulfo substituents include sulfosuccinate derivatives disclosed in British Patents 1,398,421, 1,398,422 and US Patent 3,936,448, and British Patent 1,082,179. There are sulfonated pyrolytic citrates described and polycarboxylates with phosphon substituents are described in British Patent 1,439,000.
It is disclosed in.

Cycloaliphatic and heterocyclic polycarboxylates include cyclopentane-cis,
Cis, cis-tetracarboxylate, cyclopentadienide pentacarboxylate, 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 meritic acid, pyromellitic acid, and the phthalic acid derivatives disclosed in British Patent 1,425,343. Preferred polycarboxylates among the above are hydroxycarboxylates having up to 3 carboxy groups per molecule, more particularly citrates.

Preferred builder systems for use in the composition include a water insoluble aluminosilicate builder or layered silicate (SKS-6) such as zeolite A and a water soluble carboxylate chelating agent such as citric acid. There is a mixture. Other preferred builder systems include water insoluble aluminosilicate builders such as Zeolite A,
There are mixtures with water-soluble carboxylate chelating agents 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 for use in the granular composition include carbonic acid, bicarbonates, inorganic substances such as alkali metal silicates, and organic phosphonates,
There are organic materials such as amino polyalkylene phosphonates and amino polycarboxylates. Other suitable water-soluble organic salts are homo- or copolymeric acids or their salts, in which case the polycarboxylic acids have at least two carboxyl groups separated from each other by not more than 2 carbon atoms. This type of polymer is GB-
A-1,596,756. An example of such a salt is MW2000.
~ 5000 polyacrylates, and their copolymers with maleic anhydride, such copolymers being 20,000 to 70,000, in particular about 40,000.
It has a molecular weight of 00.

The cleaning builder salt is usually included in an amount of 5 to 80% by weight of the composition, preferably 10 to 70% by weight, most commonly 30 to 60% by weight.

Conventional Detergent Enzymes In addition to the pectate lyase enzyme, the detergent composition may further include one or more enzymes that exert cleaning performance, fabric care and / or sanitizing effects. Preferably, the detergent composition of the present invention further contains pectin lyase.

The above-mentioned enzymes include cellulase, hemicellulase, peroxidase, protease, glucoamylase, amylase, xylanase, lipase, phospholipase, esterase, cutinase, other pectinases, keratanase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, There is an enzyme selected from pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase or mixtures thereof. A preferred combination is a detergent composition having a cocktail of conventional enzymes such as proteases, amylases, lipases, cutinases and / or cellulases together with one or more plant cell wall degrading enzymes.

Each type of pectin-degrading enzyme has a unique profile of substrate specificity, activity and stability under different hardness, pH, temperature, detergent and other detergent component matrix conditions. Pectin-degrading enzymes have been identified to degrade pectin substances, especially plant cell walls. In particular, the pectate lyase enzyme acts specifically on plant cell wall pectinate chains such as low methoxypectin, while pectin lyase acts more specifically on esterified pectin chains such as high methoxypectin. . Furthermore, it was found that pectate lyase is metal and especially calcium sensitive, whereas pectin lyase does not require metal for stability and optimal enzymatic activity. It was surprisingly found that a wide range of substrate specificities and high flexibility with respect to various washing conditions can be obtained by further combining the pectate lyase and the pectin lyase of the present invention. This results in synergistic cleaning and especially plant-based stain / stain and body stain removal.

Pectin lyase enzymes are classified in EC class EC 4.2.2.10, preferably substantially free of other pectin-based enzymes and act on pectic acid to non-hydrolyze the α-1,4-glycosidic bond. Cleavage is performed to form oligosaccharides with a terminal 4-deoxy-6-α-D-galactoenouronosyl group. The pectin lyase of the present invention is substantially free of other pectin-based enzymes. "Substantially free from other pectin-based enzymes" means that the pectin-based enzymes other than the pectin lyase enzyme are 25% or less, preferably 15%.
Hereinafter, it means a pectin lyase enzyme-containing composition containing 5% or less. Enzymatic activity can be measured according to "Assay of trans-eliminase activity for pectin and pectic acid" described in K. Horikoshi, Arg. Biol. Chem., Vol. 36 (2), 286.

Preferred pectin lyases for the purposes of the present invention are co-pending international patent application P, filed internationally on Nov. 24, 1998 and published in WO 99/27083.
A pectin lyase as described in CT / DK98 / 00514 as follows: i) a polypeptide produced by Bacillus licheniformis ATCC 14580, or ii) 31-494 of PCT / DK98 / 00514 SEQ ID NO: 2
A polypeptide comprising an amino acid sequence as indicated at position iii), or iii) an analog of the polypeptide defined in i) or ii) that is at least 60% homologous to the above polypeptide, or iv) one or more Derived from the above-mentioned polypeptide by substitution, deletion or addition of the amino acid of (provided that SEQ ID N of PCT / DK98 / 00514
O: 2, the arginines at positions 377 and 383 are conserved, and the derived polypeptide is at least 60% homologous to said polypeptide), or v) immunized with a polyclonal antibody against said polypeptide in purified form. Those that are reactive.

A suitable protease is subtilisin (subtilisin BPN and BPN ') obtained from specific strains of B. subtilis and B. licheniformis. One suitable protease is obtained from Bacillus strains and has maximum activity in the pH range 8-12,
Developed by Novo Industries A / S in Denmark and sold as ESPERASE ^R , hereinafter referred to as "Novo". This enzyme and similar enzymes are manufactured by Novo G
B1, 243, 784. Other suitable proteases include Novo's
ALCALASE ^R , DURAZYM ^R and SAVINASE ^R , and Gist-Brocades MAXATASE ^R ,
MAXACAL ^R, there is PROPERASE ^R and Maxapem ^R (protein engineered Maxacal). Proteolytic enzymes include modified bacterial serine proteases, eg 1987 4
Described in European Patent Application No. 87 / 303761.8 filed March 28, in particular pages 17, 24 and 98, hereinafter referred to as "Protease B" and "Protease A" below. European patent application No. 19 of Venegas published on October 29, 1986 relating to a modified bacterial serine proteolytic enzyme designated "
Some are described in the specification of No. 9,404. Lysine replaces arginine at position 27, tyrosine replaces valine at position 104, serine replaces asparagine at position 123, alanine replaces threonine at position 274, a variant of the Bacillus- derived alkaline serine protease. A protease designated Protease C "is suitable. Protease C is EP 9091595 corresponding to WO 91/06637 published May 16, 1991.
8: 4. Also included herein are genetically modified variants of Protease C.

A preferred protease, referred to as "Protease D", is a carbonyl hydrolase variant with an amino acid sequence not found in nature, and is WO95 / 10591.
, And USSN 08/3 of C. Ghosh et al., Filed October 13, 1994.
According to the numbering of Bacillus amyloliquefaciens subtilisin, as described in the patent application entitled "Bleaching Compositions Containing Protease Enzyme", 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.
Derived from the precursor carbonyl hydrolase by substituting different amino acids for multiple amino acid residues in the carbonyl hydrolase at the position corresponding to position 6. The following residues: +33, +62, +67, +76, +100, +
101, +103, +104, +107, +128, +129, +130, +1
32, +135, +156, +158, +164, +166, +167, +17
WO 95/10591, having an amino acid sequence derived by the substitution of a plurality of amino acid residues replaced on the precursor enzyme corresponding to position +210 with one or more of 0, +209, +215, +217, +218 and +222. Carbonyl hydrolase variants of the selected proteases are also suitable, but the position numbered here corresponds to the natural subtilisin from Bacillus amyloliquefaciens or to the corresponding amino acid residue of another carbonyl hydrolase or subtilisin, such as Bacillus lentus subtilisin (1997). Co-pending patent application USSN 60 / 048,550 filed June 4, 2012).

Proteases described in patent applications EP 251446 and WO 91/06637, proteases BLAP ^R described in WO 91/02792, and WO
Those variants described in 95/23221 are also suitable for the invention. Novo W
See also the high pH protease from Bacillus sp. NCIMB 40338 described in O93 / 18140A. Enzymatic detergents containing proteases, one or more other enzymes and a reversible protease inhibitor are described in Novo WO92 / 03529A. If desired, proteases with reduced adsorptivity and improved hydrolyzability are available as described in Procter & Gamble WO 95/07791. A suitable recombinant trypsin-like protease for detergents here is Novo's W
O94 / 25583. Other suitable proteases are described in Unilever EP 516200.

The proteolytic enzyme is present in 0.0001 to 2% by weight of the composition, preferably 0.0.
It is incorporated into the detergent composition of the present invention at a pure enzyme level of 01-0.2%, more preferably 0.005-0.1%.

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 Viscosity U).
nit) or higher specific activity. A suitable cellulase is described in US Patent 4, to Barbesgoard et al.
435,307, J61078384 and WO 96/02653, wherein Humicola insolens, Trichoderma, Thielavia and Sporotrichu.
discloses fungal cellulases each produced from m. EP739982
Describes a cellulase isolated from a novel Bacillus species. Suitable cellulases are GB-A-2,075,028, GB-A-2,095,275, DE-O.
It is also disclosed in S-2,247,832 and WO 95/26398.

Examples of such cellulases include strains of Humicola insolens (Humicola grisea var
.thermoidea), especially a cellulase produced by Humicola strain DSM1800. Other suitable cellulases were derived from Humicola insolens, DSM 1800, which has a molecular weight of about 50 kDa, an isoelectric point of 5.5, and contains 415 amino acids; A 43 kD endoglucanase, the preferred endoglucanase component is PCT patent application W
It has the amino acid sequence disclosed in O91 / 17243. September 2, 1994
Trichoderma described in WO 94/21801 by Genencor, published 9th
EGIII cellulase from longibrachiatum is also a suitable cellulase. Particularly suitable cellulases are those having a color-care effect. An example of such a cellulase is described in European Patent Application No. 9120287 filed Nov. 6, 1991.
Cellulase described in No. 9.2 specification. Carezyme and Celluz
yme (Novo Nordisk A / S) is especially useful. WO91 / 17244 and WO
See also 91/21801. Other cellulases suitable for fabric care and / or cleaning properties are WO96 / 34092, WO96 / 17994 and WO95 /
24471. The above cellulases are usually incorporated into detergent compositions at levels of 0.0001 to 2% pure enzyme by weight of the detergent composition.

Peroxidase enzymes are oxygen sources such as percarbonates, perborates,
Used in combination with persulfates, hydrogen peroxide, etc., and phenolic substrates as bleach enhancing molecules. They are used for "solution bleaching", ie to prevent dyes or pigments that fall off the substrate during the washing operation from migrating to other substrates in the wash liquor. Peroxidase enzymes are known in the art and include, for example, haloperoxidases such as horseradish peroxidase, ligninase, chloro and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Applications WO 89/099813, WO 89/09.
813, and European patent application EP 9120 filed Nov. 6, 1991.
EP96870013 filed 2882.6 and February 20, 1996
． 8 is disclosed. The laccase enzyme is also suitable.

Enhancers are typically included at levels of 0.1-5% 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 hydrogen peroxide source. The peroxidase is usually incorporated into detergent compositions at a pure enzyme level of 0.0001-2% by weight of the detergent composition.

Another enzyme that may be included in the detergent composition of the present invention is lipase. Suitable lipase enzymes for detergents include Pseudomona disclosed in British Patent 1,372,034.
Some are produced by microorganisms of the genus Pseudomonas, such as S. stutzeri ATCC 19.154. Suitable lipases include those produced by the microorganism Pseudomonas fluorescent IAM1057 which show a positive immune cross-reactivity with the antibodies of the lipase. This lipase is known as Lipase P "Amano" in Amano, Nagoya, Japan.
It is commercially available from Pharmaceutical Co. Ltd. and is hereinafter referred to as "Amano-P". Other suitable commercially available lipases include Amano-CES, Chromobacter viscosum such as Japan,
Lipase from Chromobacter viscosum var. Lipolyticum NRRLB 3673 from Toyo Brewery Co., Ltd .; USBiochemical Corp. of USA and Disoynth Co. of The Netherlands.
Chromobacter viscosum lipase from Pseudomonas gladioli. Particularly suitable lipases are M1 Lipase ^R and Lipomax ^R (Gist-Brocades)
And lipases such as Lipolase ^R and Lipolase Ultra ^R (Novo), which have been found to be very effective when used in combination with the compositions of the present invention. Novo
Nordisk EP258068, WO92 / 05249 and WO95 / 2261
5, Unilever's WO94 / 03578, WO95 / 35381 and WO96 /
The lipolytic enzymes described in 00292 are also suitable.

Also suitable is a special type of lipase, namely cutinase [EC 3.1.1.50], which is regarded as a lipase that does not require surface activity. The addition of cutinase to detergent compositions has been described, for example, in WO-A-88 / 09367 (Genencor), WO90 / 09446 (Plant Ge).
netic System), WO94 / 14963 and WO94 / 14964 (Unilever
). The lipase and / or cutinase is 0.0001 to 2% by weight of the detergent composition.
Is normally incorporated into detergent compositions at pure enzyme levels of.

Amylases (α and / or β) can be included for the removal of carbohydrate-based soils. WO 94/02597 of Novo Nordisk A / S, published February 3, 1994, describes a detergent composition incorporating a mutant amylase. WO95 / of Novo Nordisk A / S released on April 20, 1995
See also 10603. Other amylases known for detergent compositions include both α- and β-amylases. α-Amylase is known in the art and is US Pat. No. 5,003,257, EP252,666, WO91 / 00353, FR2,6.
76,456, EP285,123, EP525,610, EP368,341
And British Patent Specification No. 1,296,839 (Novo). Other suitable amylases are described in WO94 / 1 published Aug. 18, 1994.
8314, Genencor WO 96/0529, published February 22, 1996.
Improved amylase described in No. 5, and WO95 published April 1995
No. 10603, an amylase variant with additional modifications in the immediate parent commercially available from Novo Nordisk A / S. EP277216, WO95 / 26397 and WO96
Amylases described in / 23873 (all Novo Nordisk) are also suitable.

[0153] Examples of commercial α- amylases products, Purafect of Genencor Ox Am ^R, all Novo N
ordisk A / S Termamyl ^R , Ban ^R , Fungamyl ^R and D commercially available from Denmark
It is uramyl ^R. WO95 / 26397, the other suitable amylases: as measured by Phadebas ^R alpha-amylase activity assay, temperature and 8 of 25 to 55 ° C.
It describes an α-amylase characterized by having a specific activity of at least 25% higher than that of Termamyl ^R at pH values in the 10 range. WO96 / 23
Variants of the above enzymes described in 873 (Novo Nordisk) are suitable. Other amylolytic enzymes with improved properties in terms of activity level and combination of thermostability and high activity level 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.
Pure enzyme levels of 018-0.06%, more preferably 0.00024-0.048% are incorporated into the detergent compositions of the present invention.

The enzyme may be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. The origin may further be mesophilic or extreme (eg, psychrophilic, eutrophic, thermophilic, pressure-sensitive, alkalophilic, acidophilic, halophilic). Purified or unpurified forms of these enzymes may also be used. It is now customary to modify the wild-type enzyme by protein / genetic engineering techniques to maximize performance efficacy with the detergent compositions of the present invention. For example, variants are designed to increase the compatibility of the enzyme with the conventional ingredients of such compositions. Alternatively, the variants may be designed such that the optimum pH, bleach or chelant stability, catalytic activity, etc. of the enzyme variant are adjusted to suit a particular cleaning application.

Particular attention should be paid to amino acids that are susceptible to oxidation in terms of bleach stability and surface charge in terms of detergent compatibility. The isoelectric point of such enzymes may be modified by substituting some charged amino acids, for example increasing the isoelectric point helps 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 cherant stability. Special attention must be paid to cellulases as most cellulases have separate binding domains (CBD). The properties of such enzymes are altered by modification of these domains.

The above enzymes are usually incorporated into detergent compositions at a pure enzyme level of 0.0001-2% by weight of the detergent composition. Enzymes are separate single components (globules containing one enzyme,
Granules, stabilizing liquids, etc.) or as a mixture of two or more enzymes (eg cogranulates).

Another suitable detergent ingredient that may be added is the enzyme oxidative scavenger, which is 1
Co-pending European Patent Application No. 92870018. filed January 31, 992.
No. 6 specification. An example of such an enzymatic oxidation scavenger is ethoxylated tetraethylene polyamine.

Various enzyme materials and their means of incorporation into synthetic detergent compositions have also been described by Genencor I.
nternational WO 9307263A and WO 9307260A, Novo WO
8908694A, and McCarty et al., US Pat. No. 3,553, dated January 5, 1971.
139. The enzyme is described in US 4, US Pat.
101,457 and Hughes, US 4,507,219 dated 26 March 1985.
But it is further disclosed. Enzymatic substances useful in liquid detergent formulations and their incorporation in such formulations is described in Hora et al., US 4,261, April 14, 1981.
868. Enzymes useful in detergents can be stabilized by various techniques. Enzyme stabilization technology is described in US Pat. No. 3,600 of Gedge et al., August 17, 1971.
319, Venegas EP 199,405 and EP 29 October 1986.
200,586. The enzyme stabilization system is also, for example, US 3,
519,570. A useful Bacillus sp. AC13 that provides proteases, xylanase and cellulase is described in Novo WO9401532A.

Color Care and Fabric Care Benefits Technologies that exert certain types of color care benefits can also be included.
An example of these technologies are metal catalysts for color maintenance. Such metal catalysts are described in co-pending European patent application No. 92870181.2. Dye fixing agents, polyolefin dispersants for preventing wrinkles and improving water absorption, amino functional polymers for perfume, color care treatment and perfume maintenance (PCT / US9
7/16546) is another example of color care / fabric care technology.
It is described in co-pending patent application No. 96870140.9 filed Nov. 7, 1996.

Fabric softeners can also be incorporated into the detergent compositions according to the present invention. These agents may be inorganic or organic in type. Inorganic softeners are exemplified by the smectite clays disclosed in GB-A-1,400,898 and USP 5,019,292. Organic fabric softeners include GB-A1,514,276 and EP-B0,011.
, 340, a water-insoluble tertiary amine, EP-B-0,026,52.
7 and EP-B-0,026,528 mono _C 12 _-C disclosed in ₁₄ combination with quaternary ammonium salts and their di-long chain such as disclosed in, and EP-B-0,242,919 There is an amide. Other useful organic components of the fabric softening system include E
There are high molecular weight polyethylene oxide materials such as those disclosed in PA-0,299,575 and 0,313,146.

The level of smectite clay is usually 2 to 20% by weight, more preferably 5 to 15%.
%, The material is added to the rest of the formulation as a dry mix ingredient. Organic fabric softeners such as water insoluble tertiary amines or di-long chain amide materials have a .0.
5 to 5% by weight, usually 1 to 3% by weight, and the high molecular weight polyethylene oxide substance and water-soluble cationic substance are 0.1 to 2% by weight, usually 0.15 to 1%.
． Added at the 5% level. These substances are usually added to the spray dry portion of the composition, but in some cases they are added as dry mix particles or sprayed as a molten liquid onto other solid components of the composition. Is convenient.

Chelating Agents The detergent compositions may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctional substituted aromatic chelating agents 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 forming soluble chelates.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid,
There are ethylenediaminetetrapropionic acid, triethylenetetraaminehexaacetic acid, diethylenetriaminepentaacetic acid and ethanoldiglycine, 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 detergent compositions.
There is ethylenediaminetetrakis (methylenephosphonate) such as T. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups of more than about 7 carbon atoms. Polyfunctional substituted aromatic chelating agents are also useful in the present composition. May 1974 2
See US Pat. No. 3,812,044 issued by Connor et al. A preferred compound of this type is dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene when in the acid form.

A preferred biodegradable chelator for use herein is Hartma, Nov. 3, 1987.
n and Perkins ethylenediamine disuccinic acid (“EDDS”) as described in US Pat. No. 4,704,233, especially the [S, S] isomer. The composition may also contain a water soluble methylglycine diacetic acid (MGDA) salt (or acid form) as a cherant or cobuilder useful with insoluble builders such as zeolites, layered silicates and the like.

If utilized, these chelating agents are typically about 0.1 to about 15% by weight of the detergent composition. More preferably, the chelating agent, if utilized, is about 0.1 to about 3.0% by weight of such composition.

Foam Inhibitor Another optional ingredient is a foam suppressant exemplified by silicones and silica-silicone mixtures. Silicones are typically represented by alkylated polysiloxane materials, and silica is commonly used in finely divided form, exemplified by silica aerogels, xerogels and various types of hydrophobic silica. These materials can be formulated as particles, and the suds suppressor is advantageously releasably formulated in a water-soluble or water-dispersible, substantially non-surfactant detergent impermeable carrier. Alternatively, the suds suppressor may be dissolved or dispersed in a liquid carrier and applied by spraying on one or more other components.

A preferred silicone suds suppressor is US Pat. No. 3,933,67 to Bartollota et al.
2 is disclosed. Another particularly useful suds suppressor is a self-emulsifying silicone suds suppressor and is disclosed in German Patent Application DTOS 2,6, published Apr. 28, 1977.
46,126. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. A particularly preferred suds suppressor is a suds suppressor system consisting of a mixture of silicone oil and a 2-alkyl-alkanol. A suitable 2-alkyl-alkanol is 2-butyloctanol sold under the tradename Isofol 12R. Such suds suppressor systems are described in co-pending European patent application N928870174, filed Nov. 10, 1992. A particularly preferred silicone suds suppressor is co-pending European patent application N ° 92201.
649.8. The compositions may comprise silicone / silica mixture in combination with a molten nonporous silica such as Aerosil ^R.

The suds suppressors described above are present at 0.001 to 2% by weight of the composition, preferably 0.0.
It is usually used at a level of 1 to 1% by weight.

Other Ingredients Other ingredients such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, haze suppressants, colorants and / or encapsulated or unencapsulated perfumes may also be present in detergent compositions. May be used.

A particularly suitable encapsulating material is a water-soluble capsule consisting of a matrix of polysaccharides and polyhydroxy compounds as described in GB 1,464,616. Other suitable water-soluble encapsulants are as described in US 3,455,838,
It consists of dextrins derived from ungelatinized starch esters of substituted dicarboxylic acids. These acid ester dextrins are preferably prepared 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. The starch is modified by adding a monofunctional substituent such as octenyl succinic anhydride.

Suitable anti-redeposition and soil suspending agents here 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, as well as 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 typically used at levels of 0.5 to 10% by weight of the composition, more preferably 0.75 to 8% by weight, and most preferably 1 to 6% by weight.

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'-disulfonic acid disodium salt, 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino ) Stilbene-2,2'-
Disodium disulfonate, 4,4'-bis (2,4-dianilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonic acid disodium, 4
', 4 "-Bis (2,4-dianilino-s-triazin-6-ylamino) stilbene-2-sulfonic acid monosodium, 4,4'-bis [2-anilino-4- (
N-methyl-N-2-hydroxyethylamino) -s-triazin-6-ylamino] stilbene-2,2'-disulfonic acid disodium salt, 4,4'-bis (4
-Phenyl-2,1,3-triazol-2-yl) stilbene-2,2'-disulfonic acid disodium, 4,4'-bis [2-anilino-4- (1-methyl-
2-Hydroxyethylamino) -s-triazin-6-ylamino] stilbene-2,2'-disulfonic acid disodium, 2-stilbir-4 "-(naphtho-1
', 2', 4,5) -1, 2,3-Triazole-2 "-sodium sulfonate and 4,4'-bis (2-sulfostyryl) biphenyl. Highly preferred brighteners are EP753567. The specific brightening agent disclosed in.

Other useful polymeric materials are polyethylene glycols, especially molecular weights of 1000-1.
0000, more specifically 2000 to 8000, and most preferably about 4000. These are used at a level of 0.20-5% by weight, more preferably 0.25-2.5%. These polymers, and the homo- or copolymer polycarboxylate salts already described, maintain whiteness, fabric ash adhesion.
deposition) and in the presence of transition metal impurities to improve cleaning performance against soil, proteins and oxidative soils.

Soil release agents useful in the compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and / or propylene glycol units in various configurations. Examples of such polymers are generally assigned US Pat.
72,033. A particularly preferred polymer according to EP-A-0,272,033 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, the end groups being predominantly sulfobenzoates and secondary ethylene glycol and / or Alternatively, it consists of a monoester of propanediol. The purpose is to obtain a polymer that is capped at both ends with sulfobenzoate groups, and in this context most of the above copolymers are endcapped with sulfobenzoate groups. However, some copolymers are not fully capped, so their end groups may consist of monoesters of ethylene glycol and / or propane-1,2-diol,
"Secondarily" consists of such species. The polyester selected here is about 46% by weight dimethyl terephthalic acid, about 1%.
6% by weight of propane-1,2-diol, about 10% by weight of ethylene glycol,
It contains about 13% by weight dimethyl sulfobenzoic acid and about 15% by weight sulfoisophthalic acid and has a molecular weight of about 3000. Polyesters and their methods of manufacture are described in detail in EPA 311 and 342.

It is well known in the art that free chlorine in tap water rapidly inactivates the enzymes contained in detergent compositions. Therefore, when a chlorine scavenger such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine is used in the formulation at a level of 0.1% or more by weight of the total composition, an improved through-the-wash of detergent enzyme ( throuth the wash) Provides stability. Compositions containing chlorine scavengers are described in European patent application 92 filed January 31, 1992.
87008.6.

Alkoxylated polycarboxylates, such as those made from polyacrylates, are useful herein for exerting additional fat removal performance. Such materials are described in WO 91/08281 and PCT 90 /, incorporated herein by reference.
01815, pp. 4 et seq. Chemically, these materials consist of polyacrylates with one ethoxy side chain for every 7-8 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 are 6-12. The side chains are esterified to the polyacrylate "backbone" to form a "comb" polymer type structure. The molecular weight can vary, but is typically in the range of about 2000 to about 50,000. Such alkoxylated polycarboxylate is about 0.05 to about 10% by weight of the composition.

Dispersants The detergent compositions of the present invention may also contain dispersants. Suitable water-soluble organic salts are homo or copolymer acids, or salts thereof, the polycarboxylic acids of which have at least two carboxyl groups separated from each other by not more than 2 carbon atoms. Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000, and copolymers thereof with maleic anhydride, such copolymers being 1000-100,
It has a molecular weight of 000. In particular, copolymers of acrylates and methyl acrylates such as 480N having a molecular weight of 4000 can be added in the detergent compositions of the invention at levels of 0.5 to 20% by weight of the composition.

The compositions of the present invention may contain a lime soap peptizer compound, which has a lime soap dispersity (LSDP) of 8 or less, preferably 7 or less, and most preferably 6 or less. It is preferable that The lime soap peptizer compound is preferably present at a level of 0-20% by weight.

A numerical measure of the effectiveness of Lime Soap Peptizer is the Lime Soap Dispersion Power (LSD).
P.), HC Borghetti and CA Bergman, J. Am. Oil. Chem. Soc., Volum.
e 27, pages 88-90 (1950). Measured using the lime soap dispersion test as described. This lime soap dispersion test method is widely used by those skilled in the art, for example, the following review literature: WNLinfield, Surfactant Science Series, Volume 7, p.
3 ； WNLinfield, Tenside Surf.det., Volume 27, pages 159-163 (1990) ； MKNag
arajan, WFMasler, Cosmetics and Toiletries, volume 104, pages 71-73 (1989)
It is described in. LSDP is 333 ppm CaCo ₃ (Ca: Mg = 3
: 2) The% weight ratio of dispersant to sodium oleate necessary to disperse the lime soap precipitate formed by 0.025 g of sodium oleate in 30 ml of water of comparable hardness.

Surfactants that have good lime soap peptizer capabilities include certain amine oxides, betaines, sulfobetaines, alkyl ethoxy sulphates and ethoxylated alcohols. Exemplary surfactants having an LSDP of 8 or less for use in accordance with the present invention include C ₁₆ -C ₁₈ dimethylamine oxide, C ₁₂ -C ₁₈ alkyl ethoxy sulphates having an average degree of ethoxylation of 1 to 5, especially degrees of ethoxylation. 3 C ₁₂ -C ₁₅ alkylethoxy sulphate surfactant (LSDP = 4), and BASF Gmb
There are C ₁₄ -C ₁₅ ethoxylated alcohols with an average degree of ethoxylation of 12 (LSDP = 6) or 30 sold by H under the trade names Lutensol A012 and Lutensol A030, respectively.

Polymer lime soap peptizers suitable for use herein include Cosmetics and To
iletries, volume 104, pages 71-73 (1989), MK Nagarajan, WFMasle
It is described in the paper by r. 4- (N-octanoyl-6-aminohexanoyl) benzenesulfonate,
4- (N-nonanoyl-6-aminohexanoyl) benzenesulfonate, 4-
Hydrophobic bleaching such as (N-decanoyl-6-aminohexanoyl) benzene sulphonate and mixtures thereof; Nonanoyloxybenzene sulphonate with hydrophilic / hydrophobic bleaching formulations also used as lime soap peptizer compounds sell.

Dye Inhibition The detergent compositions of the present invention also contain a compound for inhibiting the dye transfer from the fabric with the dissolved and suspended dyes encountered during fabric washing operations involving colored fabrics to another. can do.

Polymer Transfer Inhibitor The detergent composition according to the present invention comprises 0.001 to 10% by weight, preferably 0.01 to 10.
It may also contain 2%, more preferably 0.05 to 1% of a polymer transfer inhibitor. The polymeric dye transfer inhibitors described above are commonly incorporated into detergent compositions to prevent dye migration from the colored fabric onto the washed fabric. These polymers have the ability to complex or adsorb free dye washed off from the colored fabric before the dye has the opportunity to become attached 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 enzyme according to the invention.

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

[Chemical 54] In the above formula, P is a polymerizable unit to which an R-N-O group can be attached, 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, cycloaliphatic group or a combination thereof, to which the nitrogen of the NO group can be bonded, or The nitrogen of the NO group is part of these groups.

[0187]   The NO group can be represented by the following general structure:

[Chemical 55] Wherein R1, R2 and R3 are aliphatic groups, aromatic, heterocyclic, alicyclic groups or combinations thereof, wherein x or / and y or / and z is 0 or 1 where N The nitrogen of the -O group is attached or the nitrogen of the N-O group forms part of these groups.

The N—O 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 N--O group forms part of the polymerizable unit include 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 consists of a group of polyamine N-oxides in which the nitrogen of the NO group forms part of the R group. Preferred polyamine N
-Oxide is where R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and their derivatives. 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 polyamine oxides having NO groups attached to the polymerizable units. Preferred classes of these polyamine N-oxides are those of the general formula (I) in which R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the NO functional group is part of the R group above. It is a polyamine N-oxide. Examples of these classes are polyamine oxides, where R is a heterocyclic compound such as pyridine, pyrrole, imidazole and their derivatives. Another preferred class of polyamine N-oxides is the compound of the general formula (I ) Is a polyamine oxide. Examples of these classes are polyamine oxides where the R group is aromatic such as phenyl.

Any polymeric backbone may be used as long as the amine oxide polymer formed is water soluble and dye transfer inhibiting. 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 are typically 10: 1 to 1: 1000.
It has an amine to amine N-oxide ratio 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 2: 3 to 1: 1,000,000, more preferably 1: 4 to 1: 1,000,000, most preferably 1: 7 to 1: 100,000.
It is 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 pKa <7, more preferably pKa <6. Polyamine oxides can be obtained with almost any degree of polymerization. The degree of polymerization is not critical provided the material has the desired water solubility and dye suspending power. Typically, the average molecular weight is 500 to 1,000,000, preferably 1000.
~ 50,000, more preferably 2000-30,000, most preferably 30.
It is in the range of 00 to 20,000.

B) Copolymers of N-vinylpyrrolidone and N-vinylimidazole N-vinylimidazole N-vinylpyrrolidone polymers used according to the invention have an average molecular weight of 5000 to 1,000,000, preferably 5000 to 200,000. Has a range. A highly preferred polymer for use in the detergent composition according to the present invention is a polymer selected from N-vinylimidazole N-vinylpyrrolidone copolymers, the polymer being 5000-50,000, more preferably 8000-30,000.
Most preferably, it has an average molecular weight range of 10,000 to 20,000.
The average molecular weight range is Barth HGand Mays JW, Chemical Analysis, Vol.113, ”Mo.
dern Methods of Polymer Characterization ”. Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers are 5000-50,000, more preferably 8000-30,000.
Most preferably it has an average molecular weight range of 10,000 to 20,000. The N-vinylimidazole N-vinylpyrrolidone copolymers characterized by having the above average molecular weight range exhibit excellent dye transfer inhibiting properties while not adversely affecting the cleaning performance of the detergent compositions formulated therein. The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a ratio of 1:
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 composition of the present invention, about 2500 to about 400,000, preferably about 50.
Polyvinylpyrrolidone ("PVP") having an average molecular weight of 00 to about 200,000, more preferably about 5000 to about 50,000, and most preferably about 5000 to about 15,000 may also be utilized. A suitable polyvinylpyrrolidone is 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 BASF Cooperation include Sokalan HP165 and Sok.
alan HP12; polyvinylpyrrolidone known to detergent companies (eg EP-A-
262,897 and EP-A-256,696).

D) Polyvinyloxazolidone In the detergent composition of the present invention, polyvinyloxazolidone may also be used as a polymer transfer inhibitor. The polyvinyl oxazolidone is about 2500 to about 400.
1,000, preferably about 5000 to about 200,000, more preferably about 500.
It has an average molecular weight of from 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 about 2500 to about 400,0.
00, preferably about 5000 to about 200,000, more preferably about 5000 to
It has an average molecular weight of about 50,000, most preferably about 5,000 to about 15,000.

F) Cross- Linked Polymers Cross-linked polymers are polymers in which the backbones are to some extent linked, and these links may be of chemical or physical nature, possibly with active groups on the backbone or It may be on the side chain, and the cross-linked polymer is Journal of Polymer Science, volum.
e 22, pages 1035-1039. In one aspect, the cross-linked polymer is made to form a three-dimensional rigid structure and is capable of entrapping the dye in the pores formed by the three-dimensional structure. In another embodiment, the crosslinked polymer swells to capture the dye. 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 methods, pretreatment methods, and methods involving a rinse step in which another rinse aid composition may be added. Good. The process described herein conventionally comprises contacting the fabric, dishes or any other hard surface with a cleaning liquid, exemplified below. Conventional laundry methods consist of treating the soiled fabric with an aqueous liquid in which an effective amount of laundry detergent and / or fabric care composition is dissolved or dispensed. A preferred machine dishwashing method consists of treating the soil with an aqueous liquid in which an effective amount of the machine dishwashing or rinsing composition is dissolved or dispensed. A conventional effective amount of a machine dishwashing composition means 8 to 60 g of product dissolved or dispersed in a wash volume of 3 to 10 L. According to the hand dishwashing method, soiled dishes are typically contacted with an effective amount of the dishwashing composition of 0.5 to 20 g (per treatment of 25 dishes). Preferred hand dishwashing methods include application of the concentrate to the surface of the dish, or immersion in a large amount of diluent of the detergent composition. In conventional hard surface processes, soiled hard articles / surfaces are treated with, for example, a sponge, brush, cloth or the like to dissolve or disperse an effective amount of a hard surface cleaner in an aqueous liquid and / or undiluted such composition. To process. It also involves dipping the hard product in a concentrate or a large amount of diluent of the detergent composition. The process of the invention is expediently carried out during the cleaning process. The cleaning method is preferably carried out at 5 to 95 ° C, particularly 10 to 60 ° C. The pH of the treatment solution is preferably 7-12.

Preparation Example 1: Preparation of 3- (3,4-dihydroisoquinolinium) propanesulfonate ( 4) 250 ml equipped with magnetic stir bar, argon inlet, dropping funnel and reflux condenser.
In a round bottom flask are placed 3,4-dihydroisoquinoline (2, 5.005 g) and methanol (23 ml). The mixture is cooled in an ice bath and a solution of 1,3-propane sultone (3, 4.670 g) in methanol (23 ml) is added dropwise. After completion of dropping, the ice bath is removed, and the reaction solution is heated under reflux overnight. Cool the mixture to room temperature and remove the volatiles under reduced pressure. The solid product is slurried, rinsed 3 times with acetone and air dried. The manufacturing method is represented by the following reaction:

[Chemical 56]

[0198] Production Example 2: 1- fabrication steps of (3,4-dihydro-isoquinolinium) decan-2 Sarufe bets (5) 1: Production of 3,4-dihydroisoquinoline (2)

[Chemical 57] In a 100 ml round bottom flask equipped with a stir bar and a distillation device, phenethylamine (
1, 0.0413 mol) and 88% formic acid (7.6 g, 3.5 eq) are charged and the reaction is distilled or refluxed at about 100 ° C. Starting from 1 hour later, monitor by gas chromatography until the phenethylamine is consumed by an additional 88%.
Formic acid is added in 2 ml portions at intervals of about 30 minutes. The reaction mixture is distilled (using a Dean-Stark trap) at about 200 ° C. for about 45 minutes and then allowed to cool to room temperature. In a 250 ml round bottom flask equipped with a stir bar, reflux condenser and dropping funnel, 10
． Charge phosphorus pentoxide (7.07 g) and polyphosphoric acid in a 5: 1 weight ratio. The mixture is stirred and heated at about 180 ° C for about 1 hour and then cooled to about 150 ° C. The cooled composition phenethylformamide prepared above is added dropwise to this mixture. After the addition is complete, the reaction is heated and stirred overnight at about 170 ° C. The mixture was cooled to room temperature, diluted with water (300 ml) and diethyl ether (150 ml).
) And adjust the pH to 9 with saturated potassium hydroxide while cooling with an acetone / dry ice bath. The aqueous solution was extracted with ether (3 × 150 ml), the pooled organic phases were dried over magnesium sulfate, filtered and concentrated under reduced pressure to give an oil which was Kugelrohr distilled (70 ° C., 1 mmHg). Further purification gives the compound of formula 2.

Step 2: Preparation of 1,2-decanediol cyclic sulphate (4):

[Chemical 58] A 3-neck 500 ml round bottom flask equipped with a mechanical stirrer, pressure equalizing dropping funnel and reflux condenser with Drierite ^R packed dry tube was charged with 1,2-decanediol (3,8).
． 72 g, 50.0 mmol) and 50 ml carbon tetrachloride. Once the 1,2-decanediol has dissolved, thionyl chloride (5.5 ml, 75 mmol) is added dropwise at room temperature and the reaction is heated to about 60 ° C. After 2 hours, cool the reaction slowly to about 0 ° C. Deionized water (50 ml) and acetonitrile (75 ml) are added. Ruthenium chloride hydrate (0.13 g, 0.50 mmol) and sodium periodate (21.4 g, 100 mmol) are added and the reaction mixture is stirred at room temperature for 1 hour. The mixture was extracted with diethyl ether (4 x 175 ml) and the organic phase was deionized water (5 x
100 ml), saturated sodium bicarbonate solution (3 x 100 ml) and brine (2 x
Wash with 100 ml) then filter through Celite / silica gel. The filtrate is dried over magnesium sulphate, filtered and concentrated by rotary evaporation to a clear oil.

[0200] Step 3: Preparation of 1- (3,4-dihydro-isoquinolinium) decan-2 Sarufe over preparative (5)

[Chemical 59] A 100 ml round bottom flask equipped with a magnetic stir bar is charged with 3,4-dihydroisoquinoline (2.02 g, 15.4 mmol) and acetonitrile (15.2 ml). 1,2-decanediol cyclic sulfate (3.78g, 16.0mmol)
) All at once. Once the reaction mixture thickened, acetonitrile (60 m
l) is added and the reaction is stirred overnight. The precipitate is collected, washed 5 times with acetone and air dried.

The following examples are meant to illustrate the compositions of the invention and are not necessarily meant to limit or limit the scope of the invention. In detergent compositions, enzyme levels are expressed as pure enzyme by weight of total composition, unless otherwise noted detergent ingredients are expressed as weight of total composition. The abbreviated component designations have the following meanings: LAS: sodium linear C _11-13 alkylbenzenesulfonate TAS: sodium tallow alkylsulfate CxyAS: sodium C _1x -C _1y alkylsulfate CxySAS: sodium C _1x -C _1y. Secondary (2,3) alkyl sulphate MBAS x, y: sodium intermediate chain branched alkyl sulphate having an average of x carbon atoms (on average y carbon atoms are included in the (a) branching unit) CxyEz: average z moles ethylene oxide condensed with C _1x -C _1y predominantly in linear primary alcohol CxyEzS: mean z moles of ethylene oxide condensed with C _1x -C _1y sodium alkyl sulfate CxEOy: Cy alcohol Noni o of y ethoxylated with an average Systems: mixed ethoxylated / propoxylated fatty alcohols, for example an alcohol with an average ethoxylation degree 3.8 and the average propoxylation degree _{4.5 Plurafac LF404 QAS: R 2 N} + (CH 3) 2 (C 2 H 4 OH ) (R ₂ = C ₁₂ -C ₁₄ ) SADS: Formula 2-RC ₄ H ₇ -1,4- (SO ₄ ) ₂ (R = C _10-18 ) sodium C _14-22 alkyldisulfate MES: C ₁₈ fatty acid x sulfomethyl ester soap: derived from an 80/20 mixture of tallow and coconut fatty acid Sodium linear alkylcarboxylate silicate: amorphous sodium silicate (SiO ₂ : Na ₂ O ratio = 1.6-3 .2: 1) zeolite a: formula _Na 12 having a main particle size of 0.1~10μm range _{(AlO 2 SiO 2) 12 ·} 27H 2 O of hydrated sodium aluminum waves * RIQUET Doo (anhydrous basis weight display) Na-SKS-6: crystalline layered silicate citrate of formula _{δ-Na 2 Si 2 O 5} : trisodium citrate dihydrate Citric Acid: Anhydrous Citric acid Carbonate: Anhydrous sodium carbonate Bicarbonate: Sodium hydrogen carbonate sulfate: Anhydrous sodium sulfate STPP: Sodium tripolyphosphate TSPP: Tetrasodium pyrophosphate MA / AA: 4: 1 Random copolymer of acrylate / maleate Average molecular weight about 70,000-80,000 MA / AA1: 6: 4 Random copolymer of acrylate / maleate Average molecular weight about 10,000 AA: Sodium polyacrylate polymer with average molecular weight 4500 Polycarboxylate: acrylate, maleate and methyl acrylate in the range of MW 2000-80,000. Copolymers consisting of a mixture of such carboxylated monomers, for example acrylic acid copolymer, MW4500, commercially available from BASF, Sokalan BB1: 3- (3,4-dihydroisoquinolinium) propanesulfonate BB2 as prepared in Preparation Example 1: as prepared in preparation 2 1- (3,4-dihydro-isoquinolinium) decan-2-sulfate PB1: anhydrous sodium perborate monohydrate PB4: sodium perborate empirical formula NaBO ₂ · 4H ₂ O Tetrahydrate Percarbonate: Empirical formula 2.74 Na ₂ CO ₃ .3H ₂ O ₂ anhydrous sodium percarbonate DAP1: 30% dibenzoyl peroxide, 40% sodium sulfate, 5% Acusol 480N polymer, 2% maltodextrin, 12 % Ethoxylated stearyl alcohol and left as water Part diacyl peroxide particles DAP2: Dilauroyl peroxide NaDCC from Akzo: Sodium dichloroisocyanurate TAED: Tetraacetylethylenediamine NOBS: Sodium salt form of nonanoyloxybenzene sulfonate NACA-OBS: (6-Nonamidocaproyl) oxybenzene sulfonate DOBS: Sodium salt form of decanoyloxybenzenesulfonate DTPA: Diethylenetriaminepentaacetic acid HEDP: 1,1-Hydroxyethanediphosphonic acid DETPMP: Diethyltriamine penta (methylene) phosphonate EDDS: Ethylenediamine sold by Monsanto under the trade name Dequest 2060. -N, N'-disuccinic acid Its sodium salt form of the (S, S) isomer chelant: EEDS, HEDP, DTPA DETPMP and / or chelants catalyst mixtures thereof: Mn _(bicyclam) Cl 2 MnTACN: Manganese 1,4,7-trimethyl-1,4,7-triazacyclononane photoactivatable Bleach: dextrin soluble polymer Encapsulated Sulfonated Zinc Phthalocyanine Photoactivated Bleach 1: Sulfonated Aluminophthalocyanine PAAC Encapsulated in Dextrin-Soluble Polymer: Cobalt (III) Pentaamine Acetate (III) Salt Paraffin: Paraffin Oil Sold by Wintershall under the Trade Name Winog 70 NaBz: Sodium benzoate pectate lyase: Pectate lyase protease derived from Bacillus agaradhaerens NCIMB40482 or DSM8721: Protein sold under the trade names Savinase, Alcalase, Durazym from Novo Nordisk A / S Enzymes; Gist-Brocades, sold by Maxacal, Maxapem; and patent WO91 / 06637 and / or WO95 / 10591 and / or protease-amylase described in EP251446: sold under the trade name Purafact Ox Am ^R from Genencor Starch-degrading enzymes described in WO94 / 18314 and WO96 / 05295; all Termamyl ^R , Fungamyl ^R and Duramyl ^R commercially available from Novo Nordisk A / S; and those described in WO95 / 26397 (trade name from Novo Nordisk Sold by Natalase) Lipase: Novo Nordisk A / S under the trade name Lipolase, lipolytic enzyme sold under Lipolase Ultra, and Gist-Brocades Lipomax cellulase: Novo Nordisk A / S under the trade name Carezyme, Celluzyme and / or Endolase Cellulose-degrading enzyme pectinria sold at ZE: Pectin lyase CMC produced by Bacillus licheniformis ATCC 14580: Sodium carboxymethyl cellulose PVNO: Polyvinyl pyridine-N-oxide PVPVI having an average molecular weight of 50,000: Copolymer whitening agent of vinylimidazole and vinylpyrrolidone having an average molecular weight of 20,000 1: 4,4'-bis (2-sulfostyryl) biphenyl disodium brightener 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) stilbene-2 , 2'-Disodium disulphonic acid silicone antifoam agent: Polydimethyl siloxane foam control agent blended with siloxane-oxyalkylene copolymer as dispersant in the ratio of foam control agent to dispersant of 10: 1 to 100: 1 Suds suppressor: granular form, 12% Corn / silica, 18% stearyl alcohol, 70% starch thickener: BFGoodrich Chemical Company sold Carbopol and high molecular weight crosslinked polyacrylates, such as Polygel SRP1: anionic end-capped polyester 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 to 30) PEGx: polyethylene glycol PEO having a molecular weight x: polyethylene oxide having an average molecular weight of 5000 TEPAE: tetraethylene pentaamine ethoxylate BTA: benzotriazole pH: measured as a 1% solution in distilled water at 20 ° C.

Example 1 The following high density and bleach-containing laundry detergent compositions were prepared according to the present invention: I II III IV V VI Blown Powder: Zeolite A 12.0-15.0 12.0-15.0 Sulfate-5.0-5.0 -LAS 3.0-3.0 3.0-3.0 C45AS 3.0 2.0 4.0 3.0 2.0 4.0 QAS-1.5-1.5 DETPMP 0.4 0.4 0.4 0.4 0.4 0.4 CMC 0.4 0.4 0.4 0.4 0.4 0.4 MA / AA 1.0 2.0 2.0 1.0 2.0 2.0 Aggregate: QAS 1.0 ‐ ‐ 1.0 ‐ ‐ LAS ‐ 11.0 7.0 ‐ 11.0 7.0 TAS 2.0 2.0 1.0 2.0 2.0 1.0 Silicate 3.0 ‐ 4.0 3.0 ‐ 4.0 Zeolite A 8.0 8.0 8.0 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 8.0 8.0 4.0 Aggregate: NaSKS-6 15.0 12.0 5.0 15.0 12.0 5.0 LAS 8.0 7.0 4.0 8.0 7.0 4.0 Spray-on: Fragrance 0.3 0.3 0.3 0.3 0.3 0.3 C25E3 2.0-2.0 2.0-2.0 Dry additive: QEA 1.0 0.5 0.5 1.0 0.5 0.5 Citric acid / Citric acid Rate 5.0-2.0 5.0-2.0 Bicarbonate-3.0-3.0-Carbonate 8.0 15.0 10.0 8.0 15.0 10.0 TAED and / or NACA-OBS 6.0-5.0 6.0-5.0 NOBS-2.0-2.0-DAP1--6.7 4.8 5.2 Catalyst 0.002-0.02-0.02-Percarbonate 14.0 7.0 10.0 4.15 7.0 10.0 or PB1 BB1 0.40-0.20 ‐ ‐BB2 ‐0.14 ‐‐‐ MW 5,000,000 ‐‐0.2 ‐‐0.2 Polyethylene oxide Bentonite clay ‐‐‐ 10.0 ‐ -10.0 Citrate 4.0-1.5 4.0-1.5 Pectate lyase 0.001 0.02 0.01 0.001 0.02 0.01 Protease 0.033 0.033 0.033 0.033 0.033 0.033 Lipase 0.008 0.008 0.008 0.008 0.008 0.008 Amylase 0.001 0.001 0.001 0.001 0.001 0.001 Cellulase 0.0014 0.0014 0.0014 0.0014 0.0014 0.0014 Silicone foam Agent 5.0 5.0 5.0 5.0 5.0 5.0 Sulfate-3.0-3.0-Density (g / L) 850 850 850 850 50 to 850 moisture and other 100%

Example 2 The following high density and bleached laundry detergent formulations were prepared according to the present invention: I II III blown powder: Zeolite A 12.0-15.0 Sulfate-5.0-LAS 3.0-3.0 C45AS 3.0 2.0 4.0 QAS-1.5. DETPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA / AA 1.0 2.0 2.0 Aggregate: QAS 1.0- LAS-11.0 7.0 TAS 2.0 2.0 1.0 Silicate 3.0-4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Aggregate: NaSKS-6 15.0 12.0 5.0 LAS 8.0 7.0 4.0 Spray-on: Perfume 0.3 0.3 0.3 C25E3 2.0-2.0 Dry additive: QEA 1.0 0.5 0.5 Citric acid / citrate 5.0-2.0 Bicarbonate-3.0-Carbonate 8.0 15.0 10.0 Catalyst 0.002 0.02 0.02 TAED and // Or NACA-OBS 6.0-5.0 NOBS-2.0-Percarbonate / PB1 14.0 7.0 10.0 MW 5,000,000-0.2 Polyethylene Oxide Bentonite clay --- 10.0 Citric acid 4.0-1.5 Pectate lyase 0.001 0.02 0.01 Protease 0.033 0.033 0.033 Lipase 0.008 0.008 0.008 Amylase 0.001 0.001 0.001 Cellulase 0.0014 0.0014 0.0014 Silicone antifoam 5.0 5.0 5.0 Sulfate -3.0 --Density (g / L) 850 850 850 Moisture and others up to 100%

Example 3 The following laundry composition was prepared according to the present invention, which may be in the form of granules or tablets. I II III IV V Base Preparation C45AS / TAS 8.0 5.0 5.0 3.0 3.0 3.0 LAS 8.0-8.0-7.0 C25AE3S 0.5 2.0 1.0 --- C25AE5 / AE3 2.0-5.0 2.0 2.0 2.0 QAS --- 1.0 1.0 Zeolite A 20.0 18.0 11.0-10.0 SKS-6 (I) (dry addition) ) ‐ ‐ 9.0 ‐ ‐ MA / AA 2.0 2.0 2.0 ‐ ‐ AA ‐ ‐ ‐ ‐ 4.0 Citrate ‐ 2.0 ‐ ‐ ‐ ‐ Citric acid 2.0 ‐ 1.5 2. 0-DTPA 0.2 0.2 --- EDDS --- 0.5 0.1-HEDP --- 0.2 0.1-PB1 3.0 5.0 10.0-4.0 Percarbonate --- ‐ 18.0 ‐ NOBS 3.0 4.0 ‐ ‐ 4.0 NACA‐OBS ‐ ‐ 2.0 ‐ ‐ TA ED − − 2.0 5.0 − DAP1 4.8 3.6 6.9 − 5.2 DAP2 − − − 4.9 − catalyst − 0.02 − − − carbonate 15.0 18.0 8. 0 15.0 15.0 Sulfate 5.0 12.0 2.0 17.0 3.0 Silicate-1.0-8.0 Protease 0.033 0.033 0.033 0.046 0.033 Lipase 0.008 0.008 0.008 0.008 0.006 Amylase 0.001 0.001 0.001 0.0014 0.001 Cellulase 0.0014 0.0014 0.0014 0.01-Pectin lyase 0.001 --- Pectate lyase 0.001 0.002 0.02 0.05 0.005 Other 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Perfume 0.2 0.3 0.3 0.5 2 0.1 moisture and Others the up to 100% brightener / SRP1 / CMC / photobleach _/ MgSO 4 _/ PVPV
Includes I / foam inhibitor / PEG.

Example 4 The following laundry composition was prepared according to the present invention, which may be in the form of granules or tablets. I II III IV V Base Preparation C45AS / TAS 8.0 5.0 5.0 3.0 3.0 3.0 LAS 8.0-8.0-7.0 C25AE3S 0.5 2.0 1.0 --- C25AE5 / AE3 2.0-5.0 2.0 2.0 2.0 QAS --- 1.0 1.0 Zeolite A 20.0 18.0 11.0-10.0 SKS-6 (I) (dry addition) ) ‐ ‐ 9.0 ‐ ‐ MA / AA 2.0 2.0 2.0 ‐ ‐ AA ‐ ‐ ‐ ‐ 4.0 Citrate ‐ 2.0 ‐ ‐ ‐ ‐ Citric acid 2.0 ‐ 1.5 2. 0-DTPA 0.2 0.2 --- EDDS --- 0.5 0.1-HEDP --- 0.2 0.1-PB1 3.0 5.0 10.0-4.0 Percarbonate --- ‐ 18.0 ‐ NOBS 3.0 4.0 ‐ ‐ 4.0 NACA‐OBS ‐ ‐ 2.0 ‐ ‐ TA ED ‐ ‐ 2.0 5.0 ‐ BB1 0.06 ‐ 0.34 ‐ 0.14 BB2 ‐ 0.14 ‐ 0.20 ‐ Catalyst ‐ 0.001 ‐ ‐ 0.002 Carbonate 15.0 18.0 8.0 15.0 15.0 Sulfate 5.0 12 0.0 2.0 17.0 3.0 Silicate-1.0-8.0 Protease 0.033 0.033 0.033 0.046 0.033 Lipase 0.008 0.008 0.008 0.008 0.006 Amylase 0.001 0.001 0.001 0.0014 0.001 Cellulase 0.0014 0.0014 0.0014 0.01-Pectin Lyase 0.001 --- --- Pectate lyase 0.001 0.002 0.02 0.05 0.005 Others 0.5 0.5 0.5 0.5 0.5 0.5 Perfume 0.2 0.3 0.5 0.5 0.2 0.1 Moisture and other 100% Other the brightener / SRP1 / CMC / photobleaching _/ MgSO 4 _/ PVPV
Includes I / foam inhibitor / PEG.

Example 5 The following high density laundry detergent compositions were prepared according to the present invention: I II III IV V VI Aggregates: QAS 2.0-2.0 2.0-2.0 MES-2.0-2.0-LAS 6.0-6.0- TAS ‐ 2.0 ‐ ‐ 2.0 ‐ C45AS 6.0 4.0 2.0 6.0 4.0 2.0 MBAS 16.5,1.9 4.0 ‐ ‐ 4.0 ‐ ‐ Zeolite A 15.0 6.0 ‐ 15.0 6.0 ‐ Carbonate 4.0 8.0 4.0 4.0 8.0 4.0 MA / AA 4.0 2.0 ‐ 4.0 2.0 ‐ CMC 0.5 0.5-0.5 0.5-DETPMP 0.4 0.4-0.4 0.4-Spray-on: C25E3 1.0 1.0-1.0 1.0-Perfume 0.5 0.5 0.5 0.5 0.5 0.5 Aggregate: SKS-6 7.0 15.0 20.0 7.0 15.0 20.0 LAS 5.8 9.0 15.0 5.8 9.0 15.0 Zeolite ‐0.9 ‐ ‐0.9 ‐Water 0.08 0.1 ‐0.08 0.1 ‐Drying additive: EDDS / HEDP 0.5 0.3 0.5 0.5 0.3 0.5 NaSKS-6 (I) 5.0 6.0 4.0 5.0 6.0 4.0 Citrate ‐1.0 ‐ ‐1.0 ‐Citric acid 2.0 ‐ 2.0 2.0 ‐ 2 .0 NACA-OBS 4.1-5.0 4.1-5.0 TAED 0.8 2.0-0.8 2.0-Percarbonate 20.0 20.0 15.0 20.0 20.0 15.0 DAP1 ‐ ‐ 3.2 2.6 3.2 Catalyst ‐ 0.002 ‐ 0.002 ‐ BB1 0.45 ‐ 0.30 ‐ ‐ BB2 ‐ 0.25 ‐ ‐ ‐ SRP1 0.3 0.3 ‐ 0.3 0.3 ‐ Pectate lyase 0.002 0.01 0.03 0.002 0.01 0.03 Pectin lyase 0.001 ‐ ‐ 0.001 ‐ Protease 0.046 0.046 0.033 0.046 0.046 0.033 Lipase 0.008 0.008 0.006 0.008 0.008 0.006 Cellulase 0.0014 0.0014 0.001 0.0014 0.0014 0.0014 0.0014 0.001 0.001-0.001 0.001-0.00 QEA 1.0-1.0 1.0-1.0 Silicone defoamer 1.0 0.5 0.5 1.0 0.5 0.5 Whitening agent 1 0.2 0.2-0.2 0.2-Whitening agent 2 0.2-0.2 0.2-0.2 Density (g / L) 850 850 800 850 850 800 Moisture and others up to 100%

Example 6 The following granule detergents were prepared according to the invention: I II III IV V VI VII VIII Base Granules: STPP-22.0-15.0-22.0-15.0 Zeolite A 30.0-24.0 5.0 30.0-24.0 5.0 Sulfate 5.5 5.0 7.0 7.0 5.5 5.0 7.0 7.0 MA / AA 3.0 ‐ ‐ ‐ 3.0 ‐ ‐ ‐ AA ‐ 1.6 2.0 ‐ ‐ 1.6 2.0 ‐ MA / AA (1) ‐ 12.0 ‐ 6.0 ‐ 12.0 ‐ 6.0 LAS 14.0 10.0 9.0 20.0 14.0 10.0 9.0 20.0 C45AS 8.0 7.0 9.0 7.0 8.0 7.0 9.0 7.0 C45AE11S ‐1.0 ‐1.0 ‐1.0 ‐1.0 MES 0.5 4.0 6.0 ‐0.5 4.0 6.0 ‐SADS 2.5 ‐ ‐1.0 2.5 ‐ ‐1.0 Silicate ‐1.0 0.5 10.0 ‐1.0 0.5 10.0 Soap ‐2.0 ‐ ‐ ‐ ‐ 2.0 ‐ ‐ Whitening agent 1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Carbonate 6.0 9.0 8.0 10.0 6.0 9.0 8.0 10.0 PEG4000 ‐ 1.0 1.5 ‐ ‐ 1.0 1.5 ‐ DTPA ‐ 0.4 ‐ ‐ ‐ 0.4 ‐ ‐ Spray-on: C25E9 ‐ ‐ ‐ 5.0 - ‐ 5.0 C45E7 1.0 1.0 ‐ ‐ 1.0 1.0 ‐ ‐ C23E9 ‐ 1.0 2.5 ‐ ‐ 1.0 2.5 ‐ Perfume 0.2 0.3 0.3 ‐ 0.2 0.3 0.3 ‐ Dry additive: carbonate 5.0 10.0 13.0 8.0 5.0 10.0 13.0 8.0 PVPVI / PVNO 0.5 ‐ 0.3 ‐ 0.5-0.3-Protease 0.033 0.033 0.033 .0016 0.033 0.033 0.033 .0016 Lipase 0.008 ‐ ‐ 0.008 0.008 ‐ ‐ 0.008 Amylase .0016 ‐ ‐ .0016 .0016 ‐ ‐ .0016 Cellulase .0002 .0005 .0005 .0002 .0002 .0005 .0005 .0002 Pectate lyase 0.001 0.02 0.03 0.015 0.001 0.02 0.03 0.015 DTPA 0.5 0.3 0.5 1.0 0.5 0.3 0.5 1.0 PB1 5 3.0 10 4.0 5 3.0 10 4.0 DAP1 ‐ ‐ ‐ 3.8 6.7 4.3 3.2 Catalyst 0.001 ‐ ‐ 0.002 ‐ 0.001 ‐ ‐BB1 0.2 ‐ ‐0.5 ‐ ‐ ‐ BB2 ‐ 0.3 0.4 ‐ ‐ ‐ ‐ ‐ NOBS / TAED 0.5 0.3 0.5 0.6 0.5 0.3 0.5 0.6 Sulfate 4.0 5.0 ‐ 5.0 4.0 5.0 ‐ 5.0 SRP1 ‐ 0.4 ‐ ‐ ‐ 0.4 ‐ ‐ Inhibitor - 0.5 - - - 0.5 - - 1.7 1.2 water and other 100% - speckle 0.9 - 2.7 1.2 0.9

Example 7 The following laundry detergent composition was prepared according to the present invention: I II III IV V VI VII LAS 12.0 16.0 23.0 19 18.0 20.0 16.0 C45AS -4.5 --- --- C45E3S --- 2.0 --1.0 1.0 1.0 C45E6 .5S 2.0 2.0 - 1.3 - - 0.6 C 9 -C 14 alkyl dimethyl - - - - 1.0 0.5 2.0 hydroxyethyl quaternary NH ₄ salt tallow fatty - - - - - - 1.0 STPP 23.0 25.0 24.0 22.0 20.0 15.0 20.0 carbonate 15.0 12.0 15.0 10.0 13.0 11.0 10.0 Sodium polyacrylate (45%) 0.5 0.5 0.5 0.5 0.5 ‐ ‐ MA / AA ‐ ‐ 1.0 1.0 1.0 2.0 0.5 0.5 Silicate (1: 6 ratio) 3.0 6.0 9.0 8.0 9.0 6.0 8.0 Sulfate 25.0 18.0 20.0 18.0 20.0 22.0 13.0 PB1 5.0 5.0 10.0 8.0 3.0 1.0 2.0 PEG MW4000 (50%) 1.5 1.5 1.0 1.0 ‐ ‐ 0.5 CMC 1.0 1.0 1.0 ‐ 0.5 0.5 0.5 NOBS / DOBS 0.5 1.0 0.5 0.5 1.0 0.7 0.3 TAED 1.5 1.0 2.5 3.0 0.3 0.2 0.5 BB1-0.3-0.5 0.3-0.25 BB2 0.4-0.4-0.3 0.4-SRP1 1.5 1.5 1.0 1.0-1.0-SRP2 --- 1.0-1.0 Moisture 7.5 7.5 6.0 7.0 5.0 3.0 5.0 Sulfuric acid Mg ------ 1.0 0.5 1.5 Cherant ‐ ‐ ‐ ‐ 0.8 0.6 1.0 Protease 0.033 0.033 0.033 0.046 0.033 0.033 0.033 Lipase 0.008 0.008 0.008 0.008 0.006 ‐ Amylase 0.001 0.001 0.001 .0014 0.001 ‐ Cellulase .0014 .0014 .0014 0.01 ‐ .0005 .0005 Pectin Acid lyase 0.001 0.02 0.01 0.001 0.002 0.015 0.03 Pectin lyase 0.001 ‐ ‐ 0.001 0.001 ‐ ‐ Speckl 2.5 4.1 4.2 4.4 5.6 5.0 5.2 Other 1.0 1.0 1.0 1.0 0.5 1.5 1.0

Example 8 The following laundry detergent composition was prepared according to the invention: I II III IV V VI VII LAS 12.0 16.0 23.0 19 18.0 20.0 16.0 C45AS ‐4.5 ‐ ‐ ‐ 4.0 C45E0.5S ‐ ‐ ‐ ‐ ‐ ‐. ‐ C45E3S ‐ ‐ 2.0 ‐ 1.0 1.0 1.0 C45E6.5S 2.0 2.0 ‐ 1.3 ‐ ‐ 0.6 C ₉ ‐ C ₁₄ Alkyldimethyl ‐ ‐ ‐ ‐ 1.0 0.5 2.0 Hydroxyethyl quaternary NH ₄ salt tallow fatty acid ‐ ‐ ‐ ‐ ‐ ‐ ‐ 1.0 Tallow Alcohol ‐ ‐ ‐ ‐ ‐ ‐ ‐ Ethoxylate (50) STPP 23.0 25.0 24.0 22.0 20.0 15.0 20.0 Carbonate 15.0 12.0 15.0 10.0 13.0 11.0 10.0 Sodium 0.5 0.5 0.5 0.5 ‐ ‐ Polyacrylate (45%) MA / AA ‐ ‐ 1.0 1.0 1.0 2.0 0.5 Silicate (1: 6 ratio) 3.0 6.0 9.0 8.0 9.0 6.0 8.0 Sulfate 25.0 18.0 20.0 18.0 20.0 22.0 13.0 PB1 5.0 5.0 10.0 8.0 3.0 1.0 2.0 PEG MW ~ 4000 (50%) 1.5 1.5 1.0 1. 0 ‐ ‐ 0.5 CMC 1.0 1.0 1.0 ‐ 0.5 0.5 0.5 Citric acid ‐ ‐ ‐ ‐ ‐ ‐ ‐ Catalyst 0.05 0.005 0.1 0.002 0.02 0.05 0.005 NOBS / DOBS 0.5 1.0 0.5 0.5 1.0 0.7 0.3 TAED 1.5 1.0 2.5 3.0 0.3 0.2 0.5 SRP1 1.5 1.5 1.0 1.0 ‐ 1.0 ‐ SRP2 ‐ ‐ ‐ ‐ 1.0 ‐ 1.0 Moisture 7.5 7.5 6.0 7.0 5.0 3.0 5.0 Mg sulfate ‐ ‐ ‐ ‐ 1.0 0.5 1.5 Cherant ‐ ‐ ‐ ‐ 0.8 0.6 1.0 Protease 0.033 0.033 0.033 .0016 0.033 0.016 0.033 Lipase 0.008 ‐ -0.008 0.006 -0.006 Amylase .0016--.0016 0.001 0.001 .0016 Cellulase .0002 .0005 .0005 .0002-.0015 .0002 Pectate lyase 0.001 0.02 0.01 0.001 0.002 0.015 0.03 Pectin lyase 0.001 ‐ ‐ 0.001 0.001 ‐ ‐ Spectral 2.5 4.1 4.2 4.4 5.6 5.0 5.2 Other 1.0 1.0 1.0 1.0 0.5 1.5 1.0

Example 9 The following laundry detergent composition was prepared according to the present invention: I II III IV V VI VII VIII LAS 13.3 13.7 10.4 8.0 13.3 13.7 10.4 8.0 C45AS 3.9 4.0 4.5-3.9 4.0 4.5-C45E0.5S 2.0 2.0- ‐ 2.0 2.0 ‐ ‐ C45E3S ‐ ‐ ‐ ‐ ‐ ‐ ‐ C45E6.5S 0.5 0.5 0.5 5.0 0.5 0.5 0.5 0.5 C ₉ ‐C ₁₄ alkyl 1.0 ‐ ‐ 0.5 1.0 ‐ ‐ 0.5 dimethyl hydroxyethyl quaternary NH ₄ salt tallow fatty acid 0.5 ‐ ‐ ‐ 0.5 ‐ ‐ ‐ Tallow alcohol ‐ ‐ 1.0 0.3 ‐ ‐ 1.0 0.3 Ethoxylate (50) STPP ‐ 41.0 ‐ 20.0 ‐ 41.0 ‐ 20.0 Zeolite A 26.3 ‐ 21.3 1.0 26.3 ‐ 21.3 1.0 Carbonate 23.9 12.4 25.2 17.0 23.9 12.4 25.2 17.0 Sodium 3.4 0.0 2.7 ‐ 3.4 0.0 2.7 ‐ Polyacrylate (45%) MA / AA ‐ ‐ 1.0 1.5 ‐ ‐ 1.0 1.5 Silicate (1: 6 ratio) 2.4 6.4 2.1 6.0 2.4 6.4 2.1 6.0 Sulfate 10.5 10.9 8 .2 15.0 10.5 10.9 8.2 15.0 PB1 1.0 1.0 1.0 2.0 1.0 1.0 1.0 2.0 PEG MW4000 (50%) 1.7 0.4 1.0 ‐ 1.7 0.4 1.0 ‐ CMC 1.0 ‐ ‐ 0.3 1.0 ‐ ‐ 0.3 Citric acid ‐ ‐ 3.0 ‐ ‐ ‐ 3.0 ‐ BB1 1.0 0.5 0.6 ‐ ‐ ‐ ‐ BB2 ‐ 0.2 ‐ 1.0 ‐ ‐ ‐ ‐ DAP1 ‐ ‐ ‐ ‐ 2.0 2.1 3.4 2.1 NOBS / DOBS 0.2 0.5 0.5 0.1 ‐ ‐ ‐ TAED 0.6 0.5 0.4 0.3 ‐ ‐ ‐ ‐ ‐ SRP1 1.5 ‐ ‐ ‐1.5 ‐ ‐ ‐ SRP2 ‐ 1.5 1.0 1.0 ‐ 1.5 1.0 1.0 Moisture 7.5 3.1 6.1 7.3 7.5 3.1 6.1 7.3 Mg Sulfate ‐ ‐ ‐ 1.0 ‐ ‐ 1.0 Cherant ‐ ‐ ‐ ‐ 0.5 ‐ ‐ ‐ 0.5 Speckle 0.5 1.0 3.0 0.5 0.5 1.0 3.0 0.5 Protease 0.033 0.033 0.033 0.046 0.033 0.033 0.033 0.046 Lipase 0.008 0.008 0.008 0.008 0.008 0.008 0.008 0.008 Amylase 0.001 0.001 0.001 .0014 0.001 0.001 0.001 .0014 Cellulase .0014 .0014 .0014 0.01 .0014 .0014 .0014 0.01 Pectate Lyase 0.1. 001 0.01 0.005 0.002 0.001 0.01 0.005 0.002 Other 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0

Example 10 The following laundry composition was prepared according to the present invention, which may be in the form of granules or tablets. I II III IV V Base Preparation C45AS / TAS 8.0 5.0 5.0 3.0 3.0 3.0 LAS 8.0-8.0-7.0 C25AE3S 0.5 2.0 1.0 --- C25AE5 / AE3 2.0-5.0 2.0 2.0 2.0 QAS --- 1.0 1.0 Zeolite A 20.0 18.0 11.0-10.0 SKS-6 (I) (dry addition) ) ‐ ‐ 9.0 ‐ ‐ MA / AA 2.0 2.0 2.0 ‐ ‐ AA ‐ ‐ ‐ ‐ 4.0 Citrate ‐ 2.0 ‐ ‐ ‐ Citric acid 2.0 ‐ 1.5 0-DTPA 0.2 0.2 --- EDDS --- 0.5 0.1 --HEDP --0.2 0.2 0.1 --Catalyst 0.05 0.005 0.01 0.002 0.02 PB1 3.0 5.0 5.0 10.0 --4 0.0 Percarbonate ‐ ‐ 18.0 ‐ NOBS 3.0 4.0 ‐ ‐ 4.0 NACA-OB ‐ ‐ 2.0 ‐ ‐ TAED ‐ ‐ 2.0 5.0 ‐ Carbonate 15.0 18.0 8.0 15.0 15.0 Sulfate 5.0 12.0 2.0 2.0 17.0 3.0 Silicate-1.0-8.0 Protease 0.033 0.033 0.033 0.046 0.046 Lipase 0.008 0.008 0.008 0.008 0.008 Amylase 0.001 0.001 0.001 0.0014 0.0014 Cellulase 0.0014 0.0014 0.0014 0.01 0.01 Pectate lyase 0.001 0.002 0.02 0.05 0.005 Other 0.5 0.5 0.5 .5 0.5 0.5 perfume 0.2 0.3 0.5 0.2 0.1 moisture and Others the up to 100% brightener / SRP1 / CMC / photobleach _/ MgSO 4 _/ PVPV
Includes I / foam inhibitor / PEG.

Example 11 The following high density laundry detergent compositions were prepared according to the present invention: I II III IV Aggregates: QAS 2.0-2.0-MES-2.0-LAS 6.0- TAS-2.0-C45AS 6.0 4.0 2.0-MBAS 16.5,1.9 4.0 --- Zeolite A 15.0 6.0-Carbonate 4.0 8.0 4.0 8.0 MA / AA 4.0 2.0-2.0 CMC 0.5 0.5-0.5 DETPMP 0.4 0.4-0.5 Spray-on: C25E3 1.0 1.0-Perfume 0.5 0.5 0.5 0.5 Aggregate: SKS-6 7.0 15.0 20.0 10.0 LAS 5.8 9.0 15.0 10.0 Zeolite-0.9-C45AS-3.0-Water 0.08 0.1-0.2 Dry additive: EDDS / HEDP 0.5 0.3 0.5 0.8 NaSKS-6 5.0 6.0 4.0 11.0 Citrate-1.0-Citric acid 2.0-2.0 4.0 Catalyst 0.005 0.1 0.02 0.02 NACA-OBS 4.1-5.0 4.0 TAED 0.8 2.0-2.0 Percarbonate 20.0 20.0 15.0 17.0 SRP1 0.3 0.3-0.3 Pectate lyase 0.01 0.02 0.001 0.002 Pectin lyase- 0.001 0.001 Protease 0.046 0.046 0.033 0.016 Lipase 0.008 0.008 0.006 Cellulase 0.0014 0.0014 0.001 0.001 Amylase 0.003 0.003 0.005 QEA 1.0 1.0 1.0 0.5 Silicone defoamer 1.0 0.5 0.5 1.5 Whitening agent 1 0.2 0.2-6.2 Whitening agent 2 0.2-0.2- Density (g / L) 850 850 800 775 Moisture and other up to 100%

Example 12 The following granular fabric detergent composition, which exhibits "softening through the wash" ability, was prepared according to the present invention: I II III IV C45AS -10.0- 10.0 LAS 7.6-7.6-C68AS 1.3-1.3-C45E7 4.0-4.0-C25E3-5.0-5.0 Cocoalkyldimethyl 1.4 1.0 1. 4 1.0 Hydroxyethyl ammonium chloride citrate 5.0 3.0 3.0 5.0 3.0 Na-SKS-6-11.0-11.0 Zeolite A 15.0 15.0 15.0 15.0 MA / AA 4.0 4.0 4.0 4.0 DETPMP 0.4 0.4 0.4 0.4 DAP1 4.8 6.7 --- Catalyst --- 0.001 0.001 Percarbonate ---- 5.0 PB1-- 15.0-TAED--5.0 5.0 Smectite clay 10.0 10.0 10.0 10.0 10.0 HMWPEO-0.1-0.1 Pectate lyase 0.001 0. 01 0.001 0.01 Protease 0.02 0.01 0.02 0.01 Lipase 0.02 0.01 0.02 0.01 Amylase 0.03 0.005 0.03 0.005 Cellulase 0.001 -0.001-Silicate 3.0 5.0 5.0 3.0 5.0 Carbonate 10.0 10.0 10.0 10.0 10.0 Foaming suppressor 1.0 4.0 1.0 4.0 CMC 0 .2 0.1 0.2 0.2 Others Up to 100%

Example 13 The following liquid detergent formulation was prepared according to the present invention (levels shown in parts / weight; enzymes shown as pure enzyme): I II III IV V LAS 11.59 .0-4.0-C25E2.5S-3.0 18.0-16.0 C45E2.25S 11.5 3.0-16.0-C23E9-3.0 2.0 2.0 1.0 C23E7 3.2 ‐ ‐ ‐ CFAA ‐ ‐ 5.0 ‐ 3.0 TPKFA 2.0 ‐ 2.0 0.5 2.0 2.0 Citric acid (50%) 6.5 1.0 2.5 2.5 4.0 2 0.5 Ca formate 0.1 0.06 0.1 --- Na formate 0.5 0.5 0.06 0.1 0.05 0.05 SCS 4.0 1.0 3.0 3.0 1.2 -Borate 0.6 -3.0 2.0 3.0 3.0 Na hydroxide 6.0 2.0 3.5 3.5 4.0 3.0 Ethano 2.0 1.0 4.0 4.0 3.0 1,2-Propanediol 3.0 2.0 8.0 8.0 5.0 Monoethanolamine 3.0 1.5 1.0 2.5 1.0 TEPAE 2.0-1.0 1.0 1.0 1.0 catalyst 0.01 0.01 0.005 0.005 0.1 pectate lyase 0.001 0.002 0.01 0.01 0.005 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 ‐ ‐ ‐‐‐‐‐‐ PVNO ‐ ‐0 .3 -0.2 Whitening agent 1 0.2 0.07 0.1 --Silicone defoaming agent 0.04 0.02 0.1 0.1 0.1 Water and others up to 100%

Example 14 The following solid laundry detergent composition was prepared according to the present invention (levels are given in parts / weight; enzymes are given 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 Laurate Na 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 ‐ ‐ ‐ ‐ ‐ ‐ ‐ 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 Pectate Lyase 0.01 0.001 0.005 0.02 0.02 0.001 0.01 0.01 Amylase ‐ ‐ 0.01 ‐ ‐ 0.002 ‐ Protease ‐ 0.004 ‐ 0.003 0.003 ‐ ‐ 0.003 Lipase ‐ 0.002 ‐ 0.002 ‐ ‐ ‐ ‐ Cellulase ‐ .0003 ‐ ‐ .0003 .0002 ‐ ‐ Catalyst 1.0 5.0 0.1 3.0 10.0 1.0 0.3 1.0 PEO ‐ 0.2 ‐ 0.2 0.3 ‐ ‐ 0.3 Perfume 1.0 0.5 0.3 0.2 0.4 ‐ ‐ 0.4 Sulfate Mg ‐ ‐ 3.0 3.0 3.0 ‐ ‐ -Whitening agent 0.15 0.1 0.15 ‐ ‐ ‐ ‐ 0.1 Photoactivated bleach (ppm) ‐ 15.0 15.0 15.0 15.0 ‐ ‐ 15.0

Example 15 The following solid laundry detergent composition was prepared in accordance with the present invention (levels shown in parts / weight; enzymes shown as pure enzyme): I II III VI 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 Laurate Na 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 ‐ ‐ ‐ ‐ ‐ ‐ ‐ 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 Pectate lyase 0.01 0.001 0.005 0.02 0.02 0.1 0.01 0.01 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 Perfume 1.0 0.5 0.3 0.2 0.4 ‐ ‐ 0.4 Sulfate Mg ‐ ‐ 3.0 3.0 3.0 ‐ ‐ ‐ Whitening agent 0.15 0.1 0.15 ‐ ‐ ‐ ‐ 0.1 DAP1 0.4 0.6 0.8 1.0 ‐ ‐ 0.2 1.0 DAP2 ‐ ‐ ‐ 1.0 1.0 0.8 ‐ Photoactivated bleach (ppm) ‐ 15.0 15.0 15.0 15.0 ‐ ‐ 15.0

Example 16 The following solid laundry detergent composition was prepared according to the present invention (levels are given in parts / weight; enzymes are given as pure enzyme): I II III VI 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 Laurate Na 2.5 9.0 ‐ ‐ ‐ ‐ ‐ Zeolite A 2.0 1.25 ‐ ‐ ‐ 1.25 1.25 1.25 Carbonate 8.0 3.0 1.0 8.0 10.0 15.0 3.0 10.0 Ca Carbonate 27.5 27.0 35.0 ‐ ‐ 28.0 ‐ 28.0 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 ‐ ‐ ‐ ‐ ‐ ‐ ‐ 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 Pectate lyase 0.01 0.001 0.005 0.02 0.02 0.1 0.01 0.01 Pectin lyase-0.001 ‐ ‐‐‐‐‐ 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 Perfume 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 Catalyst 0.001 ‐ ‐ 0.001 ‐ ‐ ‐ BB1 0.2 0.2 0.3 ‐ ‐ 0.4 ‐ ‐ BB2 ‐ ‐ ‐ 0.4 0.5 ‐ 0.45 0.3 TAED 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7 PB4 12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0 NOBS 0.2 0.2 0.2 0.20 0.2 0.2 0.2 0.2 Photoactivated bleach (ppm) -15.0 15.0 15.0 15.0 ‐ ‐15.0

Example 17 The following compact high density (0.96 Kg / L) dishwashing detergent composition was prepared according to the present invention: I II III IV V VI STPP -51.0 51.0 -44.3 Citrate 17.0 -50.0 40.2 Carbonate 17.5 14.0 20.0 ‐ 8.0 33.6 Bicarbonate ‐ ‐ ‐ 26.0 ‐ ‐ Silicate 15.0 15.0 8.0 ‐ 25.0 3.6 Metasilicate 2.5 4.5 4.5 ‐ ‐ PB1 10.0 8.0 8.0 ‐ ‐ PB4 ‐ ‐ ‐ 10.0 ‐ ‐ Percarbonate ‐ ‐ ‐ ‐ ‐ 11.8 4.8 BB1 -0.1 0.1 -0.5 -BB2 0.2 0.05 -0.1 -0.6 Nonionic 2.0 1.5 1.5 3.0 1.9 5.9 TAED 2.0 ‐4.0 ‐1.4 HEDP 1.0 ‐ ‐ ‐ DETPMP 0.6 ‐ ‐ ‐ ‐ ‐ ‐ ‐ 0.01-PAAC-0.01 0.01 --- paraffin 0.5 0.4 0.4 0.6-Pectate lyase 0.04 0.1 0.03 0.5 0.005 0.005 Protease 0.072 0.053 0.053 0.026 0.059 0.01 Amylase 0.012 0.012 0.012 0.021 0.021 0.006 Lipase -0.001 -0.005 --- BTA 0.3 0.2 0.2 0.3 0.3 0.3 Polycarboxylate 6.0 --- 4.0 0.9 Perfume 0.2 0.1 0.1 0.2 0.2 0.2 pH 11.0 11.0 11.3 9.6 10.8 10.9 Sulfate, water and others 100 %Until

Example 18 The following granular dishwashing detergent composition having a bulk density of 1.02 Kg / L was prepared according to the present invention: I II III IV V VI STPP 30.0 33.5 27.9 29.6 33.8 22.0 Carbonate 30.5 30.5 30.5 23.0 34.5 45.0 Silicate 7.0 7.5 12.6 13.3 3.2 6.2 Metasilicate ‐4.5 ‐ ‐ ‐ ‐ Percarbonate ‐ ‐ ‐ ‐ 4.0 ‐ PB1 4.4 4.5 4.3 ‐ ‐ ‐ BB1 ‐ 0.3 ‐ 0.2 ‐ ‐ BB2 0.4 ‐ 0.2 ‐ 0.6 0.4 Nonionic 1.0 0.7 1.0 1.9 0.7 0.5 TAED 1.0- ‐ 0.9 ‐ PAAC ‐ 0.004 ‐ ‐ ‐ ‐ ‐ Paraffin 0.25 0.25 ‐ ‐ ‐ ‐ Pectate lyase 0.4 0.005 0.001 0.02 0.02 0.1 Protease 0.036 0.021 0.03 ‐ 0.006 ‐ Amylase 0.03 0.005 0.004 ‐ 0.005 ‐ Lipase 0.005 ‐ 0.001 ‐ 0.001 BTA 0.15 0.15 ‐ ‐ 0.2 ‐ Fragrance 0.2 0.2 0.05 0.1 0.2 ‐ pH (1% solution) 10.8 11.3 11.0 10.7 11.5 10.9 Sulfate, water and others Up to 100%

Example 19 The following tablet detergent composition was prepared at 13K using a standard 12 head rotary press.
Compression of the granules dishwashing detergent composition at a pressure of N / cm ^2, was prepared in accordance with the present invention: I II III IV V VI VII VIII STPP - 48.8 54.7 38.2 - 52.4 56.1 36.0 Citrate 20.0 - - - 35.9 - - - carbonate Salt 20.0 5.0 14.0 15.4 8.0 23.0 20.0 28.0 Silicate 15.0 14.8 15.0 12.6 23.4 2.9 4.3 4.2 Pectate lyase 0.001 0.001 0.01 0.004 0.02 0.02 0.001 0.005 Protease 0.042 0.072 0.042 0.031 0.052 0.023 0.023 0.029 Amylase 0.012 0.012 0.012 0.007 0.015 0.003 0.017 0.002 Lipase 0.005 ‐ ‐ ‐ ‐ ‐ PB1 14.3 7.8 11.7 12.2 ‐ ‐ 6.7 8.5 PB4 ‐ ‐ ‐ 22.8 ‐ 3.4 ‐ Percarbonate ‐ ‐ ‐ ‐ ‐ 10.4 ‐ ‐ BB1 0.2 ‐ 0.5 ‐ 0.3 0.2 ‐ ‐ BB2 ‐ 0.2‐ 0.5‐ 0.5‐ 0.1 0.2 Nonion type 1.5 2.0 2.0 2.2 1.0 4.2 4.0 6.5 PAAC ‐ ‐ 0.02 0.009 ‐ ‐ ‐ ‐ MnTACN ‐ ‐ ‐ ‐ ‐ 0.007 ‐ ‐ ‐ TAED 2.7 2.4 ‐ ‐ 2.1 0.7 1.6 HEDP 1.0 ‐ ‐ 0.9 ‐ 0.4 0.2 ‐ DETPMP 0.7 ‐ ‐ ‐ ‐ ‐ ‐ ‐ Paraffin 0.4 0.5 0.5 0.5 ‐ ‐ 0.5 ‐ BTA 0.2 0.3 0.3 0.33 0.3 0.3 0.3 ‐ Polycarboxylate 4.0 ‐ ‐ ‐ 4.9 0.6 0.8-PEG ‐ ‐ ‐ ‐ ‐ 2.0 ‐ 2.0 Glycerol ‐ ‐ ‐ ‐ ‐ 0.4 ‐ 0.5 Flavor ‐ ‐ ‐ ‐ 0.05 0.2 0.2 0.2 0.2 Tablet Weight 20g 25g 20g 30g 18g 20g 25g 24g pH 10.7 10.6 10.7 10.7 10.9 11.2 11.0 10.8 Sulfate , Water and others up to 100%

Example 20 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 STPP -51.0 51.0 -44.3 Citrate 17.0 -50.0 40.2 Carbonate 17.5 14.0 20.0 ‐ 8.0 33.6 Bicarbonate ‐ ‐ ‐ 26.0 ‐ ‐ Silicate 15.0 15.0 8.0 ‐ 25.0 3.6 Metasilicate 2.5 4.5 4.5 ‐ ‐ PB1 10.0 8.0 8.0 ‐ ‐ PB4 ‐ ‐ ‐ 10.0 ‐ ‐ Percarbonate ‐ ‐ ‐ ‐ ‐ 11.8 4.8 Nonion type 2.0 1.5 1.5 3.0 1.9 5.9 DAP1 0.2 1.0 4.3 6.7 1.7 0.3 TAED 2.0 ‐ 4.0 ‐ 1.4 HEDP 1.0 ‐ ‐ ‐ DETPMP 0.6 ‐ ‐ ‐ ‐ MTNTACN ‐ ‐ ‐ ‐ ‐ 0.01 ‐ PAAC ‐ 0.01 0.01 ‐ --- Paraffin 0.5 0.4 0.4 0.6 --- Pectate lyase 0.04 0.001 0.03 0.005 0.005 0.005 Protease 0.072 0.053 0.053 0.026 0.059 0.01 Amylase 0.012 0.012 0.012 0.021 0.021 0.006 Lipase-0.001-0.005--BTA 0.3 0.2 0.2 0.3 0.3 0.3 Polycarboxylate 6.0--4-4.0 0.9 Perfume 0.2 0.1 0.1 0.2 0.2 0.2 pH 11.0 11.0 11.3 9.6 10.8 10.9 Sulfate, water and others up to 100%

Example 21 The following granule dishwashing detergent composition having a bulk density of 1.02 Kg / L was prepared according to the present invention: I II III IV V VI STPP 30.0 33.5 27.9 29.6 33.8 22.0 Carbonate 30.5 30.5 30.5 23.0 34.5 45.0 Silicate 7.0 7.5 12.6 13.3 3.2 6.2 Metasilicate ‐4.5 ‐ ‐ ‐ ‐ Percarbonate ‐ ‐ ‐ ‐ 4.0 ‐ DAP1 3.3 6.7 0.03 0.5 10.0 0.03 PB1 4.4 4.5 4.3 ‐ ‐ NaDCC ‐ ‐ ‐ 2.0 ‐ 0.9 Nonionic 1.0 0.7 1.0 1.9 0.7 0.5 TAED 1.0- ‐ 0.9 ‐ PAAC ‐ 0.004 ‐ ‐ ‐ ‐ ‐ Paraffin 0.25 0.25 ‐ ‐ ‐ ‐ Pectate lyase 0.4 0.005 0.001 0.02 0.02 0.1 Protease 0.036 0.021 0.03 ‐ 0.006 ‐ Amylase 0.03 0.005 0.004 ‐ 0.005 ‐ Lipase 0.005 ‐ 0.001 ‐ 0.001 BTA 0.15 0.15 ‐ ‐ 0.2 ‐ Perfume 0.2 0.2 0.05 0.1 0.2 ‐ pH 10.8 11.3 11.0 10.7 11.5 10.9 Sulfate, water and others 10 % To

Example 22 The following tablet detergent composition was prepared at 13K using a standard 12 head rotary press.
Compression of the granules dishwashing detergent composition at a pressure of N / cm ^2, was prepared in accordance with the present invention: I II III IV V VI VII VIII STPP - 48.8 54.7 38.2 - 52.4 56.1 36.0 Citrate 20.0 - - - 35.9 - - - carbonate Salt 20.0 5.0 14.0 15.4 8.0 23.0 20.0 28.0 Silicate 15.0 14.8 15.0 12.6 23.4 2.9 4.3 4.2 Pectate lyase 0.1 0.001 0.01 0.4 0.02 0.02 0.1 0.005 Protease 0.042 0.072 0.042 0.031 0.052 0.023 0.023 0.029 Amylase 0.012 0.012 0.012 0.007 0.015 0.003 0.017 0.002 Lipase 0.005- ‐ ‐ ‐ ‐ ‐ ‐PB1 14.3 7.8 11.7 12.2 ‐ ‐ 6.7 8.5 PB4 ‐ ‐ ‐ ‐ 22.8 ‐ 3.4 ‐ Percarbonate ‐ ‐ ‐ ‐ ‐ 10.4 ‐ ‐ DAP1 0.6 0.8 1.0 1.2 1.1 0.8 0.5 1.4 Nonionic 1.5 2.0 2.0 2.2 1.0 4.2 4.0 6.5 PAAC ‐ ‐ 0.02 0.009 ‐ ‐ ‐ ‐ MnTACN ‐ ‐ ‐ ‐ 0.007 ‐ ‐ ‐ TAED 2.7 2.4 ‐ ‐ ‐ 2.1 0.7 1.6 HEDP 1.0 ‐ 0.9-0.4 0.2-DETPMP 0.7- ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ Paraffin 0.4 0.5 0.5 0.5 ‐ ‐ 0.5 ‐ BTA 0.2 0.3 0.3 0.3 0.3 0.3 0.3 ‐ Polycarboxylate 4.0 ‐ ‐ ‐ 4.9 0.6 0.8 ‐ PEG ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ ‐ 2.0 -2.0 Glycerol ‐ ‐ ‐ ‐ ‐ 0.4 ‐ 0.5 Flavor ‐ ‐ ‐ ‐ 0.05 0.2 0.2 0.2 0.2 Tablet weight 20g 25g 20g 30g 18g 20g 25g 24g pH 10.7 10.6 10.7 10.7 10.9 11.2 11.0 10.8 Sulfate, water and other up to 100%

Example 23 The following compact high density (0.96 Kg / L) dishwashing detergent composition was prepared according to the present invention: I II III IV V VI STPP -51.0 51.0 -44.3 Citrate 17.0 -50.0 40.2 Carbonate 17.5 14.0 20.0 ‐ 8.0 33.6 Bicarbonate ‐ ‐ ‐ 26.0 ‐ ‐Silicate 15.0 15.0 8.0 ‐ 25.0 3.6 Metasilicate 2.5 4.5 4.5 ‐ ‐ ‐ Catalyst 0.01 0.005 0.1 2.0 0.01 0.005 PB1 10.0 8.0 8.0 ‐ ‐ PB4 ‐ ‐ ‐ 10.0 ‐ ‐Percarbonate ‐ ‐ ‐ ‐ 11.8 4.8 Nonionic 2.0 1.5 1.5 3.0 1.9 5.9 TAED 2.0 ‐ ‐ 4.0 ‐ 1.4 HEDP 1.0 ‐ ‐ ‐ DETPMP 0.6 ‐ ‐ ‐ ‐ PAAC ‐ 0.01 0.01 ‐ ‐ ‐ Paraffin 0.5 0.4 0.4 0.6 --- Pectate lyase 0.04 0.001 0.03 0.005 0.005 0.005 Protease 0.072 0.053 0.053 0.026 0.059 0.01 Amylase 0.012 0.012 0.012 0.021 0.021 0.006 Lipase-0. 001-0.005--BTA 0.3 0.2 0.2 0.3 0.3 0.3 Polycarboxylate 6.0- --- 4.0 0.9 Perfume 0.2 0.1 0.1 0.2 0.2 0.2 pH 11.0 11.0 11.3 9.6 10.8 10.9 Sulfate, water and others up to 100%

Example 24 The following granule dishwashing detergent composition having a bulk density of 1.02 Kg / L was prepared according to the present invention: I II III IV V VI STPP 30.0 33.5 27.9 29.6 33.8 22.0 Carbonate 30.5 30.5 30.5 23.0 34.5 45.0 Silicate 7.0 7.5 12.6 13.3 3.2 6.2 Metasilicate ‐4.5 ‐ ‐ ‐ ‐ Catalyst 0.01 0.2 0.005 0.1 1.00 0.5 Percarbonate ‐ ‐ ‐ ‐ 4.0 ‐ PB1 4.4 4.5 4.3 ‐ ‐ NaDCC ‐ ‐ ‐ 2.0 ‐ 0.9 Nonion 1.0 0.7 1.0 1.9 0.7 0.5 TAED 1.0- ‐ ‐ 0.9 ‐ PAAC ‐ 0.004 ‐ ‐ ‐ ‐ ‐ Paraffin 0.25 0.25 ‐ ‐ ‐ ‐ Pectate lyase 0.004 0.005 0.001 0.02 0.02 0.001 Protease 0.036 0.021 0.03 ‐ 0.006 ‐ Amylase 0.03 0.005 0.004 ‐ 0.005 ‐ 0.005‐ 0.001‐ 0.001 BTA 0.15 0.15 ‐ ‐ 0.2 ‐ Perfume 0.2 0.2 0.05 0.1 0.2 ‐ pH 10.8 11.3 11.0 10.7 11.5 10.9 Sulfate, water and others 10 % To

Example 25 The following tablet detergent composition was prepared at 13K using a standard 12 head rotary press.
Compression of the granules dishwashing detergent composition at a pressure of N / cm ^2, was prepared in accordance with the present invention: I II III IV V VI VII VIII STPP - 48.8 54.7 38.2 - 52.4 56.1 36.0 Citrate 20.0 - - - 35.9 - - - carbonate Salt 20.0 5.0 14.0 15.4 8.0 23.0 20.0 28.0 Silicate 15.0 14.8 15.0 12.6 23.4 2.9 4.3 4.2 Pectate lyase 0.001 0.001 0.01 0.004 0.02 0.02 0.001 0.005 Protease 0.042 0.072 0.042 0.031 0.052 0.023 0.023 0.029 Amylase 0.012 0.012 0.012 0.007 0.015 0.003 0.017 0.002 Lipase 0.005 ‐ ‐ ‐ ‐ ‐ ‐ Catalyst 0.001 0.003 0.05 0.001 0.001 0.003 0.01 0.001 PB1 14.3 7.8 11.7 12.2 ‐ ‐ 6.7 8.5 PB4 ‐ ‐ ‐ ‐ 22.8 ‐ 3.4 ‐ Percarbonate ‐ ‐ ‐ ‐ ‐‐ 10.4 ‐ ‐ Nonion 1.5 2.0 2.0 2.2 1.0 4.2 4.0 6.5 PAAC ‐ ‐ 0.02 0.009 ‐ ‐ ‐ ‐ TAED 2.7 2.4 ‐ ‐ ‐ 2.1 0.7 1.6 HEDP 1.0 ‐ ‐ 0.9 ‐ 0.4 0.2 ‐ DETPM 0.7- ‐ ‐ ‐ ‐ ‐ ‐ Paraffin 0.4 0.5 0.5 0.5 0.5 ‐ ‐ 0.5 ‐ BTA 0.2 0.3 0.3 0.3 0.3 0.3 0.3 ‐ Polycarboxylate 4.0 ‐ ‐ ‐ 4.9 0.6 0.8 ‐ PEG ‐ ‐ ‐ ‐ ‐ ‐ ‐ 2.0 ‐ 2.0 glycerol ‐ ‐ ‐ ‐ ‐ ‐ ‐ 0.4 ‐ 0.5 Fragrance ‐ ‐ ‐ 0.05 0.2 0.2 0.2 0.2 Tablet weight 20g 25g 20g 30g 18g 20g 25g 24g pH 10.7 10.6 10.7 10.7 10.9 11.2 11.0 10.8 Sulfate, water and others up to 100%

Example 26 The following liquid rinse aid composition was prepared according to the present invention: I II III IV Pectate Lyase 0.001 0.0005 0.01 0.001 Pectin Lyase 0.001 0.001-0.001 Catalytic 0.1 0.01 0.008 0.001 Nonionic System 10 0.0 13.6 62.3 60.0 Propylene glycol --5.0 5.0 5.5 Citric acid 3.5 4.6 --SCS 10.0 7.7 --Liquid pH 3.0 3.0 2.5 7 .2 7.2 Solvents, water and others up to 100%

Example 27 The following automatic dishwashing tablets were prepared according to the invention (raw material g; enzyme is indicated as pure enzyme) I II III IV V VI Phase I STPP 9.6 9.6 10.6 9.6 9.6 10.6 Silicate 0.5 0.7 2.9 0.5 0.7 2.9 SKS-6 1.5 1.5-1.5 1.5-Carbonate 2.3 2.7 2.8 2.3 2.7 2.8 HEDP 0.2 0.2 0.2 0.2 0.2 0.2 PB1 2.4 2.4 2.8 2.4 2.4 2.8 PAAC 0.002 0.002 ‐ ‐ ‐ ‐ ‐ ‐ ‐ 0.002 0.002 ‐ BB1 0.2 0.5- ‐ ‐ DAP1 ‐ ‐ 0.5 ‐ ‐ 0.2 Amylase 0.1 0.1 0.001 0.1 0.1 0.001 Protease 0.06 0.06 0.002 0.06 0.06 0.002 Nonionic 0.4 0.8 0.4 0.4 0.8 0.4 PEG6000 0.4 0.26 ‐ 0.4 0.26 ‐ BTA 0.04 0.04 0.06 0.04 0.04 0.06 Paraffin 0.1 0.10 0.1 0.1 0.10 0.1 perfume 0.02 0.02 0.02 0.02 0.02 0.02 total 17.7g 18.5g 20.1g 17.7g 18.5g 20.1g phase 2 pectate lyase 0.005 0.5 0.2 0.005 0.5 0.2 pectin lyase 0.001 - - 0.001 -Amylase 0.003 0.003 0.004 0.003 0.003 0.004 Protease 0.01 0.009 0.01 0.01 0.009 0.01 Citric acid 0.3-0.6 0.3-0.6 Sulfamic acid-0.3-0.3-bicarbonate 1.1 0.4 0.6 1.1 0.4 0.6 Carbonate-0.5-0.5-Triacetin- ‐ 1.2 ‐ ‐ 1.2 CaCl ₂ ‐ 0.07 0.1 ‐ 0.07 0.1 PEG6000 ‐ ‐ 1.2 ‐ ‐ 1.2 PEG3000 0.06 0.06 ‐ 0.06 0.06 ‐ Total 2.05g 2.50g 23.6g 2.05g 2.50g 23.6g

Tablet compositions I and II are prepared as follows. The first phase detergent active composition is prepared by mixing the granules and liquid ingredients and then passed through a conventional rotary press die. The press is equipped with punches of suitable shape for forming the mold. The die cross section is approximately 30 x 38 mm. A compression force of 940 kg / cm ² is then applied to the composition, after which the punch is raised to expose the first phase of the tablet containing the mold on its top surface. A second phase detergent active composition is similarly prepared and passed through the die. A compressive force of 170 kg / cm ² is then applied to the granular active composition, the punch is raised and the multiphase tablets are removed from the tableting press. The tablets obtained dissolve or disintegrate in the washing machine as described above within 12 minutes and the second phase of the tablets dissolves within 5 minutes. The tablets show improved strength, especially on long-term storage, together with excellent dissolution properties. Tablet Composition III was prepared as follows: The composition of the active detergent ingredients was placed in the punched holes of a modified rotary tableting press and the composition was compressed at a pressure of 940 kg / cm ² to give a compressed part. To prepare. The modified tabletting press provides tablets with a compressed part having a mold. For the purposes of Example III, the uncompressed portion is in granular form. Accurately insert the uncompressed part into the mold of the compressed part using the nozzle feeder. The uncompressed portion is attached to the compressed portion by coating the uncompressed portion with a coating layer that contacts the compressed portion.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C11D 3/39 C11D 3/39 3/395 3/395 D06L 1/12 D06L 1/12 3/02 3 / 02 (31) Priority claim number US9900801 (32) Priority date January 14, 1999 (January 14, 1999) (33) Priority claim country United States (US) (31) Priority claim number US9900802 (32) Priority date January 14, 1999 (January 14, 1999) (33) Priority claiming country United States (US) (31) Priority claim number US9900803 (32) Priority date January 14, 1999 (1999. 1.14) (33) Priority claiming country United States (US) (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU , MC, NL, PT, SE), OA (BF, B , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG , ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH , CN, CR, CU, CZ, DE, DK, DM, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MA, 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, N, YU, ZA, ZW (72) Inventor Michael, Stanford, Showwell United States Ohio, Cincinnati, Compton, Road, 685 (72) Inventor Yang, Two United States Ohio, Cincinnati, Bromyard, Avenue, 4348 (72) ) Inventor Rosa, Laura, Maize U.S. Ohio, West, Chester, Eagle, Creek, Court, 8815 (72) Inventor Jean-Luc, Philip, Bétior Belgian Be-1200, Brussels, Avenue, Sléger , 93 (72) Inventor Alfred, Bush Belgium-1840, Ronderzer, Handelsstraat, 210 (72) Inventor Eric, See. Wells United States of America Ohio, Cincinnati, West, Kemper, Road, Number 1601, 1440 F Term (reference) 4H003 AB19 AB27 AC08 AE06 DA01 DA05 DA12 DA17 DA19 EA12 EA15 EA16 EA20 EA28 EB08 EB10 EB12 EB32 EB21 EB32 EB21 EB21 EB24 EB24 EB24 EB24 EB42 EC03 EE05 FA04 FA43 FA47

Claims (30)

[Claims] 1. A detergent component, a pectate lyase enzyme, and a metal bleach catalyst; from a peroxygen source and a dipolar imine, an anionic imine polyion having a net negative charge of -1 to -3 and / or a mixture thereof. A detergent composition containing a bleach system selected from the group consisting of diacyl peroxide and / or mixtures thereof in combination with a bleach booster selected from the group consisting of: 2. A metal bleach catalyst having: (a) [Mn (biscyclam) Cl ₂ ] catalyst; (b) Formula: Co [(NH ₃ ) _n M _m B _b T _t Q _q P _p ] Y _y . Cobalt catalyst (in the above formula, cobalt is +3 oxidized form; n is an integer of 0-5, preferably 4-5, more preferably 5; M represents a monodentate ligand; m is 0-5, preferably Is an integer of 1 or 2, more preferably 1, B represents a bidentate ligand;
b is an integer from 0 to 2; T represents a tridentate ligand; t is 0 or 1;
Q is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p
Is 0 or 1; n + m + 2b + 3t + 4q + 5p = 6; Y is one or more appropriately selected counter anions present in the number y to obtain a charge-balanced salt, where Y is -1. When it is a valent anion, y is 1 to 3, preferably 2
To 3, more preferably 2 is an integer); cobalt catalyst (in the above formula (c) having a formula [Co _{(NH 3) 5} M] _{T y,} cobalt is the +3 oxidation state; M is formula RC ( O) is a carboxylate-containing ligand having O-; T is a number y (y is an integer) (when T is a -1 valent anion, preferably 1 in order to obtain a charge-balanced salt. ~
3 and more preferably one or more counter anions present in 2)); and / or mixtures thereof. 3. A metal bleach catalyst, and further a peroxygen source, preferably selected from the group consisting of hydrogen peroxide source, peroxyacid bleach precursor compounds and / or mixtures thereof. The detergent composition according to claim 1 or 2. 4. The metal bleach catalyst comprises 1 ppb to 10% by weight of the total composition, preferably 0.1.
The composition according to claim 2 or 3, which is present in an amount of ppm to 1%, more preferably 1 ppm to 0.1%. 5. The diacyl peroxide of claim 1, wherein the diacyl peroxide is selected from the group consisting of dibenzoyl peroxide, benzoylglutaryl peroxide, benzoylsuccinyl peroxide, di (2-methylbenzoyl) peroxide and / or mixtures thereof. The detergent composition according to any one of claims. 6. The detergent composition according to claim 5, wherein the diacyl peroxide is dibenzoyl peroxide. 7. The diacyl peroxide is contained in particles, the particles comprising 1-80% by weight of the particles.
7. A detergent composition according to any one of claims 1 to 6, which comprises 0.01 to 95% by weight of the particles of a water-soluble stabilizing additive. 8. Stabilizing additives are alkali metal sulphates and citrates, ethoxylated C _16-20 alcohols, polyethylene glycols melting above 100 ° F., maltodextrins, polyacrylate polymers, copolymers of molecular weight 1000-80,000. The detergent composition according to claim 7, which is selected from the group consisting of ethylenediaminetetraacetic acid, ethylenediaminedisuccinic acid and / or a mixture thereof. 9. The detergent composition according to any one of claims 1 to 4, wherein the diacyl peroxide is dilauroyl peroxide. 10. Diacyl peroxide is 0.01 to 20% by weight of the composition, preferably 0.5.
%, More preferably 0.2 to 3%.
The detergent composition according to claim 9. 11. The diacyl peroxide is incorporated in the fine particles, and the particles are 0% of the total composition.
． The detergent composition according to any one of claims 7 to 10, which is contained at a level of 1 to 30%, preferably 1 to 15%, more preferably 1.5 to 10%. 12. The bleach booster is selected from the group consisting of aryliminium zwitterions, aryliminium polyions with a net negative charge of -1 to -3, and / or mixtures thereof. The detergent composition according to claim 11. 13. The bleach booster has the formula: Where: R ¹ -R ³ is a moiety having a total charge of about 0 to about -1; R ¹ and R ² form part of a common ring; T is-(CH ₂ ) _B- (b is about 1
About 8),-(CH (R ⁵ ))-(R ⁵ is C ₁ -C ₈ alkyl),-
CH ₂ (C ₆ H ₄ )-, embedded image And _{- (CH 2) d (E} ) (CH 2) f - (d is 2 to 8, f is 1 to 3, E is -C (O) O -, - C (O) NR 6 Or [Chemical 3] R ⁶ is H or C ₁ -C ₄ alkyl); Z is covalently bonded to T, Z is —CO ₂ ^— , —SO ₃ ^— and —OSO ₃ ^- is selected from the group consisting of, a is 1 or 2) a detergent composition according to claim 12. 14. R ¹ and R ² are taken together to form an uncharged moiety: The detergent composition according to claim 12 or 13, wherein the detergent composition is formed. 15. The bleach booster is an aryliminium zwitterion, R ³ is H, T is — (CH ₂ ) _b — or —CH ₂ (C ₆ H ₄ ) —, and Z is —. The detergent composition according to any one of claims 12 to 14, which is SO ₃ ⁻ , a is 1, and b is 2 to 4. 16. The bleach booster is an aryliminium zwitterion having the formula: embedded image The detergent composition according to any one of claims 12 to 15. 17. The bleach booster has the formula: embedded image (In the above formula, R ¹ -R ³ are hydrogen, or phenyl, aryl, heterocyclic ring,
Is an unsubstituted or substituted group selected from the group consisting of alkyl and cycloalkyl groups; R ¹ and R ² form part of a common ring; T has the formula: In the above formula, x is 0 or 1; J is -CR ¹¹ R ¹² , -C when present.
R ¹¹ R ¹² CR ¹³ R ¹⁴ and -CR ¹¹ R ¹² CR ¹³ R ¹⁴ CR ¹⁵ R ¹⁶ are selected from the group consisting of; R ⁷ -R ¹⁶ is H, straight chain or branched C ₁ -C _{1 8} substituted or Selected from the group consisting of unsubstituted alkyl, alkylene, oxyalkylene, aryl, substituted aryl, substituted arylcarbonyl groups, and amido groups; provided that at least one of R ⁷ -R ⁸ is H or methyl. No
One of R ⁷ -R ⁸ must be H when neither R ⁹ nor R ¹⁰ is H; Z is covalently bonded to J _x when x is 1 and to C _b when x is 0. Z is selected from the group consisting of —CO ₂ ^— , —SO ₃ ^— and —OSO ₃ ^— ;
Is 1), The detergent composition according to claim 12. 18. In a bleach booster, R ¹ and R ² together form an uncharged moiety: 18. The detergent composition of claim 17, wherein R ¹ and R ² are defined as forming 19. The detergent composition according to claim 17, wherein the bleach booster is an aryliminium zwitterion, R ³ is H, Z is —OSO ₃ ^— , and a is 1. . 20. A bleach booster is an aryliminium zwitterion having the formula: embedded image The detergent composition according to any one of claims 17 to 19, wherein R ¹⁷ is selected from the group consisting of H, straight chain or branched C ₁ -C ₁₈ substituted or unsubstituted alkyl. 21. The detergent composition according to any one of claims 1 to 20, wherein the bleach booster is contained at a level of 0.01 to 10% by weight of the total composition. 22. The detergent composition according to any one of claims 12 to 21, wherein the peroxygen source is contained at a level of 0.01 to 60% by weight of the total composition. 23. Peroxygen source is percarboxylic acid and salt, percarbonate and salt, perimidic acid and salt, peroxymonosulfuric acid and salt, and / or mixtures thereof; hydrogen peroxide source, bleach activator and / or 23. A detergent composition according to any one of claims 12 to 22 which comprises a preformed peracid compound selected from the group consisting of mixtures thereof. 24. The detergent composition according to claim 23, wherein the hydrogen peroxide source is selected from the group consisting of perborate compounds, percarbonate compounds, perphosphate compounds and / or mixtures thereof. 25. The bleach activator is tetraacetylethylenediamine, sodium decanoyloxybenzenesulfonate, sodium nonanoyloxybenzenesulfonate, sodium octanoyloxybenzenesulfonate, (6-octanamidocaproyl) oxybenzenesulfonate, The detergent composition according to claim 23, which is selected from the group consisting of (6-nonanamidocaproyl) oxybenzene sulfonate, (6-decanamidocaproyl) oxybenzene sulfonate and / or mixtures thereof. 26. Pectate lyase is 0.0001 to 2% by weight of the total composition, preferably 0.0.
26. A detergent composition according to any one of claims 1 to 25 present at a pure enzyme level of 005 to 1.0%, more preferably 0.001 to 0.5%. 27. The detergent composition according to any one of claims 1 to 26, which further contains pectin lyase. 28. Use of a composition according to any one of claims 1 to 27 for the removal of plant soil based stains, highly pigmented food soils / stains and body soils. 29. Use of a composition according to any one of claims 1-27 for maintaining good fabric whiteness. 30. Use for removing highly colored stains and stains effective in plastic products and / or for preventing stains and / or discoloration of dishes with highly colored components.
Use of the composition according to any one of 11.