JP2002534593A - Detergent composition containing pectin-degrading enzyme system - Google Patents

Abstract

  (57) [Summary] The present invention relates to a detergent composition containing a pectate lyase and a pectin lyase to provide an excellent cleaning effect, that is, a plant-based stain / soil and body stain, darkness cleaning property and white maintenance property.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a detergent composition containing an enzyme system containing pectate lyase (EC 4.2.2.2) and pectin lyase (EC 4.2.2.20).

BACKGROUND OF THE INVENTION The performance of a detergent product is judged by a number of factors, including the ability to remove soil and the ability to prevent redeposition of soil or the breakdown products of soil on articles in laundry liquor. Thus, detergent compositions today comprise a complex combination of active ingredients that meet certain specific requirements. In particular, current detergent formulations generally include surfactants and cleaning enzymes that provide cleaning and knitting protection benefits.

[0003] Removal of plant, wood, loam-clay based soils, mud soils and stains from fruits is one of today's most troublesome cleaning tasks today, especially in the trend toward lower wash temperatures. . These stains typically contain a complex mixture of fibrous materials: fibers and cell wall components, mainly based on carbohydrates and their derivatives. Plant-based soils are additionally accompanied by amylose, sugar and their derivatives. Food soils are often difficult to effectively remove from soiled supports. Highly colored or "dried" stains from fruit and / or vegetable juices are particularly difficult to remove. Particular examples of such stains include orange juice, tomato juice, banana, mango or broccoli stains. In fact, pectin polymers are important components of plant cell walls. Pectin consists of alternating homogalacturonan (smooth area) and rhamnogalacturonan (hairy area)
Is a heteropolysaccharide having a main chain consisting of The smooth region is a linear polymer of 1,4-linked α-D-galacturonic acid. Galacturonic acid residues are methyl-esterified on the carboxyl groups to varying degrees, usually in a non-random manner, and the blocks of polygalacturonic acid are completely methyl-esterified. Substrates in which pectin-containing stains are commonly found may be knitted fabrics (fabrics), tableware or hard surfaces.

[0004] In addition, the complex nature of everyday "body" stains, typically found on pillowcases, T-shirts, collars and socks, provides a continuous thorough cleaning problem for detergents. These stains are difficult to completely remove, in part because of their interaction with the pectin components in the primary cell wall of the cotton fibers that make up the cotton-containing knitted fabric, and residues often form in such knitted fabrics. Accumulates on fabrics, causing darkening and yellowing. In addition, bodily fluid stains, such as blood and menstrual fluid, are often difficult to effectively remove from soiled articles, especially when the stain has become old. Routine body soils are also found on sanitary facilities and kitchen surfaces such as bathtubs, toilet bowls and dishes.

[0005]

[Prior art]

The use of enzymes in detergents is well known in the art. For example, amylase enzymes have long been used in detergent compositions to remove starchy food residues or to remove starchy films from dishes or hard surfaces, and to improve the cleaning performance of starchy soils, as well as soils commonly encountered in laundry. It has been recognized as bringing. Proteinase enzymes have long been recognized in detergent compositions for removing proteinaceous food soils from dishes and hard surfaces, and for cleaning proteinaceous soils as well as those soils commonly encountered in laundry. . In addition, the use of cellulases is also well known in the art. This activity provides the fabric with cleaning, renewal, softening, and, typically, improved hand properties in the fabric construction. It is known to include lipolytic enzymes (eg, lipases) in detergent compositions to improve cleaning performance, for example, to facilitate removal of triglyceride-containing stains and spot stains from knitted fabrics.

[0006] Pectinolytic enzymes, especially when used in washing and cleaning operations to provide a wide range of plant and fruit based stain removal and to enhance the body soil cleaning profile of detergent compositions, It is known to provide / stain removal benefits. By pectin degrading enzyme is meant herein any enzyme that acts to degrade pectin substances and pectin related substances. Pectinolytic enzymes can be classified by their preferred substrate, high or low methyl-esterified pectin and polygalacturonic acid (pectate) and their reaction mechanism, β-elimination or hydrolysis. Pectinolytic enzymes primarily act internally to cleave the polymer at random sites in the chain, resulting in a mixture of oligomers, or they act externally, starting from one end of the polymer to form monomers or dimers. obtain. Some pectinase activities that act on the blunt regions of pectin are described by the class of enzymes provided by Enzyme Nomenclature (1992), such as pectate lyase (EC 4.2.2.2), pectin lyase (EC 4.2.2). .1
0), polygalacturonase (EC 3.2.1.15), exo-polygalacturonase (EC 3.2.1.67), exo-polygalacturonase lyase (EC
EC 4.2.2.9) and exo-poly-α-galacturonosidase (EC3
. 2.1.82). Pectinolytic enzymes are natural mixtures having the enzymatic activity described above.

[0007] Each type of pectolytic enzyme has a unique profile of substrate specificity, activity and stability under different hardness, pH, temperature, surfactant and other detergent component matrix conditions. Pectin degrading enzymes are specifically directed to degrade pectin substances, especially plant cell walls. In particular, pectate lyase enzymes are specifically directed to plant cell wall pectate chains, such as low methoxy pectins (LMPs), whereas pectin lyases are more specific to esterified pectin chains, such as high methoxy pectins (HMPs). Turned to In addition, it has been found that pectate lyase is sensitive to metals, especially calcium, whereas pectin lyase does not require metals for stabilization and optimal enzyme activity.

Surprisingly, it has been found that a wide range of substrate specificities and high applicability to various washing conditions can be achieved with a combination of pectate lyase and pectin lyase. This results in synergistic cleaning, especially removal of plant-based stains / stains and body stains.

Furthermore, it has been found that the performance of the detergent composition of the present invention is enhanced by the addition of a bleach.

[0010]

[Means for Solving the Problems]

The use of pectolytic enzymes in detergents is already recognized in the art. The use of pectin enzymes has also been recognized for cleaning contact lenses (U.S. Pat. No. 4,710,313-J60196724). Enzymes with pectinase activity increase the detergent's ability to remove inorganic soils, e.g., sludge, from laundry without damaging the fiber and without fading, resulting in a lower inorganic dispersing capacity than phosphate. The use of zeolites and carbonate builders having a glycerol is described in DE 36 35 427. The advantages of using pectin enzymes in detergent formulations, especially for use in laundry, dishwashing and household cleaning operations, are recognized in WO 95/25790. JP 60226599 describes detergent compositions containing conventional detergent actives and cellulases and hydrolases, such as hemicellulases, pectinases, amylases or proteases. The combination of cellulase and hydrolase is said to produce a good cleaning effect on the inorganic fouling together with the enzymatic activity. WO 95/09909 describes an enzyme preparation containing a modifying enzyme selected from the group of amylase, lipase, oxidoreductase, pectinase or hemicellulase. In this case, the modified enzyme has improved performance due to increased alkaline pI and / or surface activity obtained by chemical modification or amino acid substitution. Modified pectin and / or pectolytic and / or hemicellulolytic and / or lipolytic enzymes are advantageously applied to the paper industry, and modified amylase and / or lipase are advantageously applied to laundry and dishwashing.

In particular, pectate lyases have been cloned from different bacterial genera, such as Erwinia, Pseudomonas, Klebsiella, Streptomyces, Penicillium, Bacteroides, Thermomonospora, Fusarium, Aspergillus and Xanthomonas. Was done. 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 describe cloning of pectate lyase. Bacillus pu
milus) (Dave and Vaughn (1971) J. Bacteriol. 108: 166-174), B. polymyxa
(Nagel and Vaughn (1961) Arch. Biochem. Biophys. 93: 344-352), B. stear
othermophilus (Karbassi and Vaughn (1980) 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) Can. J. Microbiol. 24: 116)
Purification of a pectate lyase with maximum activity in the pH range of 8 to 10 produced by 4-1172) has been reported. WO 98/45393 discloses detergent compositions containing protopectinase which have a pronounced detergency against mud soils.

Pectin enzymes are described in WO94 / 21786, WO95 / 34223 and F
As described in R2638064, it is used in the fruit / vegetable juice manufacturing industry for the clarification of juice by the degradation (depectinization) of pectin substances therein. German Patent Specification 3,635,427 (published April 23, 1985, Lion C
orporation) refers to a phosphate-free detergent containing an enzyme with pectinase activity for cleaning clothes.

However, a synergistic combination of pectate lyase (EC 4.2.2.2) and pectin lyase (EC 4.2.2.20), which provides excellent performance in detergent compositions, was previously It was never recognized.

SUMMARY OF THE INVENTION The present invention provides excellent cleaning performance, that is, excellent cleaning performance against plant-based stains / stains and body stains;
Detergent compositions, including laundry, dishwashing, and hard surface cleaner compositions, containing pectate lyase and pectin lyase.

DETAILED DESCRIPTION OF THE INVENTION Pectate Lyase Enzyme An essential element of the compositions of the present invention is the pectate lyase enzyme.

Pectate lyase is classified as EC 4.2.2.2 in the enzyme classification provided by the Enzyme Nomenclature, 1992. The enzyme cleaves the α-1,4, glucosidic bond of galacturonic acid in the pectin substrate and produces C4 and C5
And has substantially no other pectolytic activity, ie, 25
It is known to have less than 15% by weight, preferably less than 15% by weight, more preferably less than 5% by weight of other pectinolytic enzyme active compounds.

The pectate lyase is obtained from Erwinia, Pseudomonas, Klebsiella, Strepomyces, P
enicillium, Baceriodess, Thermomonospora, Fusarium, Aspergillus and Xanth
It has been cloned from different bacterial genera, such as omonas. Also, Baci
llus subtilis (Nasser et al. (1993) FEBS 335: 319-326) and Bacillus sp. YA-14 (Kim et al (1994) Biosci. Biotech. Biochem. 58
: 947-949) describes the cloning of pectate lyase. Bacillu
s pumilus (Dave and Vaughn (1971) J. Bacteriol. 108: 166-174), B. polymyxa
(Nagel and Vaughn (1961) Arch.Biochem.Biophys. 93: 344-352), B. stearot
hermophilus (Karbassi and Vaughn (1980) Can.J. Microbiol. 26: 377-384), B
acillus sp. (Hasegawa and Nagel (1966) J. Food Sci. 31: 838-845) and Bacillu
RK9 (Kelly and Fogarty (1978) Can. J. Microbiol. 24: 1164-1172). Purification of a pectate lyase having maximum activity in a pH range of 8-10 has been reported. WO98 / No. 45393 discloses a detergent composition containing protopectinase, which has a remarkable detergency against mud stains.

Further, pectate lyases suitable for use in the present invention are described in WO 98/45.
No. 393, when polygalacturonic acid is used as a substrate, protopectinase and EP having an optimum reaction pH of 7.0 or above.
Pectate lyase having the amino acid sequence of SEQ ID NO: 870843, SEQ ID NO: 1, or having one or more of its amino acid sequences deleted, added or substituted.

Preferred is PCT / DK98 / 00515 (1998)
A pectate lyase enzyme described in International Application on Nov. 24, 2012): a pectate lyase in which the first amino acid sequence consists of seven amino acid residues having the following sequence: Asn Leu Asn Ser Arg Val Pro ( NLNSRVP);

The pectate lyase is: i) by Bacillus agaradhaerens, NCIMB 40482 or DSM 8721, or by Bacil
lus agaradhaerens A polypeptide produced by a Bacillus species having at least 99% 16S rDNA sequence homology with DSM 8721, or ii) SEQ ID NO: 2-2 shown in PCT / DK98 / 00515.
A polypeptide containing the amino acid sequence at position 7-359, or iii) an analog of the polypeptide defined in i) or ii), having at least 45% homology with said polypeptide; or iv) 240 Substitution, deletion or addition of one or several amino acids of the peptide, optionally 245, provided that the arginine at position 245 is maintained and the derived polypeptide has at least 42% homology Induced by
v) It is immunologically reactive with the polyclonal antibody obtained against the peptide in purified form.

The pectate lyase is: i) according to Bacillus licheniformis, ATCC 14580 or Bacillus licheniformis
Bacillus with at least 99% 16S rDNA sequence homology to ATCC 14580
A polypeptide produced by the species, or ii) 28-341 of SEQ ID NO: 4 of PCT / DK98 / 00515.
A polypeptide containing the amino acid sequence indicated in the position, or iii) an analog of the polypeptide defined in i) or ii), having at least 45% homology with said polypeptide; or iv) 233 Substitution, deletion or addition of one or several amino acids of the peptide, optionally 238, provided that the arginine at position 238 is maintained and the derived polypeptide has at least 42% homology Induced by
v) those that are immunologically reactive with the polyclonal antibody obtained against the peptide in purified form.

The pectate lyase is: i) 16S rD of SEQ ID NO: 14 of PCT / DK98 / 00515
Depending on the Bacillus species having the NA sequence or the SE of PCT / DK98 / 00515
A polypeptide produced by a Bacillus species having greater than 97.3% 16S rDNA sequence homology to the sequence of Q ID NO: 14; or ii) 181-5 of SEQ ID NO: 6 of PCT / DK98 / 000051
A polypeptide containing the amino acid sequence shown at position 09, or iii) an analog of the polypeptide defined in i), having at least 50% homology with said polypeptide, or iv) position 390; Optionally, also at position 395, provided that arginine is maintained and the derived polypeptides have at least 44% homology,
Those derived by substitution, deletion or addition of one or several amino acids of the peptide; v) those which are immunologically reactive with the polyclonal antibody obtained against the peptide in purified form; is there.

The pectate lyase is: i) a polypeptide produced by Bacillus halodurans species, or ii) PCT / DK98 / 00115, SEQ ID NO: 8, 42-348.
A polypeptide containing the amino acid sequence indicated in the position, or iii) an analog of the polypeptide defined in i) or ii), having at least 45% homology with said polypeptide, or iv) 240 At position, optionally, and also at position 245, provided that arginine is maintained and the derived polypeptide has at least 40% homology.
Those derived by substitution, deletion or addition of one or several amino acids of the peptide; v) those which are immunologically reactive with the polyclonal antibody obtained against the peptide in purified form; is there.

The pectate lyase is: i) 16S rDNA of SEQ ID NO: 13 of PCT / DK98 / 00515
Depending on the Bacillus species having the sequence or in PCT / DK98 / 00515 SE
A polypeptide produced by a Bacillus species having a Q ID NO: 13 sequence and 16S rDNA sequence homology greater than 98.1%; or ii) 25-3 of SEQ ID NO: 10 of PCT / DK98 / 00515
A polypeptide containing the amino acid sequence shown at position 35, or iii) an analog of the polypeptide defined in i), having at least 45% homology with said polypeptide, or iv) position 227; Arginine is optionally maintained at position 232,
Derived by substitution, deletion or addition of one or several amino acids of the peptide, provided that the derived polypeptide has at least 41% homology, v) obtained against the peptide in purified form Is immunologically reactive with the polyclonal antibody obtained.

Similarly, international co-pending application PCT / DK98 / 00514 (November 1998)
The pectate lyase enzyme described in International Application 24/24) is preferred: i) a polypeptide produced by Bacillus licheniformis, ATCC 14580, or ii) 28- of SEQ ID NO: 4 of PCT / DK98 / 00514. 22
A polypeptide containing the amino acid sequence shown at one position, or iii) an analog of the polypeptide defined in i) or ii), having at least 60% homology with said polypeptide, or iv) Lysines at positions 133 and 155, arginine at position 158 are maintained, and the derived polypeptide is identified in SEQ ID NO: PCT / DK98 / 00514.
: 4. Derived by substitution, deletion or addition of one or several amino acids of the peptide, provided that they have at least 66% homology with positions 60-158 of 4); One that is immunologically reactive with the polyclonal antibody obtained against the peptide;

For the purposes of the present invention, more preferred pectate lyases have optimal activity when the pH is above 7.0, and are preferably Streptomyces fradiae, Streptomyces nitrosporeus, E.
rwinia carotovora, Bacillus spheroides, Thermomonospora fusca, Pseudomon
as solanacearum, Bacteroides thetaiotaomicron, Fusarium solani, Xanthomo
nas campestris, Bcillus agaradhaerens and / or Bacillus licheniformis. For the purposes of the present invention, the most preferred pectate lyase is Bcillus agaradhaeren
s, pectate lyase from NCIMB 40482 or DSM 8721. Pectate lyase is present in the detergent composition of the present invention in a concentration of pure enzyme, preferably 0.0001 to 2% by weight of the composition, more preferably 0.0005 to 0.1% by weight.
, Most preferably 0.001 to 0.02% by weight.

Pectin lyase enzyme The essential component of the detergent composition of the present invention is classified into EC 4.2.2.10 according to the EC classification, contains substantially no other pectin enzymes, acts on pectic acid, and acts on alpha- 1-
Resulting in non-hydrolytic cleavage of the 4-glycosidic bond and terminal 4-deoxy-6-α-D
-A pectin lyase enzyme which leads to oligosaccharides of galacto-enuronosyl groups. In a preferred embodiment, the detergent composition of the present invention contains an alkaline pectin lyase enzyme substantially free of other pectin enzymes. The term "alkali" intends a pectin lyase enzyme having an enzyme activity of at least 10%, preferably 25%, more preferably 40% of the optimal activity in the pH range 7-11, preferably in the pH range 7-11. A pectin lyase enzyme having optimal activity is contemplated. Enzyme activity was determined by K. Horikoshi in Agr. Biol. Chem, Vol 36 (2), 28
6 "Assay of trans-eliminase activities toward pectin and pectic
acid ".

The pectin lyase of the present invention is substantially free of other pectin enzymes. "Substantially free of other pectin enzymes" means less than 25%, preferably less than 15%,
More preferably, it means a pectin lyase enzyme-containing composition containing less than 5% of a pectin enzyme that is not a pectin lyase enzyme.

The pectin lyase enzyme is substantially free of other pectin enzymes and, according to the invention, is usually according to the invention in the detergent composition 0.0001 to 2% by weight of the total composition, preferably 0.1 to 0.2%. It is contained at a concentration of pure enzyme of 0005 to 0.5% by weight, more preferably 0.001 to 0.1% by weight.

Pectin substances are found in plant tissues and are a common constituent of fruit juices such as orange, tomato and grape juices. The pectin substance contains polycalacturonic acid and / or their derivatives. They contain pectin and pectic acid. Pectin is usually composed of galacturonic acid chains linked by alpha-1-4 glycosidic bonds. Normally, native pectin has about two thirds of the carboxylic acid groups esterified with methanol. Partial hydrolysis of these methyl esters results in low methoxy pectin, which is prone to calcium ions and gels. Complete hydrolysis of the methyl ester yields pectic acid.

Pectin lyase enzyme is substantially free of other pectin enzymes and includes naturally occurring pectin lyase enzymes and any variants obtained, for example, by genetic engineering techniques.

The pectin lyase enzyme is substantially free of other pectin enzymes and is used to construct a pectin lyase in a pure form or to construct a hybrid vector expressing a foreign gene, PLA, PLB, PPLC, PLE or PLE
J5613376, EP3, which discloses a DNA sequence or a deleted sequence encoding
Bacillus species, preferably B. firmus, B. circulans, as described in US Pat.
And produced from B. subtilis. A pectin lyase expression system used for the overproduction of pectin lyase in Aspergillus and / or for the construction of hybrid vectors of expressed genes in filamentous fungi is described in EP 278355. An enzyme mixture containing pectin lyase is available from Certain Asperg disclosed in HUT033216.
It can be obtained from a submerged aerobic medium of the species illus niger. J020350
No. 88 also describes a pectin lyase gene from the Erwina bacterial gene and useful for the production of the enzyme. Pectin lyase was also purified from fungal origin-pectin degrading enzyme mixtures, such as Aspergillus niger and Aspergillus japonicus
May be. Purified pectin lyase was obtained from Agr. Biol. Chem, V. by K. Horikoshi.
ol 36 (2), 288; World Journal of Microbiology and Bi by V. Shevchik et al.
otechnology, Vol 8, (1992), 116 and "Protein pu" by E. Harris et al. (1989).
rification methods, a practical approach "Ed IRL Press, Oxford, England
And can be obtained by purification and / or fractional distillation as known in the art.

Commercially available pectin lyase enzymes that are substantially free of other pectin enzymes include Sigm
From a, P7052 from Aspergillus niger, P2804 from Aspergillus japonicus, Asper
There are P5936 from gillus japonicus and P2679 from Aspergillus japonicus, which are commercially available. Also commercially available from Worthington under the trade names LS04297, LS04298 and LS04296
There is a pectin lyase enzyme from pergilus niger.

A preferred pectin lyase for the purposes of the present invention is described in co-pending international application PCT / D
K98 / 000051 (International application filed on November 24, 1998),
i) a polypeptide produced by Bacillus Licheniformis, ATCC 14580, or ii) PCT / DK98 / 00514 SEQ ID NO: 2 31-49.
A polypeptide containing the amino acid sequence shown at position 4, or iii) an analog of the polypeptide defined in i) or ii), having at least 60% homology with said polypeptide, or iv) Arginine at positions 377 and 383 of SEQ ID NO: 2 of PCT / DK98 / 00514 are maintained and the derived polypeptide is at least 60%
And a polyclonal antibody derived against the peptide in a purified form derived from the substitution, deletion or addition of one or several amino acids of the peptide, provided that the peptide has immunology. That are reactive to

Preferably, the detergent composition of the present invention comprises these two enzymes in the total composition in a concentration of pure enzyme of from 0.0001 to 4% by weight, more preferably from 0.0005 to 2% by weight, most preferably Preferably, the content is 0.001 to 1% by weight. Preferably, pectate lyase and pectin lyase are present in the detergent composition of the present invention in a weight ratio of pure enzyme of 10:
1-1: 10, more preferably 5: 1 to 1: 5, most preferably 2: 1 to 1: 2.
It is contained in.

[0036] The pectate lyase and / or pectin lyase included in the detergent composition of the present invention, in addition to the enzyme core containing the catalytic domain, also contains a cellulose binding domain (CBD) and the enzyme cellulose The binding domain and the enzyme core (catalytically active domain) are operably linked. The cellulose binding domain (CBD) can be present as an integral part of the encoding enzyme, or CBD from other species can be introduced into the enzyme to create a hybrid enzyme. In this sense, the term “cellulose-binding domain” is defined by Peter Tomme et al.
llulose-Binding Domains: Classification and Properties "in" Enzymatic De
gradatiion of Insoluble Carbohydrates ", John N. Saddler and Michael H. P
Enner (Eds.), as understood by the ACS Symposium Series, No. 618, 1996. This definition classifies more than 120 cellulose binding domains into 10 families (IX), and CBD is found in various enzymes such as cellulases, xylanases, mannanases, arabinofuranosidases, acetylesterases and chitinases. Indicates that CBD is a non-hydrolyzable polysaccharide-
As a binding protein, for example, it is found in sows such as red alga Porphyra purpurea (see Tomme et al., Op.cit.). However, most CBD is from cellulases and xylanases, and CBD is found at the N and C termini or inside the protein. Enzyme hybrids are known in the art (eg, WO90 /
00609 and WO 95/16782), the host is mannanase and / or
Or a DNA encoding a pectate lyase and / or a xyloglucanase enzyme
Prepared by transforming the sequence with or without a linker, a DNA structure containing a ligated version of at least one DNA fragment encoding a cellulose binding domain, and culturing a host expressing the fusion gene be able to. The enzyme complex is represented by the following formula:

Embedded image

Wherein the CBD is at least the N-terminal or C-terminal region of the amino acid sequence corresponding to the cellulose binding domain; the MR is preferably from about 2 to about 100, more preferably 2 to 40. An intermediate region of carbon atoms (linking group), a bond or a short linking group; preferably about 2 to about 100 amino acids, more preferably 2 to 4 amino acids
X is the N-terminal or C-terminal region of the pectate lyase and / or pectin lyase of the invention.

The above-mentioned enzymes are of suitable origin, such as of plant, animal, bacterial, fungal and yeast origin. The origin may be mesophilic or extreme (cryophilic, low-temperature, thermophilic, pressure-philic, alkaline-philic, acidophilic, salt-philic, etc.). Purified or unpurified forms of these enzymes are used. At present, it is common practice to modify natural-type enzymes by protein / gene technology to optimize their efficiency performance in the detergent compositions of the present invention. For example, variants are designed to increase the compatibility of the enzyme with commonly used components. The variants are also designed such that the optimal pH, bleaching or chelation stability, catalytic activity, etc. of the variant are suitable for a particular cleaning application.

In particular, attention should be paid to oxidation-sensitive amino acids for bleach stability and surface charges for surfactant compatibility. The isoelectric point of such enzymes can be modified by substitution of some charged amino acids, for example, increasing the isoelectric point can help improve compatibility with anionic surfactants . Enzyme stability can be further enhanced by, for example, creating additional salt bridges to increase chelator stability and reinforcing calcium binding sites.

Detergent Composition The detergent composition of the present invention must contain at least one additional detergent component. The exact nature of these additional components and their concentration will depend on the physical properties of the composition and the cleaning operation in which the composition is used.

The detergent composition of the present invention preferably further contains a bleaching agent.

[0042] The detergent composition of the present invention may be in liquid, paste, gel, rod, tablet, spray, foam, powder or granular form. Particulate compositions can be in "compact" form, and liquid compositions can be in "concentrated" form. A tablet composition may be in the form of a single layer or multiple layers.

A first aspect of the present invention relates to a laundry detergent and / or knit care composition comprising pectate lyase and pectin lyase (Examples 1 to 15). A second aspect of the present invention relates to a dishwashing or household detergent composition (Examples 16 to 24).
.

The compositions of the present invention may be formulated, for example, as hand dishwashing compositions, hand and machine wash laundry detergent compositions, including, for example, laundry additive compositions, and stained knitted fabrics. And compositions for use in general household hard surface cleaning operations. When formulated as a composition for use in a hand-washing dishwashing method, the compositions of the present invention preferably comprise a surfactant, and preferably an organic polymeric compound, a soap foam enhancer, a Group II metal ion, a solvent. , A hydrotrope and other detergent compounds selected from additional enzymes.

When formulated as a composition suitable for use in a washing machine method, the composition of the present invention preferably comprises both a surfactant and a builder compound, and additionally one or more detergent components. Ingredients, preferably detergent components selected from organic polymeric compounds, bleaches, additional enzymes, foam inhibitors, dispersants, lime soap dispersants, soil suspending and anti-redeposition agents, and corrosion inhibitors. It contains. Laundry compositions may also contain softening agents as additional detergent compositions. Such compositions containing pectate lyase and pectin lyase can provide knitted fabric cleaning, stain removal and color appearance when formulated as a laundry detergent composition.

When formulated as a composition suitable for use in a machine dishwashing method, the composition of the present invention preferably comprises an organic polymeric compound, a bleach, an additional enzyme, a foam inhibitor,
It contains one or more components preferably selected from a dispersant, a lime soap dispersant, a soil suspending agent, an anti-redeposition agent and a corrosion inhibitor, a low-foaming nonionic surfactant, and a builder system.

The compositions of the present invention may also be used as solid or liquid detergent additive materials.
Such additive materials can be added at any stage of the cleaning operation that is intended to supplement or enhance the performance of conventional detergent compositions.

If necessary, the density of the laundry detergent compositions herein can range from 400 to 1200 g / l of composition, preferably 500 to 950 g / l of composition, measured at 20 ° C. is there. The "compact" form of the compositions herein is best reflected by density and, for compositions, by the amount of inorganic filler salt. Inorganic filler salts are a conventional component of detergent compositions in powder form, where in conventional detergent compositions the filler salt is present in substantial amounts, typically 17-35% by weight of the total composition. Exists. In a compact composition, the filler salt is present in an amount not exceeding 15% by weight of the total composition,
Preferably it is present in an amount not exceeding 10%, most preferably not exceeding 5% by weight of the composition. The inorganic filler salt as meant in the composition according to the invention is selected from alkali metal and alkaline earth metal sulfates and chlorides. A preferred filler salt is sodium sulfate. The liquid detergent compositions of the present invention can also be in "concentrated form". In such a case, the liquid detergent composition of the present invention may contain a smaller amount of water than a conventional liquid detergent. usually,
The water content of the concentrated liquid detergent is preferably less than 40% by weight of the detergent composition, more preferably less than 30% by weight, and most preferably less than 20% by weight.

[0049] Suitable detergent compounds for use in the present invention are selected from the group consisting of the compounds described below.

Bleaching Agents Surprisingly, it has been found that the detergent compositions of the present invention further containing a bleaching agent, particularly a bleaching activator bleaching system, provide food stain removal and whiteness retention.
While not intending to be bound by theory, the smaller plastid particles resulting from the combined hydrolysis of pectate lyase and pectin lyase enzymes are more readily attacked with bleach activators, especially at low temperatures. I believe it will be done.

Preferred detergent components that can be included in the detergent composition of the present invention are 400 to
Bleaching agents such as hydrogen peroxide, PB1, PB4 and percarbonate having a particle size of 800 microns. These bleach components may contain one or more oxygen bleaches, and may contain one or more bleach activators, depending on the bleach selected. The oxygen bleach compounds of the present invention may typically be present at a concentration of about 1% to about 25%.

[0052] The bleach component for use herein can be any bleach useful in cleaning compositions, including oxygen bleaches as well as others known in the art. Bleaches suitable for the present invention can be activated or deactivated bleaches.

One type of oxygen bleach that may be used includes percarboxylic acid bleaches and salts thereof. Suitable examples of this type of drug include magnesium monoperoxyphthalate hexahydrate, magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4
-Oxoperoxybutyric acid and diperoxidedecanedioic acid. Such bleaching agents are disclosed in U.S. Pat. No. 4,483,781, U.S. Pat.
446, European Patent Application 0,133,354 and U.S. Pat.
No. 934. Highly preferred bleaches are described in U.S. Pat.
No. 551 also includes 6-nonylamino-6-oxoperoxycaproic acid. Another type of bleach that may be used includes halogen bleaches. Examples of hypohalite bleaches include, for example, trichloroisocyanuric acid, and sodium and potassium dichloroisocyanurate, and N-chloro and N-bromoalkanesulfonamides. Such substances are usually added at 0.5 to 10% by weight of the finished product, preferably 1 to 5% by weight.

Hydrogen peroxide releasing agents include bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzene-sulfonate (NOBS, described in US Pat. No. 4,412,934), 3,5-trimethylhexanoloxybenzene sulfonate (Described in ISONOBS, EP 120,591) or pentaacetylglucose (PAG), or N-nonanoyl-6-aminocaproic acid (NAC
A-OBS, described in WO 94/28106), which are perhydrolyzed to form peracids as active bleach species,
Provides improved bleaching effect. Further suitable activators are acylated citrate esters as disclosed in co-pending European Patent Application No. 91870207.7, as well as Procter-Gamble co-pending U.S. Patent Application No. 60/0222. 786
No. (filed July 30, 1996) and No. 60 / 028,122 (filed October 15, 1996) are asymmetric acyclic acid imide bleach activators of the following formulations: :

Embedded image

(Wherein R₁Is C₇~ C₁₃Is a linear or branched saturated or unsaturated alkyl group of_TwoIs C₁~ C₈Is a linear or branched saturated or unsaturated alkyl group of_ThreeIs C ₁ ~ C_FourIs a linear or branched saturated or unsaturated alkyl group).

Useful bleaching agents, including peroxy acids for use in the detergent compositions of the present invention and bleaching systems including bleaching activators and peroxygen bleaching compounds, are described in our co-pending application U.S. Pat.
SSN08 / 136,626, PCT / US95 / 07823, WO95 /
27772, WO95 / 27773, WO95 / 27774 and WO95
/ 27775.

[0057] Hydrogen peroxide may also be present by adding an enzyme system (ie, an enzyme and its substrate) that can generate hydrogen peroxide at the beginning or during the washing and / or rinsing step. Such an enzyme system is described in European Patent Application No. 91202655.6 (1 January 1991).
(Filed on 09:00).

[0058] Metal-containing catalysts for use in the bleach composition include cobalt-containing catalysts, such as pentaamine acetate cobalt (III) salts, and manganese-containing catalysts, such as EPA 549271, EPA 549272, EPA 458297, U
S5,246,621, EPA458398, US5,194,416 and US5,114,611. A bleaching composition comprising a peroxy compound, a manganese-containing bleaching catalyst and a chelating agent is described in Patent Application No. 94870206.3.

Bleaches other than oxygen bleaches are known to those skilled in the art and may be utilized in the present invention. Certain types of non-oxygen bleaches include light activated bleach, such as zinc sulfonated and / or aluminum phthalocyanine. These substances can deposit on the substrate during the cleaning process. Upon irradiation with light in the presence of oxygen, the sulfonated zinc phthalocyanine is activated, for example by hanging the garment to dry in sunlight, thus bleaching the substrate. A preferred zinc phthalocyanine and light activated bleaching method is described in U.S. Pat. No. 4,033,718. Detergent compositions can usually contain from about 0.025% to about 1.25% by weight of the sulfonated zinc phthalocyanine.

Surfactant System The detergent compositions of the present invention generally comprise a surfactant system, wherein the surfactant comprises:
It may be selected from nonionic and / or anionic and / or cationic and / or amphoteric and / or zwitterionic and / or semipolar surfactants.

The surfactant is usually present in a concentration from 0.1% to 60% by weight. A more preferred concentration is 1% to 35% by weight, most preferably 1% to 30% by weight of the detergent composition of the present invention.

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 such that it promotes the stability of, or at least does not degrade, any enzymes in these compositions.

A preferred surfactant system for use in accordance with the present invention includes, as surfactants,
It includes one or more nonionic and / or anionic surfactants described herein.

[0064] Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactants of the surfactant system of the present invention, with polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols with alkyl phenols having an alkyl group of about 6 to about 14, preferably about 8 to about 14, carbon atoms in straight or branched chain form. In a preferred embodiment, ethylene oxide is present in about 2 per mole of alkylphenol.
From about 25 moles, more preferably from about 3 to about 15 moles of ethylene oxide. Commercially available nonionic surfactants of this type include Igepal® CO-630 (GAF Corporation), and Triton® X-45, X-114, X-100 and X −102 (all Rohm & Haas
Company). These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

The condensation products of primary and secondary aliphatic alcohols with about 1 to about 25 moles of ethylene oxide are suitable for use as nonionic surfactants in the nonionic surfactant systems of the present invention. ing. The alkyl chain of the aliphatic alcohol is straight-chain or branched,
It can be first or second and generally contains from about 8 to about 22 carbon atoms. Preferred are those having about 8 to about 20, more preferably about 10 to about 1 carbon atoms.
A condensation product of an alcohol having 8 alkyl groups with about 2 to about 10 moles of ethylene oxide per mole of alcohol. About 2 to about 7 moles of ethylene oxide per mole of alcohol, most preferably 2 to 5 moles of ethylene oxide per mole of alcohol are present in the condensation product. Examples of this type of commercially available nonionic surfactant include Tergitol® 15-S-9.
(The condensation product of linear alcohol with 9 moles ethylene oxide C ₁₁ ~C _15),
Tergitol® 24-L-6NMW (condensation product of a C ₁₂ -C ₁₄ primary alcohol with 6 moles of ethylene oxide, showing a narrow molecular weight distribution
) (Both Union Carbide Corporation), Neodol (registered trademark) 45
-9 (the condensation product of linear alcohol with 9 moles ethylene oxide C ₁₄ -C ₁₅
), Neodol (Neodol, R) 23-3 (the condensation product of linear alcohol with 3.0 moles of ethylene oxide C ₁₂ -C _13), Neodol (Neodol, R) 45-7 (C ₁₄ ~ condensation products of linear alcohol with 7 moles of ethylene oxide C _15), Neodol (Neodol, R) 45-5 (the condensation product of linear alcohol with 5 moles of ethylene oxide C ₁₄ -C ₁₅₎ ( (Shell Chemical Company)
, Km (Kyro, R) EOB (the condensation product of alcohol with 9 moles ethylene oxide _{C 13 ~C 15) (Procter &} Gamble Company), and Genapol (
Genapol) LAO3O or O5O (the condensation product of alcohols with 3 or 5 moles of ethylene oxide C ₁₂ ~C ₁₄₎ (Hoechst) and the like. HL in these substances
A preferred range for B is 8-11, most preferably 8-10.

Further useful as the surfactant-based nonionic surfactant of the present invention are those disclosed in US Pat. No. 4,565,647 (Llenado, issued on Jan. 21, 1986). This comprises a hydrophobic group containing from about 6 to about 30, preferably from about 10 to 16, carbon atoms and from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably about 1 to about 3. A polysaccharide containing a saccharide unit of from 0.3 to 2.7, for example, a polyglycoside hydrophilic group. Any reducing sugar containing from 5 to 6 carbon atoms, such as glucose, galactose, can be used, and the galactosyl moiety can be replaced with a glucosyl moiety (optionally, the hydrophobic group can be in 2-, 3-, 4-etc. To yield glucose or galactose as opposed to glucoside or galactoside). The intersugar linkage can be, for example, between one position of the additional sugar unit and the 2-, 3-, 4- and / or 6-position on the preceding sugar unit. Preferred alkyl polyglycosides have the formula:

Embedded image

Wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl group has about 10 to 18, preferably about 12 carbon atoms. To about 14, n is 2 or 3, preferably 2, t is 0 to about 10, preferably 0, and x is about 1.3 to about 10, preferably about 1.3 to about 3, most preferably from about 1.3 to about 2.
7). Glycosyl is preferably derived from glucose. To prepare these compounds, an alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose, or a source of glucose, to form a glucoside (linked at the 1-position). The additional glycosyl units may then be linked between their 1-position and the preceding glycosyl unit 2-, 3-, 4- and / or 6-position, preferably predominantly 2-position.

[0068] 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 about 1500-
It has a molecular weight of about 1800 and is water-insoluble. The addition of a polyoxyethylene component to this hydrophobic moiety tends to increase the overall water solubility of the molecule, and the liquid character of the material is such that the polyoxyethylene content is about 5% of the total weight of the condensation product.
It is kept to a point of 0%, which corresponds to a condensation with up to about 40 mol of ethylene oxide. Examples of such compounds include commercially available Plurafac,
® LF404 and Pluronic ® surfactants (BA
SF).

Also suitable for use as nonionic surfactants in the nonionic surfactant systems of the present invention are the condensation products of ethylene oxide with materials resulting from the reaction of propylene oxide and ethylenediamine. . The hydrophobic component of these substances is
It consists of the reaction product of ethylenediamine and an excess of propylene oxide and generally has a molecular weight of about 2500 to about 3000. The hydrophobic component is condensed with ethylene oxide to an extent that the condensation product contains from about 40% to about 80% by weight polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain commercially available Tetronic® compounds (BASF).

Suitable as nonionic surfactants for the surfactant system of the present invention are polyethylene oxide condensates of alkyl phenols, primary and secondary aliphatic alcohols with about 1 to about 25 moles of Condensation products with ethylene oxide, alkyl polysaccharides, and mixtures thereof. Most preferred are 3-15 alkylphenol ethoxylates C ₈ -C ₁₄ having ethoxy groups, and 2-10 alcohol ethoxylate of C ₈ -C ₁₈ having ethoxy groups (preferably having an average C ₁₀₎
, As well as mixtures thereof.

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

Embedded image

Wherein R ¹ is H, or R ¹ is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, and R ² is C _5-31 A hydrocarbyl, and Z has a linear hydrocarbyl chain and is at least 3
Polyhydroxyhydrocarbyl or an alkoxylated derivative thereof in which two hydroxyls are attached directly to the chain. Preferably R ¹ is methyl, R ² is a linear C _{11-1 5} alkyl or C _16-18 alkyl or alkenyl chain such coconut alkyl or mixtures thereof, and Z is in the reductive amination reaction Reducing sugars such as glucose, fructose, maltose, lactose).

Suitable anionic surfactants used are linear alkyl benzene sulfonate, alkyl ester sulfonate surfactants, as described in “The Journal
of the American Oil Chemists Society ", 52 (1975), include linear esters of C ₈ -C ₂₀ carboxylic acids sulfonated (e.g. fatty acid) using a gas SO ₃ according Pp.323-329. Suitable Examples of such starting materials include natural fatty substances obtained from tallow, coconut oil and the like.

Preferred alkyl ester sulfonate surfactants, especially for laundry applications, include:
Including an alkyl ester sulfonate surfactant of the following structural formula:

Embedded image

Wherein R ³ is a C ₈ -C ₂₀ hydrocarbyl, preferably alkyl, or a combination thereof, R ⁴ is a C ₁ -C ₆ hydrocarbyl, preferably alkyl, or a combination thereof, and M is a cation that forms a water soluble salt with the alkyl ester sulfonate Suitable salt forming cations include metals such as sodium,
Potassium and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine and triethanolamine. Preferred R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Particularly preferred is methyl ester sulfonate, wherein R ³ is C ₁₀ -C ₁₆ alkyl.

Other suitable anionic surfactants include those of the formula ROSO ₃ M, wherein R is preferably a C ₁₀ -C ₂₄ hydrocarbyl, preferably an alkyl having a C ₁₀ -C ₂₀ alkyl component. hydroxyalkyl, more preferably an alkyl or hydroxyalkyl of C ₁₂ -C _18, M is H or a cation, such as alkali metal cations (e.g., sodium, potassium, lithium), or a, or ammonium or substituted ammonium ( For example, methyl-, dimethyl- and trimethylammonium cations, and quaternary ammonium cations such as tetramethylammonium and dimethylpiperazinium cations, and alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof. Alkyl sulphate surfactant which is a water-soluble salt or acid). Typically, C ₁₂ -C ₁₆ alkyl chains are preferred at low wash temperatures (eg, below about 50 ° C.), and C ₁₆ -C ₁₈ alkyl chains at higher wash temperatures (eg, above about 50 ° C.). Alkyl chains are preferred.

[0077] Other anionic surfactants useful for cleaning purposes can also be included in the detergent compositions of the present invention. Examples of these include soap salts (eg, sodium, potassium,
Ammonium and mono-, - di - and substituted ammonium salts such as triethanolamine salt), primary or secondary alkane sulfonates of C ₈ -C _22, olefin sulfonates of C ₈ -C _24, for example, British Patent Specification No. 1,082,179, a sulfonated polycarboxylic acid prepared by sulfonation of a pyrrolated product of an alkaline earth metal citrate, a C ₈ -C ₂₄ alkyl polyglycol ether sulfate (10 Moles of ethylene oxide), alkyl glycerol sulphonate, fatty acyl glycerol sulphonate, fatty oleyl glycerol sulphate, alkyl phenol ethylene oxide ether sulphate, paraffin sulphonate, alkyl phosphate, isethionate, e.g. acyl isothione DOO, N- acyl taurates, alkyl succinamates Mart and sulfosuccinates, (monoester especially saturated and unsaturated C ₁₂ -C ₁₈₎ sulfosulfuron monoesters of succinate, and sulfosuccinate diesters (especially Saturated and unsaturated C ₆ -C ₁₂ monoesters), acyl sarcosinates, sulfates of alkyl polysaccharides, such as sulfates of alkyl polyglucosides (nonionic non-sulfated compounds described below), branched primary alkyls sulfates, and alkyl polyethoxy carboxylates such as formula _{RO (CH 2 CH 2 O)} k -CH 2 COO-M + ( wherein, R is alkyl of C ₈ -C _22, k is from 1 to 10 And M is a soluble salt-forming cation). Resin acids and hydrogenated resin acids, such as rosin, hardened rosin, and resin acids and hydrogenated resin acids present or derived from tall oil are also suitable.

Further examples are described in “Surface Active Agents and Detergents” (Vol. I and II by
Schwartz, Perry and Berch). A variety of such surfactants are generally described in U.S. Patent No. 3,929,678 (issued December 30, 1975; Laughlin, et al.).
(Column 23, line 58 to column 29, line 23) (the contents of which are included herein by reference). When included therein, the laundry detergent compositions of the invention typically comprise from about 1 to about 4
It contains 0% by weight, preferably about 3 to about 20% by weight of such anionic surfactant.

Highly preferred anionic surfactants include those of the formula RO (A)_mSO_ThreeM Archi
Alkoxylated sulfate surfactants and their water-soluble salts or acids.
Where R is C_Ten~ C_{twenty four}Unsubstituted C with alkyl moiety_Ten~ C_{twenty four}The alkyl or
Is a hydroxyalkyl group, preferably C₁₂~ C₂₀Alkyl or hydroxyal
Kill, more preferably C₁₂~ C₁₈Alkyl or hydroxyalkyl of the
A is 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 cation.
Such as metal cations (eg, sodium, potassium, lithium, calcium)
, Magnesium, etc.), ammonium or substituted ammonium cation
Can be. Alkyl ethoxylated sulfate, and alkyl propoxyl
Fluoride sulfates are contemplated in the present invention. Characteristics of substituted ammonium cations
Specific examples include methyl-, dimethyl-, trimethyl-ammonium cations,
And quaternary ammonium cations such as tetramethyl-ammonium and
Tylpiperdinium cation, as well as alkylamines such as ethylamine,
Such as those obtained from diethylamine, triethylamine, and mixtures thereof
Is mentioned. Representative examples of surfactants include C₁₂~ C₁₈Alkyl polyethoxylate
(1.0) sulfate (C₁₂~ C₁₈E (1.0) M), C₁₂~ C₁₈Alkyl poly
Ethoxylate (2.25) sulfate (C₁₂~ C₁₈E (2.25) M), C₁₂~ C ₁₈ Of alkyl polyethoxylate (3.0) sulfate (C₁₂~ C₁₈E (3.0)
M) and C₁₂~ C₁₈Alkylpolyethoxylate (4.0) sulfate (C₁₂~
C₁₈E (4.0) M, where M is selected from sodium and potassium
Is convenient).

The detergent compositions of the present invention include cationic, amphoteric, zwitterionic and semipolar surfactants, as well as nonionic and / or anionic surfactants other than those already described herein. Agents may also be included.

[0081] Suitable cationic detergent surfactants for use in the detergent compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants, such as alkyltrimethylammonium halides, as well as those having the formula:

Embedded image

(Wherein, R ² is an alkyl or alkylbenzyl group having about 8 to about 18 carbon atoms in the alkyl chain, and each R ³ represents —CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) -, - CH ₂ CH
(CH ₂ OH) —, —CH ₂ CH ₂ CH ₂ —, and mixtures thereof, wherein each R ⁴ is C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, A benzyl ring structure formed by joining R ⁴ groups, —CH ₂ CHO—CHO
HCOR ⁶ CHOHCH ₂ OH (where R ⁶ is any hexose or hexose polymer having a molecular weight of less than about 1000), and if y is not 0, hydrogen is selected from the group consisting of hydrogen and R ⁵ is R ⁴ Or an alkyl chain, wherein the total number of carbon atoms in R ² + R ⁵ is about 18 or less, and each y is from 0 to about 10
Wherein the sum of y is from 0 to about 15 and X is any of the compatible anions.
.

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

Embedded image

Wherein R ₁ is a short chain alkyl (C ₆ -C ₁₀ ) or an alkylamidoalkyl of the formula (II):

Embedded image Wherein y is 2-4, preferably 3. R ₂ is H or C ₁ -C ₃ alkyl; x is 0-4, preferably 0-2, most preferably 0; R ₃ , R ₄ and R ₅ can all be the same or different and can all be short-chain alkyl (C ₁ -C ₃ ) or alkoxylated alkyl of formula III;

X ^- is a counter ion, preferably a halide, such as chloride or methyl sulphate;

Embedded image (Wherein R ₆ is C ₁ -C ₄ and z is 1 or 2)). Preferred quaternary (quat) ammonium surfactants are as described in Formula I, wherein R ₁ is C ₈ , C ₁₀ or a mixture thereof, x = 0 and R _3, R ₄ = CH ₃ and _{R 5 = CH 2 CH 2 OH} .

Highly preferred cationic surfactants are water-soluble quaternary ammonium compounds useful in the compositions of the present invention having the formula:

Embedded image

(Wherein R₁Is C₈~ C₁₆And R is_Two, R_ThreeAnd R_FourAre independently
, C₁~ C_FourAlkyl, C₁~ C_FourHydroxyalkyl, benzyl and-(C_Two
H₄₀)_xH (where x has a value of 2 to 5) and X is an anion
). R_Two, R_ThreeOr R_FourShould be only one of benzyl. R ₁ Preferred alkyl chain lengths for₁₂~ C_FifteenIn particular, the alkyl group is
It is a mixture of chain lengths derived from nuts or palm palm kernel fat, or olefin storage.
Product or obtained synthetically by OXO alcohol synthesis. R_Two, R_ThreeAnd R_FourAbout
More preferred groups are methyl and hydroxyethyl groups, wherein the anion X is a halide,
It may be selected from meso sulphate, acetate and phosphate ions. Honcho
Examples of suitable quaternary ammonium compounds of formula (i) for use in the text are set forth below.
Indicate: coconut trimethylammonium chloride or bromide, coconut methyldihydroxyethylammonium chloride or bromide, decyltriethylammonium chloride, decyldimethylhydroxyethylammonium chloride or bromide, C_12-15Dimethylhydroxyethylammonium chloride or bromide, coconut dimethylhydroxyethylammonium chloride or bromide, myristyltrimethylammonium methylsulfate, lauryldimethylbenzylammonium chloride or bromide, lauryldimethyl (ethenoxy)_FourAmmonium chloride or bromide, choline ester (compound of formula (i), wherein R₁But,

Embedded image And R ₂ , R ₃ and R ₄ are methyl). Dialkylimidazoline [compound of formula (i)]

Other cationic surfactants useful herein are described in US Pat. No. 4,228,
No. 044 (Cambre, published October 14, 1980) and European patent application EP000,224.
It is also mentioned in the issue.

[0089] Typical cationic textile softening components include water-insoluble quaternary ammonium textile softening activators or their corresponding amine precursors, but are most commonly used. Is a long alkyl chain ammonium chloride or methyl sulfate. Examples of preferred cationic softeners are: 1) ditallow dimethyl ammonium chloride (DTDMAC), 2) dihydrogenated tallow dimethyl ammonium chloride, 3) dihydrogenated tallow dimethyl ammonium methyl sulfate, 4) distearyl Dimethylammonium chloride, 5) dioleyldimethylammonium chloride 6) dipalmitylhydroxyethylmethylammonium chloride, 7) stearylbenzyldimethylammonium chloride, 8) tallow trimethylammonium chloride 9) hydrogenated tallow trimethylammonium chloride, 10) _{C12- 14} alkylhydroxyethylammonium dimethyl ammonium chloride, 11) C _12-18 alkyl dihydroxyethyl methyl ammonium chloride, 12) di (stearoyl oxy ethyl) dimethicone Ammonium chloride (DSO
EDMAC), 13) di (tallow-oxy-ethyl) dimethylammonium chloride, 14) ditallow imidazolinium methylsulfate, 15) 1- (2-tallowylamidoethyl) -2-tallowylimidazolinium methylsulfate Fate.

[0090] Biodegradable quaternary ammonium compounds have been shown as alternatives to the two long-chain alkylammonium chlorides and methyl sulfates traditionally used. Such quaternary ammonium compounds contain long chain alkyl (alkenyl) groups that are hindered by a functional group such as a carboxy group. Such substances and textile softening compositions containing them are disclosed in a number of publications, such as EP-A-0,040,562 and EP-A-0,239,910.

The quaternary ammonium compounds and amine precursors herein have the following formula (I) or (II):

Embedded image

(Wherein Q is —OC (O) —, —C (O) —O—, —OC (O) —O—, —
^{NR 4 -C (O) -,} - C (O) -NR 4 - is selected from, R ¹ is _{(CH 2) n -Q-T} 2 or T ^3, R ² is (CH _{2) m} - a Q-T ⁴ or T ⁵ or R ^3, R ³ is hydroxyalkyl or H alkyl, or C ₁ -C ₄ a C ₁ ~C ^_4, R ₄ is H or alkyl of C ₁ -C ₄ 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 of 1-4 And X ^- is a softener-compatible anion). Examples of softener compatible anions include, but are not limited to, chloride or methyl sulfate.

The alkyl or alkenyl chains T ¹ , T ² , T ³ , T ⁴ , T ⁵ must contain at least 11 carbon atoms, preferably at least 16 carbon atoms. The chains can be straight or branched. Tallow is a convenient and inexpensive source of long-chain alkyl and alkenyl materials. Compounds in which T ¹ , T ² , T ³ , T ⁴ , T ⁵ represent a mixture of long chain substances typical of tallow are particularly preferred.

The following are specific examples of quaternary ammonium compounds suitable for use in the aqueous textile soft composition of the present invention: 1) N, N-di (tallowyl-oxy-ethyl) -N , N-dimethylammonium chloride, 2) N, N-di (tallowyl-oxy-ethyl) -N-methyl, N (2-hydroxyethyl) ammonium methyl sulfate, 3) N, N-di (2-tallow) Yl-oxy-2-oxo-ethyl) -N, N-dimethylammonium chloride; 4) N, N-di (2-tallowyl-oxy-ethylcarbonyl-oxy-ethyl)
-N, N-dimethylammonium chloride, 5) N- (2-tallowyl-oxy-2-ethyl) -N- (2-tallowyl-oxy-2-oxo-ethyl) -N, N-dimethylammonium chloride 6) N, N, N-tri (tallowyl-oxy-ethyl) -N-methylammonium chloride 7) N- (2-tallowyl-oxy-2-oxo-ethyl) -N- (tallowyl- N
, N-dimethylammonium chloride, and 8) 1,2-ditallowyl-oxy-3-trimethylammoniopropane chloride and mixtures of any of the foregoing. When included therein, the detergent compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about 1% to about 8%, by weight of such a cationic surfactant. .

[0095] Amphoteric surfactants are also suitable for use in the detergent compositions of the present invention. These surfactants are widely described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, wherein the aliphatic group can be straight or branched. obtain. One of the aliphatic substituents has at least about 8, and typically from about 8 to about 18, carbon atoms and at least one contains an anionic water-soluble group, such as carboxy, sulfonate, sulfate. For examples of amphoteric surfactants, see US Pat. No. 3,929,678 (Laughlin et al., Issued Dec. 30, 1975) at column 19-18.
See ~ line 35. When included therein, the detergent compositions of the present invention typically contain from 0.2% by weight to
It contains about 15% by weight, preferably about 1% to about 10% by weight of such amphoteric surfactant.

[0096] Zwitterionic surfactants are also suitable for use in the cleaning compositions.
These surfactants are widely described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. obtain. For examples of zwitterionic surfactants, see US Pat. No. 3,929,678 (Laughlin et al., December 1975).
See column 38, line 38 to column 22, line 48, issued on 30th). When included therein, the detergent compositions of the present invention typically contain from 0.2% by weight to
It contains about 15%, preferably about 1% to about 10%, by weight of such zwitterionic surfactants.

The semipolar nonionic surfactant comprises one alkyl component having about 10 to about 18 carbon atoms and two components selected from the group consisting of an alkyl group having about 1 to about 3 carbon atoms and a hydroxyalkyl group. A water-soluble amine oxide containing one or more alkyl components having about 10 to about 18 carbon atoms and two components selected from the group consisting of an alkyl group and a hydroxyalkyl group having about 1 to about 3 carbon atoms. A phosphine oxide; and a water-soluble sulfoxide containing one alkyl component having about 10 to about 18 carbon atoms and one component selected from the group consisting of an alkyl group having about 1 to about 3 carbon atoms and a hydroxyalkyl group. A special type of nonionic surfactant.

[0098] Semipolar nonionic detergent surfactants include amine oxide surfactants having the formula:

Embedded image Wherein R ³ is an alkyl, hydroxyalkyl, or alkylphenyl group having about 8 to about 22 carbon atoms or a mixture thereof, and R ⁴ is an alkylene or hydroxyalkylene group having about 2 to about 3 carbon atoms, or a group thereof. A mixture wherein x is 0 to about 3 and R ⁵ is an alkyl or hydroxyalkyl group each having about 1 to about 3 carbon atoms, or a polyethylene oxide group containing about 1 to about 3 ethylene oxide groups R ⁵ groups are linked to each other, for example via an oxygen or nitrogen atom,
A ring structure can be formed).

These amine oxide surfactants include, in particular, C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₈ -C ₁₂ alkoxyethyldihydroxyethylamine oxides. When included therein, the cleaning composition of the present invention typically comprises 0.2
% To about 15%, preferably about 1% to about 10%, by weight of such semipolar nonionic surfactants.

The detergent composition according to the invention comprises a co-surfactant selected from the group of primary or tertiary amines
An agent may be further included. Primary amines suitable for use in the present invention include those of formula R₁
NH_Two(Where R₁Is C₆~ C₁₂Of, preferably C₆~ C_TenAn alkyl chain of_Four
X (CH_Two)_n(Wherein X is -O-, -C (O) NH- or NH-, and R is_FourIs C₆~
C₁₂Wherein n is from 1 to 5, preferably 3.
Is mentioned. R₁Alkyl chains are straight or branched and up to 12 are preferred.
Preferably it can be broken by less than 5 ethylene oxide components. The said in this specification
A preferred amine of the formula is an n-alkylamine. Suitable for use herein.
The amines obtained are 1-hexylamine, 1-octylamine, 1-decylamine and
And laurylamine. Other preferred primary amines include C ₈ ~ C_TenOxypropylamine, octyloxypropylamine, 2-ethyl
Hexyloxypropylamine, laurylamidopropylamine and amidopro
Pyramine.

[0101] Tertiary amines suitable for use herein are tertiary amines having the formula R ₁ R ₂ R ₃ N, wherein R ₁ and R ₂ are C ₁ -C ₄ . A C ₈ alkyl chain or

Embedded imageAnd R_ThreeIs C₆~ C₁₂Of, preferably C₆~ C_TenIs an alkyl chain of
R_ThreeIs R_FourX (CH_Two)_n(Wherein X is -O-, -C (O) NH- or NH-, and R is _Four Is C_Four~ C₁₂And n is 1-5, preferably 2-3. R_FiveIs H
Or C₁~ C_TwoAlkyl and x is 1-6. R_ThreeAnd R_FourIs a straight or branched chain
And R_ThreeThe alkyl chain has up to 12, preferably less than 5, ethylene oxide components.
Can be interrupted in minutes.

A preferred tertiary amine is R ₁ R ₂ R ₃ N, where R ₁ is a C ₆ -C ₁₂ alkyl chain and R ₂ and R ₃ are C ₁ -C ₃ Alkyl or

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

Also preferred are amidoamines of the formula:

Embedded image Wherein 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 .

The most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C ₈ -C ₁₀ oxypropylamine, Ncoco 1-3 diaminopropane, coconut Alkyldimethylamine, lauryldimethylamine, laurylbis (hydroxyethyl) amine, cocobis (hydroxyethyl) amine, laurylamine 2 mol propoxylation, octylamine 2 mol propoxylation, laurylamidopropyldimethylamine, C _8-10 amide amidopropyl dimethylamine dimethylamine and C ₁₀ and the like. The most preferred amines for use in the compositions of the present invention are 1-hexylamine,
-Octylamine, 1-decylamine and 1-dodecylamine. Particularly preferred are n-dodecyldimethylamine and bishydroxyethyl coconut alkylamine and oleylamine 7-fold ethoxylation, laurylamidopropylamine and cocoamidopropylamine.

Conventional detergents The enzyme detergent composition comprises, in addition to pectate lyase and pectin lyase, one more
More than one enzyme may be provided that provides a cleaning effect, a textile care and / or a hygiene effect.

Examples of the enzymes include cellulase, hemicellulase, peroxidase, protease, gluco-amylase, amylase, xylanase, lipase, phospholipase, esterase, cutinase, other pectinases, keratanase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase. , Pullulanases, tannases, pentosanases, malanases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases or mixtures thereof.

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they have an optimal pH value in the range of 5-12,
Has a specific activity higher than EVU / mg (cellulose viscosity unit). Suitable cellulases are described in U.S. Patent No. 4,435,307 (Barbesgoard et al.), J610783.
No. 84, and each Humicola insolens,
Trichoderma, Thielavia and Sporotricum (
WO96 / 02653 which discloses fungal cellulases produced from Sporotrichum)
Issue. EP 739982 describes a novel cellulase isolated from Bacillus sp. A suitable cellulase is GB-A-2.075.0
No. 28, GB-A-2.095.275, DE-OS-2.2477.832 and WO 95/26398. An example of such a cellulase is Humicola grisea
var. thermoidea), in particular a cellulase produced by the Humicola DSM 1800 strain.

Other suitable cellulases have a molecular weight of about 50 KDa, an isoelectric point of 5.5, and 41
Cellulase originating from the Humicola insolens of 5 amino acids, and ^~ 43 kD from Humicola insolens DSM1800 exhibiting cellulase activity
Endoglucanase. A preferred endoglucanase component is PCT
It has the amino acid sequence disclosed in patent application WO 91/17243.

Suitable cellulases are also described in WO 94/21801 (Genencor, September 29, 1994).
Trichoderma longibatumatum (Trichoderma longib)
rachiatum). Particularly suitable cellulases are those having a color care effect. Examples of such cellulases are the cellulases described in European Patent Application No. 91202879.2, filed Nov. 6, 1991 (Novo). Kalezyme and cellzyme (Novo Nordisk A / S) are particularly useful. See also WO 91/17244 and WO 91/21801. Other suitable cellulases for textile care and / or cleaning properties are WO 96/34092, WO 96/17994 and WO 95/244.
No. 71. The cellulase is usually contained in the detergent composition at a concentration of 0.0001% to 2% by weight of the pure enzyme of the detergent composition.

The peroxidase enzyme is a source of oxygen such as percarbonate, perborate, persulfate
Used in combination with salts, hydrogen peroxide, etc., and phenolic substrates as bleach enhancers
It is. They are removed from the substrate for "solution bleaching", i.e. during the washing operation.
Used to prevent the transfer of dyes or pigments to other substrates in the washing solution.
You. Peroxidase enzymes are known in the art and include, for example,
Horseradish peroxidase, ligninase and haloperoxidase, such as
Chloro and bromo-peroxidase. Peroxidase-containing washing
Agent compositions are described, for example, in PCT International Applications WO 89/099813, WO 89/09
813 and European Patent Application EP 91202882.6 (November 6, 1991).
And EP 968700133.8 (filed on February 20, 1996).
It has been disclosed. Laccase enzymes are also suitable. Enhancers are generally included at a level of from 0.1% to 5% by weight of the total composition. Good
Preferred enhancers are substituted phenthiazine and phenoxazine 10-phenothiazi.
Propionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (E
PC), 10-phenoxazine propionic acid (POP) and 10-methylphen
Noxazine (described in WO 94/12621), and substituted syringates (C _Three ~ C_FiveAnd phenol. Sodium overcarbon
Acid salts or perborates are preferred sources of hydrogen peroxide.

The peroxidase is usually included in the detergent composition at a concentration of 0.0001% to 2% by weight of the active enzyme of the detergent composition.

Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes for detergents include Pseudomonas (Pseu
domonas) group of microorganisms, such as those produced by Pseudomonas stutzeri ATCC 19.154 as disclosed in GB 1,372,034. Suitable lipases include those that show a positive immunological cross-reactivity with antibodies to the lipase produced by the microorganism Pseudomonas fluorescent IAM1057. This lipase is trade name of lipase P "Amano" and is available from Amano Pharmaceutical Co. Ltd.
d., Nagoya, Japan, hereinafter referred to as "Amano-P". Other suitable commercially available lipases include Amano-CES, Chromobacter viscosum (eg, Chromobacter viscosum var.
lipase derived from lipolyticum NRRLB3663) (Toyo Jozo Co., Tagata, J
apan), Chromobacter viscosum lipase and Pseudomonas gladioli (Pseu) from US Biochemical Corp., USA and Disoiynth Co., The Netherland.
domonas gladioli). Particularly suitable lipases have been found to be very effective when used in combination with the compositions of the present invention.
Lipase (registered trademark) and Lipomax (Lipomax®) (Gist-
Brocades), and lipases such as Lipolase (registered trademark) and Lipolase Ultra (registered trademark) (Novo). Further suitable are EP258068, WO92 / 05249 and WO95 / 2261.
No. 5 (Novo Nordisk) and WO 94/03578, WO 95/35381
And lipolytic enzymes described in WO 96/00292 (Unilever).

Also suitable are cutinases [EC 3.1.1.50], which can be considered to be a special type of lipase, a lipase that does not require surface activation. Addition of cutinase to the detergent composition is described, for example, in WO-A-88 / 09367.
(Genencor), WO 90/09446 (Plant Genetic System), and WO 94/14963 and WO 94/14964 (Unilever). The lipase and / or cutinase is usually included in the detergent composition at a concentration of 0.0001% to 2% pure enzyme by weight of the detergent composition.

Suitable proteases are subtilisins (subtilisins BPN and BPN ') obtained from certain strains of B. subtilis and B. licheniformis. One suitable protease is Novo, Denmark
It is obtained from one strain of the genus Bacillus which has been developed and marketed by Industries A / S (hereinafter referred to as "Novo") as ESPERASE (R) and exhibits maximum activity over the pH range of 8-12. Preparation of this and similar (analog) enzymes
It is described in British Patent 1,243,784 (Novo). Other suitable proteases include ALCALASE®, Durazyme (DUR
AZYN® and SAVINASE® (Novo), and maxatase (MAXATASE®), maxacal (MAXACAL®), properase (PROPERASE®) and maxapem (MAXAPEM®) ( (Gist-Brocades). Proteolytic enzymes are modified bacterial serine proteases, for example European Patent Application 87 303761
. No. 8 (filed on April 28, 1987) (especially pages 17, 24 and 98)
What is referred to herein as "Protease B" and European Patent Application No. 19
No. 9,404 (Venegas, published Oct. 29, 1986) and modified bacterial serine proteases, such as those referred to herein as "protease A", also referred to as modified protease serine proteases. Including. Suitable is what is referred to herein as "Protease C", which replaces lysine for arginine at position 27, tyrosine for valine at position 104, and serine for asparagine at position 123. It is a variant of the alkaline serine protease from Bacillus that replaces and replaces threonine with alanine at position 274. Protease C is described in EP 90915958: 4 corresponding to WO 91/06637 (published May 16, 1991). In particular, genetically modified variants of protease C are also included in the present invention.

A preferred protease, referred to as “Protease D”, is a mutation of a carbonyl hydrolase in which the amino acid sequence is not found in nature, but is described in WO 95/105.
No. 91 and C.I. In a patent application by Gauche et al., US Serial No. 08 / 322,6
No. 77 (filed on October 13, 1994, “Bleaching composition containing protease enzyme”)
According to the numbering of Bacillus amyloliquefaciens subtilisin described in above, the position corresponding to +76 of the carbonyl hydrolase, and preferably +99, +101
, +103, +104, +107, +123, +27, +105, +109, +
126, +128, +135, +156, +166, +195, +197, +2
04, +206, +210, +216, +217, +218, +222, +26
A plurality of amino acid residues in the carbonyl hydrolase at different positions in combination with one or more amino acid residue positions corresponding to positions selected from the group consisting of 0, +265, and / or +274; And obtained from a carbonyl hydrolase precursor by substituting

Also suitable are variants of the carbonyl hydrolase of the protease described in WO 95/10591, obtained by replacing a plurality of amino acid residues in the carbonyl hydrolase precursor with different amino acids. Wherein the plurality of substituted amino acid residues in the precursor enzyme are position number +210 and one or more of the following residues: +3
3, +62, +67, +76, +100, +101, +103, +104, +1
07, +128, +129, +130, +132, +135, +156, +15
8, +164, +166, +167, +170, +209, +215, +217
, +218 and +222, where the position numbers are the naturally occurring Bacill
position numbers of subtilisin from C. us amyloliquefaciens, or position numbers of equivalent amino acid residues in other carbonyl hydrolase or subtilisin such as Bacillus lentus subtilisin (co-pending patent application US Serial No. 60 / 048,550 ( (June 4, 1997).

Also suitable for the present invention are the patent applications EP 251 446 and WO 91 /
066637, the protease described in WO 91/02792, the protease BLAP®, and variants thereof described in WO 95/23221. Bacillus sp. NCIMB403 described in WO93 / 18140A (Novo)
See also the high pH protease from 38. Enzyme detergents containing proteases, one or more other enzymes and a reversible protease inhibitor are described in WO 92 /
No. 03529A (Novo). If desired, WO 95/07
No. 791 (Procter & Gamble) can be used which exhibits reduced adsorption and increased hydrolysis. Recombinant trypsin-like proteases for detergents suitable herein are described in WO 94/25583 (Novo).
Other suitable proteases are described in EP 516200 (Unilever). Proteolytic enzymes comprise from 0.0001% to 2%, preferably from 0.001% to 0.2%, more preferably from 0.005% to 0.1% by weight of the composition.
Included in the detergent compositions of the present invention at the level of wt% pure enzyme.

Amylases (α and / or β) may be included for the removal of carbohydrate-based stains. WO 94/02597 (Novo Nordisk A / S, published February 03, 1994) describes a cleaning composition containing a mutant amylase (WO 95/10603 (N
ovo Nordisk A / S, published April 20, 1995). Other known amylases for use in the cleaning compositions include both α- and β-amylases. Alpha-amylases are known in the art and include, for example, U.S. Patent Nos. 5,003,257, EP252,666, WO91 / 00353, F.
R2,676,456, EP285,123, EP525,610, EP
368,341 and British Patent Specification No. 1,296,839 (Novo). Other suitable amylases are described in WO 94/1831
No. 4 (published August 18, 1994) and WO 96/05295 (Genencor, February 1996)
Amylase described in WO95 / 10603 (published April 1995) and amylase variants with additional modifications in the direct parent available from Novo Nordisk A / S disclosed in WO95 / 10603 (published April 1995) It is. Also appropriate is EP27
7216, WO95 / 26397 and WO96 / 23873 (all Novo
Amylase described in Nordisk).

Examples of commercially available α-amylase products are Purafect Ox Am® (Genencor), as well as Termamyl®, Ban,
(Registered trademark), Fungamyl (registered trademark) and Duramil (registered trademark) (all Novo Nordisk A / S Denmark). WO 95/26397 describes another suitable amylase, namely as measured by the Phadebas® α-amylase activity assay at a temperature range of 25 ° C. to 55 ° C. and at a pH value in the range of 8 to 10. Describe an α-amylase characterized by having a specific activity at least 25% higher than the specific activity of Termamyl (registered trademark). Suitable are variants of the aforementioned enzymes described in WO 96/23873 (Novo Nordisk). Other amylolytic enzymes exhibiting improved properties with respect to activity levels as well as the combination of thermostability and higher activity levels are described in WO 95/35382. The amylolytic enzyme is present in an amount of 0.0001% to 2%, preferably 0% by weight of the composition.
. 00018% by weight to 0.06% by weight, more preferably 0.00024% by weight
A pure enzyme at a concentration of ０．０0.048% by weight may be included in the detergent composition of the present invention.

The enzymes can be of any suitable origin, for example, of plant, animal, bacterial, fungal and yeast origin. The origin can also be mesophilic or extremophilic (cryophilic, cryogenic, thermophilic, barophilic, alkaliphilic, acidophilic, halophilic, etc). Purified or unpurified forms of these enzymes may be used. In recent years, it is common practice to modify wild-type enzymes by protein / genetic engineering techniques to optimize their performance efficiency in the detergent compositions of the present invention. For example, variants can be designed to increase the suitability of the enzyme for commonly encountered components of such compositions. Alternatively, the variants can be designed such that the optimal pH of the enzyme variant, the stability of the bleach or chelating agent, the enzymatic activity, etc., are tailored to the particular cleaning application.

In particular, attention should be paid to oxidation sensitive amino acids for bleach stability and surface charge for surfactant compatibility. The isoelectric point of such enzymes can be modified by substitution of some charged amino acids, for example, increasing the isoelectric point can help improve compatibility with anionic surfactants . Enzyme stability can be further enhanced, for example, by creating additional salt bridges and enhancing calcium binding sites to increase chelator stability. Particular attention must be paid to cellulases, as most cellulases have a discrete binding region (CBD). The properties of such enzymes can be altered by altering these regions.

The enzymes are generally included in the detergent composition at a concentration of 0.0001% to 2% pure enzyme by weight of the detergent composition. Enzymes can be separate single components (granules, granules, stabilized liquids, etc. containing one enzyme) or as a mixture of two or more enzymes (
(Eg, auxiliary granules). Other suitable detergent ingredients that may be added are described in co-pending European Patent Application 928700
No. 18.6 (filed on Jan. 31, 1992) is an enzyme oxidizing scavenger (scavenger). An example of such a scavenger is ethoxylated tetraethylene polyamine.

The range of enzyme substances and their means of inclusion in synthetic detergent compositions are described in WO 9307
No. 263A and WO 9307260 A (Genencor International), WO 89
No. 08694A (Novo) and U.S. Pat. No. 3,553,139 (January 5, 1971, McCarty et al.). The enzyme is further disclosed in U.S. Pat. No. 4,101,45.
No. 7 (Place et al., July 18, 1978) and U.S. Pat. No. 4,507,219 (Hughes).
, March 26, 1985). Enzyme substances useful in liquid detergent formulations and their inclusion in such formulations are described in U.S. Pat. No. 4,261,868 (Hora
Et al., April 14, 1981). The enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described in U.S. Pat. No. 3,600,319 (19
Gedge et al., Aug. 17, 71), EP 199,405 and EP 200,
No. 586 (October 29, 1986, Venegas) and is exemplified. Enzyme stabilization systems are also described, for example, in US Pat. No. 3,519,570. Useful Bacillus sp. AC13 that produces proteases, xylanases and cellulases is described in WO
No. 9401532A (Novo).

Color Care and Knitted Fabric Care Effects Techniques that provide one type of color care effect may also be included. Examples of these techniques are metal catalysts for color retention. Such metal catalysts are described in co-pending European Patent Application No. 92870181.2. Dye fixatives, polyolefin dispersions for anti-shrinkage and improved water absorption, perfume, and amino-functional polymers for color care treatment and perfume directness are also additional examples of color care / textile care techniques and co-pending patent applications No. 96870140.9 (filed on Nov. 7, 1996).

[0125] Fabric softeners may also be included in the cleaning compositions of the present invention. These agents can be of inorganic or organic type. Inorganic softeners are exemplified by smectite clay (green clay) disclosed in GB-A-1400898 and US Pat. No. 5,019,292. GB-A-154276 and EP as organic knit fabric softeners
The water-insoluble tertiary amines as disclosed in JP -B0011340 and the like, a combination of a mono C ₁₂ -C ₁₄ quaternary ammonium salts is disclosed in Patent EP-B-0026527 and EP-B-0026528 Patent And the long-chain amide is EP-B-02
No. 42919. Other useful organic components of the fabric softening system include high molecular weight polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0313146.

The concentration of smectite (green clay) is usually in the range from 2% to 20% by weight, more preferably from 5% to 15% by weight, the substance being present as a dry-mix component in the remaining formulation. Will be added. Organic knitting fabric softeners, such as water-insoluble tertiary amines or bilong chain amide materials, are included at a concentration of 0.5% to 5% by weight, usually 1% to 3% by weight, while The high molecular weight polyethylene oxide material and the water-soluble cationic material are included at a concentration of 0.1% to 2% by weight, usually 0.15% to 1.5% by weight. These materials are usually added to the spray-dried portion of the composition, but in some cases, add them as dry mixed particles, or as a melt, the multiple solid constituents of other compositions. Spraying over the ingredients is more convenient.

Builder type The detergent composition of the present invention may further contain a builder type. Any conventional builder system is suitable for use herein, such as aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenyl succinic acids and fatty acids, ethylenediaminetetraacetic acid, diethylenetriaminepentamethylene. Substances such as acetate, sequestering agents such as aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Phosphate builders can also be used in the present invention.

Suitable builders are inorganic ion exchange materials, generally inorganic hydrated aluminosilicate materials, especially hydrated synthetic zeolites, such as hydrated zeolites A, X, B, HS or MA
P. Another suitable inorganic builder material is a laminated silicate, such as SKS-6 (
Hoechst). SKS-6 is a crystalline laminated silicate composed of sodium silicate (Na ₂ Si ₂ O ₅ ). Suitable polycarboxylates containing one carboxy group include lactic acid, glycolic acid, and the like as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370. Ether derivatives thereof. Polycarboxylates containing two carboxy groups include salts of succinic acid, malonic acid, (ethylenedioxy) diacetate, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, and German published patents. Gazette No. 2,44
6,686 and 2,446,687 and U.S. Patent 3,935,25
No. 7 and Belgian Patent 840,
No. 623, for example. Examples of the polycarboxylate containing three carboxy groups include water-soluble citrate,
Aconitate and citraconic acid salts and succinate derivatives such as carboxymethyloxysuccinate as described in GB 1,379,241 and lactoxis as described in Netherlands application 72050873 Succinate, and the 2-oxa-1 described in GB 1,387,447.
Oxypolycarboxylate materials such as 1,1,3-propanetricarboxylate.

Polycarboxylates containing four carboxy groups include British Patent No. 1
Oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,1,2,3-propanetetracarboxylate described in JP-A-261,829. Rates. Examples of the polycarboxylate containing a sulfo substituent include British Patent No. 1,398,421,
No. 1,398,422 and U.S. Pat. No. 3,936,448 as well as sulfosuccinate derivatives and heats of sulfonation as described in GB 1,082,179. Polycarboxylates containing phosphon substituents, while degraded citrates are mentioned, are disclosed in British Patent 1,439,000.

The alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,
Cis, cis-tetracarboxylate, cyclopentadienidepentacarboxylate, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,
2,5,5-tetrahydrofuran-tetracarboxylate, 1,2,3,4
5,6-hexane-hexacarboxylate and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. As the aromatic polycarboxylate, British Patent No. 1,425,343
And the derivatives of melitic acid, pyromellitic acid and phthalic acid disclosed in US Pat. Among the above, preferred polycarboxylates are hydroxycarboxylates containing up to 3 carboxy groups per molecule, especially citrate.

Preferred builder systems for use in the compositions of the present invention include a mixture of a water-soluble carboxylate chelating agent, such as citric acid, and a water-insoluble aluminosilicate builder, such as zeolite A, or laminated silicate (SKS-6). And mixtures thereof. Other preferred builder systems include a mixture of a water-insoluble aluminosilicate builder, such as zeolite A, and a water-soluble carboxylate chelating agent, such as citric acid. Preferred builder systems for use in the liquid detergent compositions of the present invention are soaps and polycarboxylates.

Other builder substances which may form part of the builder system for use in the particulate composition include inorganic substances such as alkali metal carbonates, bicarbonates, silicates, and organic substances such as organic Phosphonates, aminopolyalkylenephosphonates and aminopolycarboxylates are mentioned. Other suitable water-soluble organic salts are homo- or copolymeric acids or salts thereof, in which case the polycarboxylic acid contains at least two carboxyl groups separated from each other by no more than two carbon atoms. This type of polymer is known as GB-A-1,
No. 596,756. Examples of such salts have a molecular weight of 2000-5.
000 polyacrylates and their copolymers with maleic anhydride, for example copolymers having a molecular weight of 20,000 to 70,000, especially about 40,000. Detergent builder salts usually comprise 5% to 80%, preferably 10% by weight of the composition.
% By weight, most usually 30% to 60% by weight.

Chelating Agents The detergent compositions of the present invention may also optionally contain one or more iron and / or manganese chelating agents. Such chelators may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelators, and mixtures thereof, all as described below. Without being bound by theory, it is believed that the benefits of these materials are due, in part, to their exceptional ability to remove iron and manganese ions from the wash solution by the formation of soluble chelators. .

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate, and ethanol. Diglycine, its 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, provided that at least low levels of total phosphorus are found in the detergent composition;
Examples include ethylenediaminetetrakis (methylene phosphonate) such as DEQUEST. These aminophosphonates preferably do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Polyfunctionally substituted aromatic chelators are also useful in the compositions of the present invention (see U.S. Pat. No. 3,812,044, Conner et al., Issued May 21, 1974). A preferred compound of this type in the acid form is dihydroxydisulfobenzene, for example 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use in the present invention is ethylenediaminedisuccinate (“EDDS”), particularly US Pat. No. 4,704,233 (Hartma).
n and Perkins, November 3, 1987).

The compositions herein are useful with water-soluble methyl glycine diacetate (MGDA) salt (or acid form) together with a chelating agent or an insoluble builder such as, for example, a zeolite, a layered silicate. As an auxiliary builder.

When these chelating agents are used, generally about 0.1% of the detergent composition of the present invention is used.
% By weight to about 15% by weight. More preferably, when used, the chelating agent contains from about 0.1% to about 3.0% by weight of such a composition.

Foam Inhibitors Another optional ingredient is a foam inhibitor, exemplified by silicones and silica-silicone mixtures. Silicones can generally be represented by alkylated polysiloxane materials, while silica is commonly used in finely divided form and is exemplified by silica airgels and xerogels, and various types of hydrophobic silica. These materials may be included as particles in which the suds suppressor is beneficially releasably included 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. Preferred silicone foam control agents are disclosed in U.S. Pat. No. 3,933,672 (Bartol).
lota et al.). Other particularly useful foam control agents are described in German Patent Application D
It is a self-emulsifying silicone foam inhibitor described in TOS 2646126 (published on April 28, 1977). An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Particularly preferred suds control agents are suds suppressor systems comprising mixtures of silicone oils and 2-alkyl-alkanols. A suitable 2-alkyl-alkanol is 2-butyl-octanol, which is commercially available under the trade name Isophor 12R. Such a suds suppressor system is disclosed in co-pending European Patent Application N9887904.
. 7 (filed on November 10, 1992). Particularly preferred silicone foam control agents are described in co-pending European Patent Application N9220.
1649.8. The composition can include a silicone / silica mixture in combination with a fumed non-porous silica, such as Aerosil®. Said suds suppressor is usually used at a concentration of 0.001% to 2%, preferably 0.01% to 1% by weight of the composition.

Other Constituents Other constituents used in the detergent composition include, for example, soil suspending agents, soil releasing agents, optical brighteners, abrasives, bactericides, anti-fogging agents, coloring agents and the like. And / or encapsulated or unencapsulated fragrances may be used. A particularly suitable encapsulating material is a water-soluble capsule consisting of a matrix of a polysaccharide and a polyhydroxy compound as described in GB 1,464,616. Other suitable water soluble encapsulating materials include dextrins derived from non-gelatinized starch-esters of substituted dicarboxylic acids as described in U.S. Patent No. 3,455,838. These acid-ester dextrins are preferably prepared from starches such as waxy corn, waxy sorghum, sago palm, tapioca and potato. Suitable examples of such encapsulation materials include National Sta
N-Lok manufactured by rch. The N-Lok encapsulant consists of denatured corn starch and glucose. Starch is modified by adding a monofunctional substituent, such as octenyl succinic anhydride.

Suitable anti-redeposition agents and soil suspending agents for the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymeric polycarboxylic acids or salts thereof. Such polymers include the polyacrylates and maleic anhydride-acrylic acid copolymers described above as builders, and copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid. Here, maleic anhydride makes up at least 20 mol% of the copolymer. These materials usually comprise 0.5% to 10%, more preferably 0.75% by weight of the composition.
It is used at a concentration of from 8% to 8%, most preferably from 1% to 6% by weight.

Preferred optical brighteners are anionic substances of a suitable nature, examples of which are disodium 4,4′-bis- (2-diethanolamino-4-anilino-s-triazine-6- 6 Ilamino) stilbene-2: 2'disulfonate, disodium 4,4'-bis- (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2: 2'-disulfonate, disodium 4 , 4'-Bis- (2,4-dianilino-s-triazin-6-ylamino) stilbene-2:
2 ′ disulfonate, monosodium 4 ′, 4 ″ -bis- (2,4-dianilino-s-triazin-6-ylamino) stilbene-2-sulfonate, disodium 4,4′-bis- (2-anilino- 4- (N-methyl-N-2-hydroxyethylamino) -s-triazin-6-ylamino) stilbene-2,2'disulfonate, disodium 4,4'-bis- (4-phenyl-2,1 , 3-Triazol-2-yl) stilbene-2,2'disulfonate, disodium 4,
4'-bis- (2-anilino-4- (1-methyl-2-hydroxyethylamino) -s-triazin-6-ylamino) stilbene-2,2'disulfonate,
Sodium 2 (stilbill-4 "-(naphth-1 ', 2': 4,5) -1,2,2
3-Triazole-2 "-sulfonate and 4,4'-bis (2-sulfostyryl) biphenyl. Highly preferred brighteners are the specific brighteners disclosed in EP 755567.

Other useful polymeric substances are polyethylene glycols, especially those having a molecular weight of 100
0-10000, more preferably 2000-8000, most preferably about 40
00. They are used at a concentration of 0.20% to 5% by weight, more preferably 0.25% to 2.5% by weight. These polymers and the aforementioned homo- or copolymeric polycarboxylate salts, in the presence of transition metal impurities, improve whiteness retention, textile ash deposition, and cleaning performance on clay, protein and oxidative soils. It is useful to.

The soil release agents useful in the compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid and ethylene glycol and / or propylene glycol units in various arrangements. Examples of such polymers are described in commonly assigned U.S. Pat.
No. 2033. Particularly preferred polymers according to EP-A-0272033 have the following formula:

Embedded image (Wherein, PEG is - (OC ₂ H ₄₎ a O-, PO is (OC ₃ H ₆ O), and T is _{(pcOC 6 H 4 CO))} .

Also very useful are modified polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1-2 propanediol, where the end groups are primarily sulfobenzoate and secondary It consists of a monoester of glycol and / or propane-diol. The goal is to obtain a polymer capped at both ends with sulfobenzoate groups, and "primarily", in the context of the present invention, most of the copolymers mentioned herein above are capped by sulfobenzoate groups. However,
Some copolymers are not yet completely capped, so their end groups consist of monoesters of ethylene glycol and / or propane 1-2 diol, and are then "secondarily" composed of such species. obtain.

The polyester selected herein has about 46% by weight dimethyl terephthalic acid, about 16% by weight propane-1,2-diol, about 10% by weight ethylene glycol, about 13% by weight dimethyl It contains sulfobenzoic acid and about 15% by weight sulfoisophthalic acid and has a molecular weight of about 3000. Polyesters and their method of manufacture are described in detail in EPA 311342.

It is well known in the art that free chlorine in tap water rapidly inactivates enzymes included in detergent compositions. Thus, the use of chlorine scavengers such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine at levels greater than 0.1% by weight of the total composition in the formulation will improve the wash-through stability of detergent enzymes. Can be provided. Compositions containing chlorine scavengers are described in European Patent Application No. 928700.
No. 18.6 (filed on Jan. 31, 1992).

[0147] Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are useful herein to provide additional fat removal. Such materials are described in WO 91/08281 and PCT 90/01815 (see page 4).
) (This description is included herein by reference). Chemically, these materials include polyacrylates having one ethoxy side chain for each 7-8 acrylate unit. The side chains have the formula _{- (CH 2 CH 2 O)} m (CH 2) n CH 3 (
Wherein m is 2-3 and n is 6-12). The side chains are esterified with the polyacrylate "backbone" to provide a "comb" polymer type structure. Molecular weights can vary, but typically range from about 2000 to about 50,000. Such alkoxylated polycarboxylates may be present in the compositions herein at about 0.
It may comprise from 05% to about 10% by weight.

Dispersant The detergent composition of the present invention may also contain a dispersant. Suitable water-soluble organic salts are homo-
Or a copolymer acid or a salt thereof, wherein the polycarboxylic acid contains at least two carboxyl groups separated from each other by no more than two carbon atoms. Such polymers are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates having a molecular weight of 2000 to 5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 1,000 to 1
It has a molecular weight of 00,000. In particular, copolymers of acrylate and methyl acrylate, for example with a molecular weight of 40
480N of 00 may be added to the detergent composition of the present invention at a concentration of 0.5 to 20% by weight of the composition.

The compositions of the present invention may contain a lime soap peptiser compound, which is preferably less than 8, preferably less than 7, most preferably less than 6, as described below. It has the following lime soap dispersing power (LSDP). The lime soap peptizer compound is preferably present at a concentration of 0% to 20% by weight.

Numerical measurements of the effectiveness of lime soap deflocculants are described in HC Borghetty and CA Bergman, J.
Lime soap dispersant power (LSDP) determined using the lime soap dispersant test as described in the editorial by Am. Oil. Chem. Soc., Volume 27, pages 88-90, (1950).
Is indicated by This lime soap dispersion test method is widely used by those skilled in the art, for example as mentioned in the following review article: WN Linfeld, Surfactant science S
eries, Volume 7, page 3; WN Linfield, Tenside surf. Det. volume 27, pa
ges 159-163, (1990); and MK Nagarajan, WF Masler, Cosmetics and Toile
tries, volume 104, pages 71-73, (1989). LSDP is 333 ppm CaC
With the weight percentage ratio of dispersant to sodium oleate required to disperse the lime soap precipitate formed by 0.025 g of sodium oleate in 30 ml of O ₃ (Ca: Mg = 3: 2) equivalent hardness water. is there.

Surfactants having good lime soap deflocculant capabilities include certain amine oxides,
Includes betaines, sulfobetaines, alkyl ethoxy sulfates and ethoxylated alcohols.

Exemplary surfactants having an LSDP of 8 or less for use in the invention include C ₁₆ -C ₁₈ dimethylamine oxide, C ₁₂ -C with an average degree of ethoxylation of 1-5.
Alkyl ethoxy sulfates C _18, in particular 3 alkyl ethoxy sulfate surfactant of C ₁₂ -C ₁₅ having a degree of ethoxylation (LSDP = 4), and 12 (
LSDP = 6) or include ethoxylated alcohols C ₁₄ -C ₁₅ having an average degree of ethoxylation of 30, sold by BASF GmbH under the trade name each Lutensol (Lutensol) A012 and Lutensol (Lutensol) A030.

Polymeric lime soap peptizers suitable for use herein are described in Cosmetics and Toil
MK Nagarajan, WF Ma found in etries, volume 104, pages 71-73 (1989).
It is described in an article by sler.

Hydrophobic bleaches such as 4- [N-octanoyl-6-aminohexanoyl] benzenesulfonate, 4- [N-nonanoyl-6-aminohexanoyl] benzenesulfonate, 4- [N-decanoyl-6 [Aminohexanoyl] benzenesulfonates and their mixtures, as well as nonanoyloxybenzenesulfonates, can also be used as lime soap peptizer compounds, along with hydrophilic / hydrophobic bleach formulations.

Detergency Inhibition The detergent compositions of the present invention inhibit solubilization from one textile to another and migration of suspended dyes encountered during a textile laundering operation on colored textiles. May also be included.

Polymer transfer inhibitor The detergent composition of the present invention comprises 0.001% by weight to 10% by weight, preferably 0.01% by weight.
It also contains from 2% by weight to 2% by weight, more preferably from 0.05% by weight to 1% by weight of a polymeric migration inhibitor. Said polymeric dye transfer inhibitors are usually included in the cleaning composition to suppress dye transfer from the colored fabric to the fabric with which it has been washed.
These polymers have the ability to bind or adsorb fading dyes that have been washed off the dyed fabric before the dyes have a chance to adhere to others during washing. Particularly suitable polymeric dye transfer inhibitors are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidone and polyvinylimidazole, or mixtures thereof. The addition of such polymers also enhances the performance of the enzymes of the present invention.

A) Polyamine N-Oxide Polymers Polyamine N-oxide polymers suitable for use contain units having the following structural formula:

Embedded image (Wherein P is a polymerizable unit to which an R-N-O group may be attached, or an R-N-O group forms part of the polymerizable unit, or both. Combination

[0158]

Embedded image x is 0 or 1, and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group, or any combination thereof, to which the nitrogen of the NO group is attached. Get or N-
The nitrogen of the O group is part of these groups).

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

Embedded image Wherein R ₁ , R ₂ and R ₃ are an aliphatic group, aromatic, heterocyclic or alicyclic group, or a combination thereof, and x and / or y and / or z are 0 or 1 And
The nitrogen of the NO group can be attached or the nitrogen of the NO group forms part of these groups).

The N—O group may be part of the polymerizable unit (P), or may be associated with the polymer backbone, or may be 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. Certain of the polyamine N-oxides include a polyamine N-oxide group in which the nitrogen of the NO group forms part of the R group. Preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Another class of such polyamine N-oxides comprises a polyamine N-oxide group, wherein the nitrogen of the NO group is attached to the R group.

Other suitable polyamine N-oxides are those in which the N—O group is attached to a polymerizable unit. Preferred types of these polyamine N-oxides are those of the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the NO functional group is Is a polyamine N-oxide. Examples of these types are polyamine oxides where R is a heterocyclic compound, such as pyridine, pyrrole, imidazole and derivatives thereof. Another preferred class of polyamine N-oxides is the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the NO functional group is Is bonded to a polyamine oxide. Examples of these types are polyamine oxides in which the R groups can be aromatic, for example phenyl.

As long as the resulting amine oxide polymer is water-soluble and has dye transfer inhibiting properties,
Any polymer backbone can be used. Examples of suitable polymer backbones are polyvinyl, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate and mixtures thereof.

The amine N-oxide polymers of the present invention typically have an amine to amine N-oxide ratio of from 10: 1 to 1: 1,000,000. However, the amount of amine oxide groups present in the polyamine oxide polymer can be adjusted by appropriate copolymerization.
Or it may vary depending on the appropriate degree of N oxidation. Preferably, the ratio of amine to amine N-oxide is from 2: 3 to 1: 1,000,000. More preferably, 1: 4-1.
: 1,000,000, most preferably from 1: 7 to 1: 1,000,000. The polymers of the present invention include, in fact, random or block copolymers in which one type of monomer is an amine N-oxide and the other type is or is not an amine N-oxide. The amine oxide units of the polyamine N-oxide have a PKa value such that PKa <10, preferably PKa <7, more preferably PKa <6. Polyamine oxides can obtain almost any degree of polymerization. The degree of polymerization is not important if the material has the desired water solubility and dye suspending power. Typically, the average molecular weight is between 500 and 1,000,000, preferably 1,000.
~ 50,000, more preferably in the range of 2,000-30,000, most preferably in the range of 3,000-20,000.

B) Copolymer of N-vinylpyrrolidone and N-vinylimidazole The N-vinylimidazole N-vinylpyrrolidone polymer used in the present invention is 5,000 to 1,000,000, preferably 5,000 to 200, It has an average molecular weight in the range of 000. A highly preferred polymer for use in the detergent composition of the present invention is an N-vinylimidazole N-vinylpyrrolidone copolymer, which is 5,000 to 50,000.
00, more preferably 8,000 to 30,000, most preferably 10,000.
A polymer selected from polymers having an average molecular weight in the range of 0 to 20,000. The average molecular weight range is based on Barth HG and Mays JW Chemical Analysis Vol 113,
Determined by light scattering as described in “Modern Methods of Polymer Characterization”. Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers are
It has an average molecular weight ranging from 5,000 to 50,000, more preferably from 8,000 to 30,000, and most preferably from 10,000 to 20,000.

N-vinylimidazole N- having the above average molecular weight range
While vinylpyrrolidone copolymers provide excellent dye transfer inhibition properties, they do not adversely affect the cleaning performance of detergent compositions formulated therewith. The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a 1 to 0.2, more preferably 0.8 to 0.3, most preferably 0.6 to 0.4 N
-Having a molar ratio of vinylimidazole to N-vinylpyrrolidone.

C) Polyvinylpyrrolidone The detergent composition of the present invention comprises from about 2,500 to about 400,000, preferably about 5,
000 to about 200,000, more preferably about 5,000 to about 50,000,
And most preferably, polyvinylpyrrolidone ("PVP") having an average molecular weight of about 5,000 to about 15,000 may also be utilized. Suitable polyvinylpyrrolidone are the product names PVP K-15 (viscosity molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000) and PVP K-90 (average molecular weight). Molecular weight 360,000) at ISP Corporation, New York,
Commercially available from NY and Montreal, Canada. Other suitable polyvinylpyrrolidones commercially available from BASF Cooperatio include Sokalan HP165 and Sokalan (Socalane) which are polyvinylpyrrolidones known to those skilled in the detergent art.
kalan) HP12 (eg EP-A-262,897 and EP-A
-256,696).

D) Polyvinyl oxazolidone: The detergent compositions of the present invention may also utilize polyvinyl oxazolidone as a polymeric dye transfer inhibitor. The polyvinyl oxazolidone is present in an amount from about 2,500 to about 400,000.
0, preferably about 5,000 to about 200,000, more preferably about 5,000
It has an average molecular weight from 0 to about 50,000, and most preferably from about 5,000 to about 15,000.

E) Polyvinylimidazole: The detergent compositions of the present invention may also utilize polyvinylimidazole as a polymeric dye transfer inhibitor. The polyvinyl imidazole is from about 2,500 to about 400,000;
Preferably from about 5,000 to about 200,000, more preferably from about 5,000 to
It has an average molecular weight of about 50,000, and most preferably from about 5,000 to about 15,000.

F) Crosslinked polymer: A crosslinked polymer is a polymer whose backbone is interconnected to a certain extent. These bonds are of chemical or physical nature, probably due to active groups on the backbone or side chains. Crosslinked polymers are available from Journal of Polymer Science, volume 2
2, pages 1035-1039. In one embodiment, the crosslinked polymers are made such that they constitute a three-dimensional rigid structure, and are capable of confining the dye in the pores formed by the three-dimensional structure. In another embodiment, the cross-linked polymer confines the dye by swelling. Such crosslinked polymers are described in co-pending patent application 94870213.9.

Cleaning Methods The compositions of the present invention may be used in essentially any cleaning or cleaning method, including, for example, dipping methods, pretreatment methods and rinsing to which a separate rinse aid composition can be added. Methods involving steps are included.

The method described herein comprises the step of contacting a knitted fabric with a cleaning solution in a conventional manner as exemplified below. The method of the invention is conventionally performed according to a cleaning operation. The cleaning method is preferably carried out at 5C to 95C, especially at 10C to 60C. The pH of the treatment solution is preferably 7-12.

A preferred machine dishwashing method involves treating the soil with an aqueous liquid having an effective amount of the machine dishwashing or rinsing composition dissolved or dispersed therein. A conventionally effective amount of a machine dishwashing composition means an amount of 8 to 60 g of material dissolved or dispersed in a 3 to 10 liter washing volume. According to the manual dishwashing method, an effective amount of the dishwashing composition, typically 0.5 to 20 g (per 25 dishes to be treated), is brought into contact with the soiled dish. A preferred manual dishwashing method involves applying a concentrated solution to the surface of the dish or dipping into a large dilution of the detergent composition.

The following examples are intended to illustrate the compositions of the present invention and are not necessarily meant to limit or define the scope of the present invention.

In detergent compositions, enzyme concentration is expressed as the amount of pure enzyme relative to the weight of the total composition, and unless otherwise specified, detergent components are expressed relative to the weight of the total composition. Abbreviations used in the text have the following meanings:

LAS: straight chain C _11-13 sodium alkylbenzene sulfonate. TAS: tallow sodium alkyl sulfate. CxyAS: C _{1x to} C _1y sodium alkyl sulfate. CxySAS: Second (2,3) sodium alkyl sulfate C _1x -C _1y. MBAS: Mid-branched alkyl sulfate. CxyEz: a C _{1x to} C _1y predominantly linear primary alcohol condensed with an average of z moles of ethylene oxide. CxyEzS: C _1x ~C sodium alkyl sulfate _1y condensed with an average z moles of ethylene oxide. CxEOy: Cy alcohol with average degree of ethoxylation _y Nonionic: Mixed ethoxylated / propoxylated fatty alcohol, for example
Pluraf with an average ethoxylation degree of alcohol of 3.8 and an average propoxylation degree of 4.5
ac LF404. QAS: R _{2 ·} N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH), where R ₂ = C ₁₂ -C ₁₄ . SADS: Formula 2-R. C4H7. -1,4- (SO4-) 2 (wherein R = C _10-18
C ₁₄ -C ₂₂ alkyl disodium sulfate)

MES: x-sulfomethyl ester of C18 fatty acid APA: _{Amidopropyldimethylamine} of C8-10. Soap: sodium linear alkyl carboxylate obtained from an 80/20 mixture of tallow and coconut fatty acids. Neodol xy-z: C _{1x to} C _1y linear primary alcohol z ethoxylate. CFAA: alkyl N- methyl glucamide of C ₁₂ -C _14. TFAA: alkyl N- methyl glucamide of C ₁₆ -C _18. TPKFA: Toppudo total cleavage of _{C 12 ~C 14 (topped whole cut} ) fatty acids. DEQA: di- (tallow-oxy-ethyl) dimethylammonium chloride. DEQA (2): di- (soft tallowyloxyethyl) hydroxyethylmethylammonium methyl sulfate. DTDMAMS: ditallow dimethyl ammonium methyl sulfate. SDASA in a 1: 2 ratio of stearyl dimethylamine: triple presed (triple pres
sed) Stearic acid. Silicate: amorphous sodium silicate (ratio of SiO ₂ : Na ₂ O = 1.6-3.2: 1)
.

Metasilicate: sodium metasilicate (ratio of SiO ₂ : Na ₂ O = 1.0). Zeolite A: hydrated sodium aluminosilicate having a primary particle size of 0.1 to 10 μm (weight based on anhydride), formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ · 27
H ₂ O. (Na-) SKS-6: a crystalline layered silicate of formula δ-Na ₂ Si ₂ O ₅ . Citrate: trisodium citrate dihydrate. Citric acid: citric anhydride. Borate: sodium borate. Carbonate: anhydrous sodium carbonate. Bicarbonate: anhydrous sodium bicarbonate. Sulfate: anhydrous sodium sulfate. STPP: sodium tripolyphosphate. TSPP: tetrasodium pyrophosphate. MA / AA: 4: 1 acrylate having an average molecular weight of about 70,000 to 80,000 /
Maleate random copolymer. MA / AA1: a random copolymer of 6: 4 acrylate / maleate with an average molecular weight of about 10,000. AA: sodium polyacrylate polymer having an average molecular weight of about 4,500.

Polycarboxylate: a copolymer of acrylic acid with a molecular weight of 4,500, BAS
Copolymers consisting of a mixture of carboxylate monomers, such as acrylates, maleates and methyl acrylates, with molecular weights ranging from 2,000 to 80,000, such as Sokolan, commercially available from F. PB1: anhydrous sodium perborate monohydrate. PB4: sodium perborate tetrahydrate of nominal formula NaBO ₃ .4H ₂ O. Percarbonate: anhydrous sodium percarbonate with a nominal formula of 2.74 Na ₂ CO ₃ .3H ₂ O ₂ . NaDCC: sodium dichloroisocyanurate. TAED: tetraacetylethylenediamine. NOBS: Nonanoyloxybenzenesulfonate in the form of its sodium salt. NACA-OBS: (6-nonamidocaproyl) oxybenzenesulfonate.

DOBS: sodium salt of decanoyloxybenzenesulfonate. DTPA: diethylenetriaminepentaacetic acid. HEDP: 1,1-hydroxyethanediphosphonic acid. DETPMP: diethyltriaminepenta (methylene) phosphonate, sold by Monsanto under the trade name Dequest 2060. EDDS: Sodium salt form of the (S, S) isomer ethylenediamine-N, N '
-Disuccinic acid. Chelating agent: a chelating agent selected from EEDS, HEDP, DTPA, DETPMP and / or a mixture thereof. MnTACN: manganese 1,4,7-trimethyl-1,4,7-triazacyclononane. Light activated bleach: sulfonated zinc phthalocyanine encapsulated in a dextrin soluble polymer. Light activated bleach 1: sulfonated aluminophthalocyanine encapsulated in dextrin soluble polymer. PAAC: pentaamine acetate cobalt (III) salt. Paraffin: Paraffin oil sold by Wintershall under the name Winog 70.

NaBz: sodium benzoate. Pectate lyase: pectate lyase from Bacillus agaradhaerens, NCIMB 40482 or DSM8721. Pectin lyase: Pectin lyase produced by Bacillus licheniformis, ATCC 14580. Proteases: Savinase, Alcalase, Durazyme
Proteolytic enzymes sold by Novo Nordisk A / S under the trade name of (Durazyme), by Gist-Brocades under the trade name of Maxacal, Maxapem, patents WO91 / 06637 and / or WO95 / 10591 And / or the proteases described in EP 251446. Amylase: described in WO 94/18314, WO 96/05295 and under the trade name Purafact Ox AM® by Genencor, WO
Novo under the tradenames Termamyl (registered trademark), Fungamyl (registered trademark) and Duramyl (registered trademark) described in US Patent No. 95/26397.
An amylolytic enzyme sold by Nordisk A / S.

Lipases: Novo Nordisk A / S under the trade name of Lipolase, Lipolase Ultra and Gist-Broc under the trade name of Lipomax
A lipolytic enzyme sold by ades. Cellulase: Cellulolytic enzyme sold by Novo Nordisk A / S under the trade name of Carezyme, Celluzyme and / or Endolase. CMC: sodium carboxymethyl cellulose. PVNO: polyvinyl pyridine-N-oxide having an average molecular weight of 50,000. PVPVI: a copolymer of vinylimidazole and vinylpyrrolidone with an average molecular weight of 20,000. Brightener 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 disulfonate. Silicone defoamer: a polydimethylsiloxane foam control agent containing a siloxaneoxyalkylene copolymer as a dispersant and having a foam control agent to dispersant ratio of 10: 1 to 100: 1. Foaming inhibitor: 12% silicone / silica, 18% stearyl alcohol, 70%
Starch (granular form).

Opacifying agent: aqueous monostyrene latex mixture (sold by BASF Aktiengesellschaft under the trade name Lytron 621). Thickener: high molecular weight crosslinked polyacrylate such as Carbopol from BFGoodrich Chemical Company and Polygel SRP1: anionic end-capped polyester. SRP2: Diethoxylated poly (1,2 propylene terephthalate) short block polymer. QEA: bis _{((C 2 H 5 O)} (C 2 H 4 O) n) (CH 3) -N + -C 6 H 12 -N + - (CH 3) bis _{((C 2 H 5 O)} - _{(C 2 H 4 O))} n ( where, n = 20~30). SCS: sodium cumene sulfonate. HMWPEO: high molecular weight polyethylene oxide. PEGx: polyethylene glycol of molecular weight x. PEO: polyethylene oxide having an average molecular weight of 5,000. TEPAE: tetraethylene pentaamine ethoxylate. BTA: benzotriazole. pH: Measured as a 1% solution in distilled water at 20 ° C.

[0183]

【Example】

 Example 1 The following high density, bleach-containing, laundry detergent composition was prepared according to the present invention.

[Table 1]

[Table 2]

Example 2 The following particulate or tablet laundry composition was prepared in accordance with the present invention.

[Table 3]

[Table 4]

Example 3 The following high density laundry detergent composition was prepared according to the present invention.

[Table 5]

[Table 6]

Example 4 The following particulate or tablet laundry composition was prepared according to the present invention.

[Table 7]

[Table 8]

Example 5 The following high density laundry detergent composition was prepared in accordance with the present invention.

[Table 9]

[Table 10]

Example 6 The following particulate detergent was prepared according to the present invention.

[Table 11]

[Table 12]

Example 7 The following laundry detergent composition was prepared according to the present invention.

[Table 13]

[Table 14]

Example 8 The following laundry detergent composition was prepared according to the present invention.

[Table 15]

[Table 16]

Example 9 The following liquid detergent composition was prepared according to the present invention (concentrations are given in parts by weight, the enzyme is expressed as pure enzyme).

[Table 17]

Example 10 The following liquid detergent composition was prepared according to the present invention (concentrations are given in parts by weight, the enzyme is expressed as pure enzyme).

[Table 18]

[Table 19]

Example 11 The following liquid detergent composition was prepared according to the present invention (concentrations are given in parts by weight, the enzyme is expressed as pure enzyme).

[Table 20]

Example 12 A particulate knitted textile detergent composition providing the following "softening by washing" ability was prepared in accordance with the present invention (concentrations are given in parts by weight, enzymes are expressed as pure enzymes).

[Table 21]

Example 13 The following rinsed knitted fabric softener composition was prepared in accordance with the present invention.

[Table 22]

Example 14 The following knitted fabric softener and dry-added knitted fabric conditioner composition was prepared in accordance with the present invention.

[Table 23]

Example 15 The following laundry bar detergent composition was prepared in accordance with the present invention (concentrations are given in parts by weight, enzyme is expressed as pure enzyme).

[Table 24]

Example 16 The following compact high density (0.96 Kg / l) dishwashing detergent composition was prepared according to the present invention.

[Table 25]

Example 17 The following particulate dishwashing detergent composition having a bulk density of 1.02 Kg / L was prepared according to the present invention.

[Table 26]

Example 18 A particulate dishwashing detergent composition was prepared using a standard 12 head rotary press,
The following tablet detergent composition was prepared according to the present invention by compressing at a pressure of KN / cm ² .

[Table 27]

Example 19 The following liquid automatic dishwashing detergent composition having a density of 1.40 Kg / L was prepared according to the present invention.

[Table 28]

Example 20 The following liquid rinse aid composition was prepared according to the present invention.

[Table 29]

Example 21 The following manual liquid dishwashing composition was prepared according to the present invention.

[Table 30]

Example 22 The following liquid hard surface cleaning composition was prepared in accordance with the present invention.

[Table 31] * Na4 ethylenediamine diacetic acid ** diethylene glycol monohexyl ether

Example 23 The following spray composition for cleaning hard surfaces and removing household mold was prepared in accordance with the present invention.

[Table 32] * Diethylene glycol monobutyl ether

Example 24 The following antiseptic composition was prepared in accordance with the present invention.

[Table 33]

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE , KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (72) Inventor Showell, Michael Stamford Cincinnati, Compton, Ohio, USA Road 685 (72) Inventor Jew, Yong, Ohio, Cincinnati, Bromyard, Avenue 4348 (72) Inventor Moses, Rosa Laura, Ohio, USA, West, Chester, Eagle, Creek, Court 8815 (72) Inventor Betty All, Jean-Luc Philippe Belgium 1200, Brussels, Avigne, Sreger 93 (72) Inventor Schuhl, Alfred Belgium 1840, Ronderserl, Handelsstraat 210 (72) Inventor Wells, Eric United States Ohio, Cincinnati, AW, Kemper, Road, number 1601 1440 F-term (reference) 4H003 AB19 AB27 AC08 AE06 DA01 DA05 DA17 DA19 EA12 EA15 EA16 EA20 EA27 EA28 EB08 EB12 EB19 EB22 EB24 EB32 EB36 EB37 EB42 EC01 EC02 EC03 EE05 FA04 FA43 FA47

Claims (7)

[Claims] 1. Detergent component, pectate lyase enzyme (EC 4.2.2.2)
And a pectin lyase (EC 4.2.2.10) enzyme. 2. The pectate lyase comprises 0.0001 to 2% by weight of the total composition, preferably 0.0005 to 0.5% by weight, more preferably 0.001 to 0.5%.
The detergent composition according to claim 1, which is present at a concentration of 1% by weight of pure enzyme. 3. The pectin lyase comprises 0.0001 to 2% by weight of the total composition.
, Preferably 0.0005 to 0.5% by weight, more preferably 0.001 to 0.1% by weight.
3. The detergent composition according to claim 1 or 2, wherein the detergent composition is present in a concentration of pure enzyme by weight. 4. The pectin lyase and the pectate lyase are used in an amount of 0.00
01 to 4% by weight, preferably 0.0005 to 2% by weight, more preferably 0.00
4. The detergent composition according to claim 1, which contains a total concentration of 1 to 1% by weight. 5. The pectate lyase and the pectin lyase in a weight ratio of pure enzyme of 10: 1 to 1:10, more preferably 5: 1 to 1: 5, most preferably 2: 1 to 1: 5. The detergent composition according to claim 1, wherein 6. The detergent composition according to claim 1, wherein said detergent component is a bleaching agent, preferably a bleaching activator bleaching system. 7. A method for cleaning knitted fabrics, tableware and / or hard surfaces with the composition according to claim 1.