CN1276825A

CN1276825A - Detergent compositions comprising mannanase and soil release polymer

Info

Publication number: CN1276825A
Application number: CN98810236A
Authority: CN
Inventors: J·L·P·贝蒂奥尔; C·A·J·K·托恩
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1997-08-14
Filing date: 1998-06-10
Publication date: 2000-12-13
Also published as: CN1469919A; CA2301156A1; MXPA00001610A; HUP0003670A3; WO1999009127A1; AU7832798A; DE69837850D1; CN1336953A; BR9811195A; JP4090688B2; DE69810309T2; CA2299410A1; MXPA00001614A; BR9811189A; CN1276826A; ATE276344T1; BR9811190A; CA2301167A1; JP2001515132A; EP1009794A1

Abstract

The present invention relates to laundry detergent compositions, comprising a saccharide gum degrading enzyme and cotton fabric soil removal polymer providing excellent abstersion and soil removal performance.

Description

The detergent composition that contains mannase and soil release polymer

Invention field

The present invention relates to contain the laundry detergent composition of mannase and cotton goods soil release polymer.This soil release polymer is water-soluble and/or dispersible modified polyamine, and it contains functionalized skeleton part, SYNTHETIC OPTICAL WHITNER is had the stability of improvement.

Background of invention

Known in the prior art various family and the technical fabric treating processes of being used for, for example various stain removers that use in laundry, the fabric drying in the warm air clothes dryer etc.The commercialization of various stain removers is used for detergent composition and fabric softener/antistatic article and composition at present.This soil release polymer contains oligomerisation or polymeric ester " skeleton " usually.

Until now, effective cotton goods stain remover that exploitation is used for detergent for washing clothes remains unintelligible, other people attempts adopting the example with the structure matching soil release polymer structure of fabric, does not produce MIN result in polyester soil release polymers field successful method when being used for the cotton goods stain remover.Use methylcellulose gum, have the unitary cotton goods glycocalix of the oligomerisation of improvement and confirm polyester comparison cotton goods more effective.For example on April 26th, 1973, disclosed U.K.1314897 instructed the Vltra tears that is used to avoid wet soil redeposition and improves the fabric decontaminating of washing.The US3897026 of Kearney discloses the decontamination with improvement and the cellulose textile material of stain resistance, and it obtains by the hydroxylic moiety reaction of ethene-maleic anhydride copolymers and cotton polymkeric substance.The US3912681 of Dickson discloses and has been used for the composition that the impermanency decontamination is handled, and it contains the polycarboxylate polymer less than 3 o'clock cotton goods at pH.The US3948838 of Hinton etc. has described high molecular (500000-1500000) the polyacrylic acid based polymer that is used for decontamination, and it preferably uses with other fabric-treating agent.The US4559056 of Leigh etc. discloses the method with compositions-treated cotton or synthetic textiles, and described composition contains organopolysiloxane elastomerics, organo-siloxane oxyalkylene copolymers linking agent and siloxanes curing catalysts.Other stain remover that does not contain terephthalate and polyoxyethylene/oxypropylene mixture is by disclosed caprolactam resin in US4579681 and 4614519 such as Rupert.The example of alkoxylate polyamine and quaternized alkoxylate polyamine is open in EP206513, is suitable as dirt dispersant.WO97/42288 describes the effective stain remover be used for cotton products, and it can be by acceptable some modified polyamine preparation of all cotton products, no matter does washing to be in the presence of SYNTHETIC OPTICAL WHITNER or not to be.Except that the above-mentioned prior art of enumerating, following various soil release polymers or the modified polyamine of disclosing: the US5565145 of the Watson of promulgation on October 15th, 1996 etc., the US4548744 of the Connor of promulgation on October 22nd, 1985, the US4597898 of the Vander Meer of promulgation on July 1st, 1986, the US4877896 of the Maldonado of promulgation on October 31st, 1989 etc., the US4891160 of the Vander Meer of promulgation on January 2 nineteen ninety, the US4976879 of the Maldonado of promulgation on December 11 nineteen ninety etc., the US5415807 of the Gosselink of promulgation on May 16 nineteen ninety-five, the US4235735 of the Marco of promulgation on November 25th, 1980 etc., November 30 nineteen ninety-five disclosed WO95/32272, on December 29th, 1978 disclosed GB1537288, on January 18th, 1978 disclosed GB1498520, the DE2829022 of promulgation on January 10th, 1980, on April 27th, 1994 disclosed JP06313271.

Yet, use this cotton goods soil release polymer to be not sufficient to protect clothes to avoid spot and surround, especially for makeup and food stain.In fact, modern makeup and food compositions contain increasing additive, for example are used as the hydro-colloid glue of thickening material.Mannosans, guar gum and carob bean gum be used for many makeup and food compositions (referring to Industrial Gum, the 2nd edition, R.L.Whistler, the 308th page, Academic Press, 1973, ISBN, 0-12-74-6252-x).Known these hydro-colloid glue of people have very high avidity to cellulosic material, thereby are difficult to remove.At present, making the soil release polymer that uses cotton goods be not enough to solve this makeup/food stain surrounds.

The foods and cosmetics stain has been represented most of stain relevant with the human consumer, contains foodstuff additive usually, for example thickeners/stabilizers.In fact, hydro-colloid glue and emulsifying agent are usually as foodstuff additive.Polysaccharide (long chain polymer) or their derivative that one group of industry of term " glue " expression is used, their hydrations in heat or cold water form viscous soln, dispersion or gel.Glue is categorized into natural and modification.Natural gum comprises Seaweed Extract, plant milk extract, the glue that is obtained by seed or root and the glue that is obtained by microbial fermentation.(semi-synthetic) glue of modification comprises Mierocrystalline cellulose and starch derivative and some synthetical glue, for example rudimentary methoxypectin, propylene glycol alginate and carboxyl methyl and the hydroxypropyl guar gum (natural gum in the chemical technology encyclopaedia (Gums in Encyclopedia Chemical Technology) 4th Ed.12 volume, the 842-862 page or leaf, J.Baird, Kelco division of Merck).Also (EaganPress-1997) referring to the carbohydrate chemistry (Carbohydrate Chemistry for Food Scientists) of Food science, R.L.Whistler and J.N.BeMiller, the 4th chapter, direct food additive in 63-89 page or leaf and the processing fruits (Direct Food Additives in FruitProcessing), P.Laslo, Bioprinciples and Applications, the 1st volume, the II chapter, 313-325 page or leaf (1996) Technomie publishing.The part of these glue, for example guar gum (E412), carob bean gum (E410) are widely used in food applications (Gums in ECT 4th Ed. the 12nd volume, 842-862 page or leaf, J.Baird, Kelco divisionof Merck) separately or in combination.

The guar gum that uses in these foods and cosmetics spots is obtained by the seed endosperm of bean Cyamopsistetragonoloba.The guar gum (being also referred to as melon ear sugar) that is extracted by dicotyledonous seed is by 1-4, b-D-pyran-mannose glycosylation unit skeleton is formed, in seasonings and refrigerated products and makeup, be used as thickening material (H.-D.Belitz, Food Chemistry, the 243rd page, second edition English copy, Springer-verlag, 1987, ISBN 0-387-15043-9 (US)) ﹠amp; (Carbohydrate Chemistry for Food Scientists, R.L.Wilstler, eagan press, 1977, ISBN 0-913250-92-9) ﹠amp; (Industrial Gum, second edition, 308 pages of R.L.Whistler, Academic Press, 1973, ISBN, 0-12-74-6252-x).Carob bean gum (being also referred to as tragon or St Jon ' s bread) also is used for foodstuffs industry, by the seed extraction of the evergreen plant of planting in the mediterranean region.The difference of the structure of carob bean gum and guar gum only is fewer purpose D-galactosyl side chain, has identical 1-4, b-D-pyran-mannose glycosylation skeleton.In legume-seeds, water-soluble gala mannosans is main storage carbohydrate, in some cases, accounts for 20% of gross dry weight amount at the most.Polygalactomannan has α-semi-lactosi of the O-6 that is connected in mannose residue, also can be acetylation into various degree on the O-2 of mannose residue and O-3.

As mentioned above, people still constantly need prepare laundry detergent composition, and it provides outstanding scourability, especially to makeup and food stain and clean effect.This purpose can satisfy by the laundry detergent composition that preparation contains mannase and cotton goods soil release polymer.

We find that also the performance of laundry detergent composition of the present invention is selected from washing assistant by adding, especially zeolite, tripoly phosphate sodium STPP and/or layered silicate; Tensio-active agent, preferred nonionic surfactants, for example alkylethoxylate or alkyl methyl glucamide; Other detergent component of conventional soil release polymer and/or their mixture and improving.

Mannase is discerned in some bacillus biologies.The Appl.Environ.Microbiol. of Talbot etc. for example, 56 volumes, No.11,3505-3510 page or leaf (1990) have described a kind of 'beta '-mannase of the dimeric forms that is obtained by bacstearothermophilus, and it has the molecular weight of 162kDa and the best pH of 5.5-7.5.The World J.MicobioBoitech. of Mendoza etc., the 10th volume, no.5, it is 38kDa that 551-555 (1994) has described the MW that is obtained by subtilis, optimum activity is 4.8 'beta '-mannase at pH5.0/55 ℃ and pl.J0304706 disclose by having of obtaining of bacillus with the MW of gel filteration determining be 37+/-3kDa, best pH is that 8-10 and pl are the 'beta '-mannase of 5.3-5.4.J63056289 has described alkalescence, the heat-staple 'beta '-mannase of preparation, and its hydrolysis is the β of mannosans-1 for example, and 4-D-mannopyranose glycosidic bond produces manna oligosaccharide.J63036774 relates to micro-organisms bacillus FERM P-8856, and it produces 'beta '-mannase and beta-Mannosidase under alkaline pH.It is open at WO97/11164 that a kind of mannase of the purifying from bacillus amyloliquefaciens and they are used for the preparation method of bleached pulp.WO91/18974 described a kind of under limit pH and temperature active hemicellulase, for example dextranase, zytase or mannase and their preparation method.WO94/25576 has described the active enzyme of demonstration mannase that is obtained by Aspergillus aculeatus CBS101.43, and it can be used for various uses, and the degraded or the modification of plant or alga cells wall material are desirable.WO93/24622 discloses the isolating mannase that is used for the bleaching lignin cellulose pulp by Trichoderma reesie.

Yet people do not recognize that yet mannase and the synergistic combination of cotton goods soil release polymer in laundry detergent composition are to provide outstanding washing and detergency ability so far.

Summary of the invention

The present invention relates to contain the laundry detergent composition of mannase and cotton goods soil release polymer, these compositions provide outstanding washing and detergency ability.

The detailed description of invention

The basal component of laundry detergent composition of the present invention is a mannase.Mannase

Comprise in the present invention be following three kinds of mannosans degrading enzyme: EC3.2.1.25: beta-Mannosidase, EC3.2.1.78: inscribe-1, the 4-beta-Mannosidase, hereinafter referred to as " mannase " and EC3.2.1.100:1, the biological Glycosylase (IUPAC classification-enzyme nomenclature, 1992 ISBN 0-12-227165-3 Academic Press) of 4-β-sweet dew.

Laundry laundry detergent composition of the present invention more preferably contains the β-1 that is called mannase, 4-mannosidase (E.C.3.2.1.78).The mannase that term " mannase " or " polygalactomannan enzyme " expression define officially according to prior art, it is called mannosans inscribe-1, the 4-beta-Mannosidase, and be called 'beta '-mannase and inscribe-1 in addition, the 4-mannase, and catalysis is in mannosans, polygalactomannan, glucomannan and galactoglucomannan 1, the random hydrolysis reaction of 4-β-D-seminose glycosidic bond.

Mannase (EC 3.2.1.78) especially constitutes one group of polysaccharidase, its mannosans of degrading, expression can be ruptured and be contained the enzyme of the unitary polysaccharide chain of seminose, promptly can break at the enzyme of the glycosidic link in mannosans, polygalactomannan, glucomannan and the galactoglucomannan.Mannosans is to contain by β-1, the polysaccharide of the skeleton that the seminose that 4-connects is formed; Glucomannan is to contain more or less alternative β-1 regularly, the polysaccharide of the seminose that 4-connects and the skeleton of glucose; Polygalactomannan and galactoglucomannan are to have α-1, the mannosans and the glucomannan of the galactose side that 6-connects.These compounds can be acetylation.

The degraded of polygalactomannan and galactoglucomannan becomes easy by removing galactose side wholly or in part.In addition, the degraded of acetylizad mannosans, glucomannan, polygalactomannan and galactoglucomannan becomes easy by deacetylated wholly or in part.Ethanoyl can be removed by alkali or mannosans acetylase.Can further degrade to discharge free maltose by the oligopolymer that the mixture of mannase or mannase and alpha-galactosidase and/or mannosans acetylase discharges by beta-Mannosidase and/or beta-glucosidase enzyme.

Mannase is discerned in some bacillus biologies.The Appl.Environ.Microbiol. of Talbot etc. for example, 56 volumes, No.11,3505-3510 page or leaf (1990) have described a kind of 'beta '-mannase of the dimeric forms that is obtained by bacstearothermophilus, and it has the molecular weight of 162kDa and the best pH of 5.5-7.5.The World J.Microbiol of Mendoza etc., Biotech., the 10th volume, No.5, it is 38kDa that 551-555 (1994) has described the MW that is obtained by subtilis, optimum activity is 4.8 'beta '-mannase at pH5.0/55 ℃ and pl.It is 373kDa that JP-0304706 discloses the MW that has with gel filteration determining that is obtained by Bacillaceae, and best pH is that 8-10 and p1 are the 'beta '-mannase of 5.3-5.4.JP-63056289 has described alkalescence, the heat-staple 'beta '-mannase of preparation, and its hydrolysis is the β of mannosans-1 for example, and 4-D-mannopyranose glycosidic bond produces manna oligosaccharide.JP-63036774 relates to bacillus micro-organism FERM P-8856, and it produces 'beta '-mannase and beta-Mannosidase under alkaline pH.JP-08051975 discloses the alkaline ' beta '-mannase that is obtained by close alkali bacillus AM-001.A kind of purifying mannase that is used for bleached pulp and their preparation method from bacillus amyloliquefaciens is open at WO97/11164.WO91/18974 described a kind of under limit pH and temperature active hemicellulase, for example dextranase, zytase or mannase.WO94/25576 discloses the active enzyme of demonstration mannase that is obtained by Aspergillus aculeatus CBS 101.43, and it can be used for degraded or improved plant or alga cells wall material.WO93/24622 discloses the isolating mannase that is used for the bleaching lignin cellulose pulp by Trichoderma reseei.The hemicellulase of the hemicellulose that contains mannosans of can degrading in WO91/18974, describe and the purifying mannase that obtains by bacillus amyloliquefaciens open in WO97/11164.

This mannase is the alkali mannanase as giving a definition especially, most preferably the mannase that is obtained by bacterial origin.Laundry detergent composition of the present invention especially contains alkali mannanase, and it is selected from by bacterial strain Bacillus agaradherens and/or bacillus subtilis strain 168, the mannase that gene yght obtains.

Term " alkali mannanase " is meant and is included in 7-12, has at least 10% of its maximum activity in the given pH scope of preferred 7.5-10.5, preferably at least 25%, and the more preferably enzyme of at least 40% enzymic activity.

Laundry detergent composition of the present invention most preferably contains the alkali mannanase that is obtained by Bacillus agaradherens, and described mannase is:

I) by Bacillus agaradherens, the polypeptide of NCIMB40482 preparation, or

Ii) contain just like the polypeptide of the aminoacid sequence shown in the position 32-343 of SEQ ID NO:2 or

Iii) at i) or ii) in the analogue of polypeptide of definition, it at least 70% with described homologous peptide, or obtain by described polypeptide, or the polyclonal antibody reaction of the pure form that produces with relative described polypeptide by displacement, disappearance or additional one or more amino acid.

The present invention also comprises having the active isolated polypeptide of mannase, and it is selected from:

(a) polynucleotide molecule of coded polypeptide, it has the mannosans enzymic activity, and contain just like among the SEQID NO:1 by the nucleotide sequence shown in the Nucleotide 97-Nucleotide 1029;

(b) kind homologue (a);

(c) polynucleotide molecule, its coding has a mannosans enzymic activity, with among the SEQ ID NO:2 by the identical polypeptide of the aminoacid sequence at least 70% of amino-acid residue 32-amino-acid residue 343;

(d) with (a) and (b) or (c) complementary molecule; With

(e) (a) and (b), (c) or degenerate core nucleotide sequence (d).

The plasmid pSJ1678 that contains the polynucleotide molecule (dna sequence dna) of the mannase of the present invention of encoding is converted into coli strain, it by the inventor according to budapest treaty about the international endorsement (Budapest Treaty on theInternational Recognition of the Deposit of Microorganisms forthe Purposes of Patent Procedure) of patented procedure microbial preservation at the Deutsche Sammlung vonMikroorganismen und Zellkulturen GmbH, Mascheroder Weg 1b, D-38124 Braunschweig, Federal Republic of Germany is in preservation on May 18 in 1998, preserving number DSM12180.

Second kind of most preferred enzyme is the mannase that is obtained by bacillus subtilis strain 168, this mannase:

I) by the encoding part coding of the analogue of dna sequence dna shown in the SEQ ID No.5 or described sequence and/or

Ii) contain the aminoacid sequence shown in the SEQ ID NO:6 polypeptide or

Iii) ii) in the analogue of polypeptide of definition, it at least 70% with described homologous peptide, or obtain by described polypeptide, or the polyclonal antibody reaction of the purified form that produces with relative described polypeptide by displacement, disappearance or additional one or more amino acid.

(a) polynucleotide molecule of coded polypeptide, described polypeptide has the mannosans enzymic activity, and contains just like the nucleotide sequence shown in the SEQ ID NO:5;

(b) kind homologue (a);

(c) polynucleotide molecule, its coding has a mannosans enzymic activity, the polypeptide identical with the aminoacid sequence at least 70% of SEQ ID NO:6;

(d) with (a) and (b) or (c) complementary molecule; With

(e) (a) and (b), (c) or degenerate core nucleotide sequence (d).Definition

Before further going through the present invention, at first be defined as follows term:

Polypeptide or protein that term " directly to autoploid (ortholog) " (or " kind homologue ") expression is obtained by a kind, this kind with have homology from similar polypeptide not of the same race or protein.

Polypeptide or protein that term " symbiosis autoploid (paralog) " expression is obtained by given kind, this kind with have homology from not homopolypeptide or protein mutually of the same race.

Term " expression vector " expression straight chain or Circular DNA molecular structure, it contains the fragment of the interested polypeptide of encoding, and the additional clip that provides it to transcribe is provided described polypeptide.This additional clip can comprise promotor and terminator sequence, but optionally comprises one or more replication orgin, one or more selection markers, enhanser, polyadenylation signal etc.Expression vector is obtained by plasmid or viral DNA usually, or can contain this two portions simultaneously.Expression vector of the present invention can be any expression vector, and it can carry out the recombinant DNA process easily, and the host cell that carrier is introduced is depended in the selection of carrier usually.Therefore, carrier can be an autonomously replicationg vector, i.e. the carrier that exists as the extrachromosome entity, it duplicate and chromosome duplication irrelevant, plasmid for example.Carrier can be a kind of carrier in addition, and when it introduced host cell, it was integrated in the host cell gene group, duplicates with the karyomit(e) of being integrated.

Be used for the term " recombinant expressed " relevant of the present invention or " express on reorganization ground " standard definition definition according to prior art with polypeptide or protein expression.Recombinant expression of proteins is usually by using above-mentioned expression vector to carry out.

When being used for polynucleotide molecule, term " isolating " expression polynucleotide are by taking out in its natural gene environment, thereby do not have other external or unwanted encoding sequence, are the forms that is suitable for the engineered protein production system.This isolating molecule is by the isolating material of their natural surroundings, comprises cDNA and genomic clone.Isolated DNA molecule of the present invention does not have other gene associating with it usually, but can comprise 5 ' and 3 ' non-translational region of natural generation, for example promotor and terminator.The identification in zone of associating is obvious (referring to for example, Dynan and Tijan, Nature316:774-78,1985) for those of ordinary skills.

In addition, term " isolating polynucleotide " can be described as " clone's polynucleotide ".When being used for protein/polypeptide, term " isolating " is illustrated in the protein of finding under the condition outside its natural surroundings.In a preferred form, isolating protein does not have other protein on substantially, especially other homologous protein (i.e. " homology impurity " (seeing below)).Preferably with greater than 40% pure form, the pure form more preferably greater than 60% provides protein.More preferably, preferably with high-purity form, promptly by SDS-PAGE measure greater than 80% purity, the purity more preferably greater than 95% and most preferably provide protein greater than 99% purity.

In addition, term " isolating protein/polypeptide " can be described as " protein/polypeptide of purifying ".

Any impurity (other polypeptide outside the polypeptide for example of the present invention) represented in term " homology impurity ", and it is by the therefrom original homologous cell generation that obtains polypeptide of the present invention.Term when being used for this paper specified microorganisms source " by ... obtaining " expression is by particular source or the polynucleotide and/or the polypeptide that are made by the cell that has wherein inserted from the gene in source.

Term when relating to dna fragmentation " is operably connected " and represents that the arrangement fragment makes that they are that its required purposes as one man works, and for example transcribes from promotor, and encoded fragment proceeds to terminator.

Term " polynucleotide " expression is read the deoxyribonucleotide of 3 ' end or the strand or the dichain polymer of ribonucleotide base by 5 '.Polynucleotide comprise RNA and DNA, can be separated by natural origin, external synthetic or by natural and synthetic molecules in conjunction with preparation.

The polynucleotide molecule with complementary base sequence and inverted orientation is compared in term " complementation of polynucleotide molecule " expression with reference sequences.For example sequence 5 ' ATGCACGGG3 ' and 5 ' CCCGTGCAT3 ' complementation.

A kind of nucleotide sequence that comprises one or more degenerate codons (comparing) of term " degenerate core nucleotide sequence " expression with the reference polynucleotide molecule of coded polypeptide.Degenerate codon contains the different triplets of Nucleotide, but the identical amino-acid residue of encoding (be GAU and GAC triplet all encode Asp).

Term " promotor " expression contains the part of the gene of dna sequence dna, and it provides the combination of RNA polymerase and the beginning of transcribing.Promoter sequence is common, but does not always find in 5 ' non-coding region of gene.

Dna sequence dna represented in term " secretory signal sequence ", its coded polypeptide (" secrete polypeptide "), and as the component of big polypeptide, the Secretory Pathway of the cell of polypeptide instructs polypeptide greatly by wherein synthesizing greatly.When transporting by Secretory Pathway, big polypeptide ruptures usually to remove the secretion peptide.How to use sequence of the present invention to obtain other correlated series:

The sequence information that relates to the polynucleotide sequence of the mannase of the present invention of encoding disclosed by the invention can be used as the instrument of identifying other homology mannase.For example, polymerase chain reaction (PCR) can be used for amplifying coding from various microbial sources, the sequence of other homology mannase of the microbial source of especially different bacillus.Be used for the analysis of activity test

Having the active polypeptide of the present invention of mannase can be according to standard test methods test mannosans enzymic activity well known in the prior art, for example be applied in the 4mm diametric hole of on the agar plate that contains 0.2%AZCL polygalactomannan (carob bean gum), getting by the solution that will be tested, promptly be used for inscribe-1, substrate (the Internet address of Megazyme: http://www.megazyme.com/Purchase/index.html) that 4-β-D-mannase is analyzed as CatNo.1-AZGMA with what per 3 gram US$110.00 obtained by Megazyme company.Polynucleotide:

Isolating polynucleotide of the present invention under medium at least stringent condition, will hybridize in SEQ IDNo.1 or with the similar size area of its complementary sequence.

Polynucleotide of the present invention are at as detailed below medium at least stringent condition, but preferably especially hybridize in the denatured double stranded dna probe of the full sequence shown in the position 97-1029 that contains SEQ ID NO:1 under high stringent condition or comprise any probe that has at least about the subsequence of the SEQ IDNO:1 of 100 base pair length.The suitable experiment condition that is used to measure hybridization under the medium or high strictness between nucleotide probe and homologous dna or the RNA sequence is included in 5 * SSC (sodium chloride/sodium citrate, Sambrook etc., 1989) pre-soaking contains the strainer of dna fragmentation or RNA to hybridize 10 minutes in, at 5 * SSC, 5 * Denhardt ' s solution (Sambrook etc., 1989), salmon sperm DNA (the Sambrook etc. of 0.5%SDS and 100 μ g/ml sex change sonications, 1989) solution middle filtrator prehybridization, containing the random primer (Feinberg that concentration is 10ng/ml subsequently, A.P. with Vogelstein B. (1983) Anal.Biochem.132:6-13), hybridized 12 hours down at about 45 ℃ in the same solution of 32P-dCTP mark (being higher than 1 * 109cpm/ μ g) probe than living.Strainer is subsequently at least 60 ℃ (medium strictnesses), more preferably at least 65 ℃ (medium/high strict), also preferably under at least 70 ℃ (high strict) and most preferably at least 75 ℃ (very high strictness) at 2 * SSC, washed twice among the 0.5%SDS.

The molecule of oligonucleotide probe hybridization detects with the x mating plate under these conditions.

As mentioned above, isolating polynucleotide of the present invention comprise DNA and RNA.The method that is used for DNA isolation and RNA is well known in the prior art.Interested DNA and RNA encoding gene can be by currently known methods clones of the prior art in gene pool or DNA library.

The polynucleotide with the active polypeptide of mannase of the present invention of encoding are identified and are separated by for example hybridization or PCR subsequently.

The present invention also provides pairing polypeptide and the polynucleotide from different bacterium bacterial strain (directly to autoploid or symbiosis autoploid).What cherish a special interest is by Gram-positive parent alkali bacterial strain, comprises the mannosans enzyme polypeptide that the kind of genus bacillus obtains.

Kind homologue with the active polypeptide of mannase of the present invention can be with information provided by the invention and composition and in conjunction with conventional clone technology clone.The chromosomal DNA clone that dna sequence dna for example of the present invention can use the cell type by marking protein to obtain.The suitable source of DNA can be determined by surveying the Northern trace by the probe with sequences Design disclosed herein.Chromosomal DNA by positive cell line prepares the library subsequently.The dna sequence dna of the present invention that coding has the active polypeptide of mannase can separate by the whole bag of tricks subsequently, for example by surveying with the probe of disclosed sequences Design in specification sheets of the present invention and claims or based on one or more groups degeneracy probe of disclosed sequence.(Mullis US4683202), uses the primer clone according to sequences Design disclosed herein for also available polymerase chain reaction of dna sequence dna of the present invention or PCR.In other method, the DNA library can be used for transforming or transfection host cell, the expression of interested DNA can be expressed and purifying described in Materials and Methods and embodiment 1, use from B.agaradherens the antibody (mono-clonal or polyclone) that the clone's of NCIMB 40482 mannase produces or detect by the activity test relevant with having the active polypeptide of mannase.

Encoding part is cloned among the intestinal bacteria DSM 12180 mannase of the plasmid pSJ1678 that exists and/or the dna sequence dna in the similar DNA sequence of the present invention can be by the bacterial strain of the bacterium kind Bacillus agaradherens of the enzyme that produces the mannosans degrading activity, preferred strain NCIMB40482, or other or associated biomolecule described herein clone.

In addition; similar sequence can be according to the dna sequence dna that can be obtained by the plasmid of existence among the intestinal bacteria DSM 12180 (it is considered to identical with appended SEQ ID NO:1); for example its subsequence constitutes; and/or by introducing the nucleotide subsitution formation; described displacement does not produce other aminoacid sequence by the mannase of dna sequence encoding; but it uses corresponding to the codon that produces the required host living beings of enzyme; or by introducing the nucleotide subsitution formation, described displacement can produce different aminoacids sequence (being the mutation of mannosans degrading enzyme of the present invention).Polypeptide:

The sequence of the amino acid nos.32-343 of SEQ ID NO:2 is ripe mannosans enzyme sequence.

The present invention also provides the mannosans enzyme polypeptide, and the polypeptide of it and SEQ ID NO:2 and its kind homologue (symbiosis autoploid or directly to autoploid) is homology basically.Term " homology basically " expression that is used for this paper has 70%, preferably at least 80%, more preferably at least 85%, most preferably at least 90% with SEQ ID NO:2 or its symbiosis autoploid or straight to the identical polypeptide of sequence shown in the amino acid nos.32-343 of autoploid.This polypeptide more preferably at least 95%, most preferably 98% or higher and SEQ ID NO:2 or its symbiosis autoploid or straight identical to the sequence shown in the amino acid nos.32-343 of autoploid.Sequence identity percentage ratio is measured by ordinary method, for example use computer program well known in the prior art, the GAP that in the GCG routine package, provides (Program Manualfor the Wisconsin Package for example, the 8th edition, in August, 1994, Genetics ComputerGroup, 575 Science Drive, Madison, Wisconsin, USA 53711), as Needleman, S.B. and Wunsch, C.D. (1970), molecular biology magazine (Journalof Molecular Biology), 48, disclosed in 443 453, all be hereby incorporated by.GAP carries out peptide sequence relatively with following setting: GAP produces compensation (penalty) 3.0, and GAP extends compensation 0.1.

The sequence identity of peptide molecule is measured by similar approach, and GAP carries out dna sequence dna relatively with following setting: GAP produces compensation 5.0, and GAP extends compensation 0.3.

Zymin of the present invention is preferably by microorganism, preferably obtain by bacterium, archea or fungi, especially by bacterium, for example belong to bacillus, the bacterium of preferred close alkali Bacillus strain obtains, it can be selected from kind of Bacillus agaradherens and very relevant genus bacillus kind, and wherein all plant Bacillus agaradherens at least 95% preferred and based on the 16S rDNA sequence of arranging, more preferably at least 98% homology.Basically homologous protein and polypeptide it is characterized by have one or more amino-acid substitutions, disappearance or additional.These change secondary properties preferably, i.e. conservative amino acid replacement (referring to table 2) and not obviously influence protein or polypeptide is folding or active other displacement; A small amount of disappearance, about 30 amino acid of 1-usually; Extend aminoterminal methionine residues for example, the little joint peptide of about at the most 20-25 residue or help the little extension (affinity tag) of purifying with little ammonia cardinal extremity or carboxyl terminal, polyhistidine section for example, a-protein (Nilsson etc., EMBOJ.4:1075,1985; Nilsson etc., Methods Enzymol.198:3,1991).Usually referring to Ford etc., protein expression and purifying (Protein Expression andPurification) 2:95-107,1991, classify this paper reference as.The affinity tag of dna encoding obtains (Pharmacia Biotech for example, Piscataway, NJ by commercial supplier; New England Biolabs, Beverly, MA).Yet even above-mentioned change secondary properties preferably, but this change also can be big character, and for example nearly 300 amino acid or more big polypeptide extend as aminoterminal or carboxyl terminal and be fused to mannosans enzyme polypeptide of the present invention.

Table 1

Conservative amino acid replacement

Alkalescence: arginine, Methionin, Histidine

Tart: L-glutamic acid, aspartic acid

Polar: glutamine, l-asparagine

Hydrophobic: leucine, Isoleucine, Xie Ansuan

Fragrance: phenylalanine, tryptophane, tyrosine

On a small quantity: glycine, L-Ala, Serine, Threonine, methionine(Met)

Except 20 kinds of standard amino acids, non-standard amino acid (for example 4-oxyproline, 6-N-methyllysine, 2-aminoisobutyric acid, isovaline and a-methyl Serine) can be used for replacing the amino-acid residue of polypeptide of the present invention.The non-conserved amino acid that limits the number, do not use gene-code amino acids coding and the replaceable amino-acid residue of alpha-non-natural amino acid." alpha-non-natural amino acid " is being modified behind the protein synthesis and/or has the chemical structure different with standard amino acid in its side chain.But alpha-non-natural amino acid chemosynthesis, or preferred commercial obtaining, it comprises pipecolinic acid, thiazolidine carboxylic acid, dehydroproline, 3-and 4-methylproline and 3,3-dimethyl proline(Pro).

Indispensable amino acid in mannosans enzyme polypeptide of the present invention can be definite according to method well known in the prior art, for example site-directed mutagenesis or alanine scanning mutagenesis (Cunningham and Wells, Science 244:1081-1085,1989).In one technology of back, introduce single alanine mutation on each residue in molecule, the biological activity (being the mannosans enzymic activity) of the mutant molecule that test obtains is to determine the amino-acid residue to the molecular activity key.Also referring to Hilton etc., J.Biol.Chem.271:4699-4708,1996.The reactive site of enzyme or other biological interaction also can be measured by the physical analysis of structure, as by this technology, as nucleus magnetic resonance, crystallography, electron diffraction or photoaffinity labeling, measure with the amino acid whose sudden change combination in site that contacts of inferring.Referring to for example de Vos etc., Science 255:306-312,1992; Smith etc., J.Mol.Biol.224:899-904,1992; Wlodaver etc., FEBS Lett.309:59-64,1992.The identity of primary amino acid also can be inferred by the analysis of the homologue with polypeptide relevant with polypeptide of the present invention.

Amino acids is replaced available mutagenesis, recombinates and/or confuses subsequently currently known methods preparation and the test by relevant scanning technique, for example by Reidhaar-Olson and Sauer (Science241:53-57,1988), Bowie and Sauer (Proc.Natl.Acad.Sci.USA 86:2152-2156,1989), described in WO95/17413 or the WO95/22625.In brief, these authors disclose following method, the two or more positions of randomization simultaneously in polypeptide, or the different sudden change (WO95/17413 that recombinate/confuse, WO95/22625), the selection official can polypeptide subsequently, and the polypeptide of the mutagenesis of checking order then is to be determined at admissible metathetical spectrum on each position.Spendable other method comprises phage display (Lowman etc. for example, Biochem.30:10832-10837,1991; Ladner etc., US5223409; Huse WIPO is WO92/06204 openly) and fixed regional mutagenesis (Derbyshire etc., Gene 46:145,1986; Ner etc., DNA 7:127,1988).

Above-mentioned mutagenesis/the method for confusing can combine with high-throughput, automatic scanning method to detect the activity of polypeptide that clone, mutagenesis in host cell.The mutagenized dna molecule of coding active polypeptide can be reclaimed by host cell, checks order rapidly with modern comfort.These methods can rapid test single amino acids residue in interested polypeptide importance, can be used for the polypeptide of unknown structure.Use aforesaid method, those of ordinary skills can identify and/or the residue 32-343 of preparation and SEQ ID NO:2 each peptide species of homologous basically the mannosans enzymic activity of maintenance wild-type protein.The protein preparation:

Protein of the present invention and polypeptide comprise full length protein, its fragment and fusion protein, can prepare in genetically engineered host cell according to routine techniques.Proper host cell is those cell types, and its available foreign DNA transforms or transfection, grows in substratum, comprises bacterium, fungal cell and the senior eukaryotic cell of cultivating.Preferred bacterium cell, the especially culturing cell of Gram-positive biology.Especially the preferred gram-positive cell that obtains by bacillus, for example by subtilis, the slow cell that obtains of genus bacillus, bacillus brevis, bacstearothermophilus, Alkaliphilic bacillus, bacillus amyloliquefaciens, Bacillus coagulans, Bacillus circulans, bacillus lautus (Bacillus lautus), bacillus thuringiensis, Bacillus licheniformis and Bacillus agaradherens, especially Bacillus agaradherens.

The technology that is used for handling clone's dna molecular and introduces foreign DNAs at various host cells is by Sambrook etc., Molecular Cloning:A Laboratory Manual, second edition, Cold Spring Harbor Laboratory Press, Cold Spring Harbor, NY, 1989; Ausubel etc., (eds.), the current programme in the molecular biology (Current Protocolsin Molecular Biology), John Wiley and Sons, Inc., NY, 1987; " subtilis and other gram positive bacterium ", Sonensheim etc., 1993, U.S. microbiology association (American Society for Microbiology), Washington D.C. is open, classifies this paper reference as.Usually the dna sequence dna of coding mannase of the present invention is operably connected to because it expresses other required gene, is usually included in transcripting promoter and terminator in the expression vector.This carrier also contains one or more selectable signs and one or more replication orgin usually, though person of skill in the art will appreciate that in some system, selectable sign can provide on independent carrier, and duplicating of foreign DNA can provide by being incorporated in the host cell gene group.The selection of promotor, terminator, selectable sign, carrier and other element is those of ordinary skills' a daily design transaction.Many these elements are described in the literature and can be obtained by commercial supplier.

For instructing polypeptide to enter the Secretory Pathway of host cell, in expression vector, provide secretory signal sequence (being also referred to as leader sequence, preceding former sequence or presequence).Secretory signal sequence can be peptide sequence or can be obtained or de novo synthesis by other secreted protein.Various suitable secretory signal sequences are known in the prior art, referring to " subtilis and other gram-bacteria ", Sonensheim etc., 1993, U.S. microbiology association (American Society forMicrobiology), Washington D.C.; And Cutting, S.M. (eds) " the molecular biosciences method of bacillus ", John Wiley and Sons, 1990, it has further described the suitable secretory signal sequence that is particularly useful for the genus bacillus secretory host cell.Secretory signal sequence is connected in dna sequence dna with correct reading frame.Secretory signal sequence is positioned the 5 ' dna sequence dna to the interested polypeptide of encoding usually, although some signal sequence can be positioned other position of dna sequence dna of interested polypeptide (referring to for example Welch etc., US5037743; Holland etc., US5143830).

The host cell of conversion or transfection is cultivated in the substratum medium that contains other required component of nutrient substance and selected host cell growth according to conventional methods.Various suitable medium comprise that the substratum and the complex medium of principal component are known in the prior art, generally include carbon source, nitrogenous source, indispensable amino acid, VITAMIN and mineral substance.Substratum also can comprise component as required, as somatomedin or serum.Growth medium will be selected or select according to the defective in the basic nutrition element according to the cell that contains the DNA that external source adds usually by medicament selection for example, but described defective is by the selection marker complementation of transfection that have in expression vector or common in the host cell.Protein separation:

When the recombinant polypeptide of expressing was secreted, polypeptide can be by purifying in the growth medium.Expression host cell preferably took out (for example by centrifugal) from substratum before peptide purification.

When the recombinant polypeptide of expressing is not during by secretory host cell, host cell preferably breaks, and during polypeptide was released into moisture " extract ", this was the fs of this purification technique.Expression host cell preferably before cell rupture by collecting (for example by centrifugal) in the substratum.

Cell rupture can be undertaken by routine techniques, for example exerts pressure to cell by N,O-Diacetylmuramidase digestion or by high pressure.Referring to (Robert K.Scobes, " protein purification ", Springer-Verlag), have further described this cell rupture technology by the 2nd edition.

No matter whether the recombinant polypeptide (or chimeric polyeptides) of expressing secretes its available classification and/or conventional purification process and medium purification.

Ammonium sulfate precipitation and acid or chaotropic agent extract the classification that can be used for sample.Purification step for example can comprise hydroxyapatite, size exclusion, FPLC and RPLC.Suitable anionic exchange medium comprises dextrin, agarose, Mierocrystalline cellulose, polyacrylamide, special silica of derivatize etc.PEI, DEAE, QAE and Q derivative are preferred, and especially preferred DEAE Fast-FlowSepharose (Pharmacia, Piscataway, NJ).Chromatographic media for example comprises the medium with phenyl, butyl or octyl group derivatize, Phenyl-Sepharose FF (Pharmacia) for example, Toyopearl butyl 650 (Toso Haas, Montgomeryville, PA), Octyl-Sepharose (Pharmacia) etc.; Or polyacrylic resin, for example Amberchrom CG71 (Toso Haas) etc.Suitable solid carrier comprises glass bead, silicon dioxide base resin, celluosic resin, the thin pearl of agarose, the thin pearl of Sepharose, the thin pearl of polystyrene, cross-linked polyacrylamide resin etc., and they are undissolved under its working conditions.These carriers can be used the reactive group modification, can partly connect protein by amino, carboxyl, sulfydryl, hydroxyl and/or carbohydrate like this.The example of coupling chemical process comprises cyanogen bromide-activated, N-hydroxy-succinamide activation, epoxide activation, sulfydryl activation, hydrazides activation and is used for the carboxyl and the aminoderivative of carbodiimide coupling chemistry.These and other solid dielectric is well known in the prior art and widely used, can be obtained by commercial supplier.

The selection of concrete grammar is to be the conventional design problem, partly by selected carrier character decision.Referring to for example affinity chromatography: principle and method (Affinity Chromatography:Principles ﹠amp; Methods), Pharmacia LKB Biotechnology, Uppsala, Sweden, 1988.

Polypeptide of the present invention or its fragment also can prepare by chemosynthesis.Polypeptide of the present invention can be monomer or polymer, glycosylation or nonglycosylated; Pegylated or non-pegylated; With can comprise or not comprise initial methionine(Met) amino-acid residue.

Based on sequence information disclosed herein, but clones coding mannase of the present invention and comprise the dna sequence dna shown in the SEQ ID No1, at least from the full length DNA sequence of the dna sequence dna of 97-position, position 1029.

The clone is undertaken by standard technique well known in the prior art, for example passes through

By Bacillus strain, bacterial strain B.agaradherens especially, NCIMB 40482 preparation genomic libraries;

Inoculate this library at suitable substrate plate upper flat plate;

The clone who contains polynucleotide sequence of the present invention by use based on the standard hybridization technique identification of the probe of SEQ ID No1; Or pass through

Use is cloned by described Bacillus agaradherens NCIMB 40482 genomic libraries identification by the inverse PCR strategy based on the primer of the sequence information of SEQ ID No1.Referring to (" PCR, a kind of practical approach (PCR A practicalapproach) " Information Press Ltd, Oxford England) such as M.J.MCPherson, it describes in further detail inverse PCR.

According to sequence information disclosed herein (SEQ ID No1, SEQ ID No2), by similar strategy, use is by the genomic library of related microorganisms, especially from other bacterial strain of bacillus, for example the homology polynucleotide sequence of the genomic library of the close alkali kind of bacillus separation coding homology mannase of the present invention is daily work for those skilled in the art.

In addition, encoding the DNA of mannosans of the present invention or galactomannan degradation enzyme can be according to known method easily by suitable source, for example any above-mentioned biology is by using the synthetic oligonucleotide probe clone based on the dna sequence dna preparation that obtains from the plasmid that exists among the intestinal bacteria DSM 12180.

Therefore, polynucleotide molecule of the present invention can be separated by intestinal bacteria DSM 12180, and wherein the plasmid that obtains by for example above-mentioned clone is deposited.Also have, the present invention relates to the isolating pure basically biological culture thing of bacterial strain intestinal bacteria DSM12180.In the present invention, term " zymin " is meant the conventional enzymic fermentation product that the microorganism by single kind obtains, and separable and purifying, said preparation contain many different enzymic activity materials usually; Or the mixture of single component enzyme, the preferred enzyme by using conventional recombinant technology to be obtained by bacterium or fungi kind, this enzyme are by fermentation with may separate respectively and purifying, and it can be obtained by different plant species, preferred fungi or bacterial species; Or the tunning of microorganism, this microorganism is as the host cell of express recombinant mannase, but this microorganism produces other enzyme simultaneously, for example pectin degrading enzyme, proteolytic enzyme or cellulase, be the tunning of the natural generation of this microorganism, promptly by the conventional enzyme complex for preparing of the microorganism of corresponding natural generation.

The method for preparing zymin of the present invention, this method comprises culturing micro-organisms, for example can produce the wild type strain of mannase and reclaim enzyme by culture under the generation condition that enzyme allowed.Cultivation can use conventional fermentation technique to carry out, and for example at the vibration flask or have in the fermentation container of stirring and cultivate to guarantee the abundant ventilation of growth medium, induces mannase to produce.Growth medium can contain conventional N-source, peptone for example, the conventional C-source of yeast extract or casamino acids, reduction amount, for example glucose or sucrose, and inductor, for example guar gum or carob bean gum.Recovery can use routine techniques to carry out, for example by centrifugal or filtering separation biological substance and supernatant liquor, if interested enzyme is intercellular, reclaim supernatant liquor or cell rupture thing, perhaps described in EP0406314 or described in WO97/15660, be further purified subsequently by crystallization.The immunological cross-reaction activity:

Being used to measure the active polyclonal antibody of immunological cross-reaction can be by using the mannase preparation of purifying.More particularly, the antiserum(antisera) of mannase of the present invention relatively can be according to N.Axelsen etc. at " quantitatively immunoelectrophoresis handbook ", Blackwell ScientificPublications, 1973, the 23rd chapter or A.Johnstone and R.Thorpe, " immunochemistry is put into practice ", Blackwell Scientific Publications, 1982, the method described in (27-31 page or leaf more specifically) produces by immune rabbit (or other rodents).The immunoglobulin (Ig) of purifying can by dialysis and ion exchange chromatography, for example obtain in DEAE-Sephadex subsequently by antiserum(antisera) by for example salt precipitation (ammonium sulfate).Proteinic immunochemistry sign can adopt Outcherlony double diffusion analysis, and (O.Ouchterlony is at " experiment immunization learns to do volume " (D.M.Weir, Ed) Blackwell Scientific Publications, 1967, the 655-706 page or leaf), by crossed immunoelectrophoresis (above-mentioned N.Axelsen etc., the 3rd and 4 chapters) or by rocket immunoelectrophoresis (N.Axelsen etc., the 2nd chapter).

The example bag that produces the useful bacterium of enzyme of the present invention or zymin is a gram positive bacterium, preferably obtain by genus bacillus/Bacterium lacticum group, preferably by the bacterial strain of bacillus, the more preferably bacterial strain of Bacillus agaradherens, especially bacterial strain Bacillus agaradherens, NCIMB40482 obtains.

The present invention includes the isolating mannase with above-mentioned character, it does not have homology impurity and uses conventional recombinant technology to produce.The mensuration of mannosans enzymatic activity (ManU)

Colorimetric test: substrate: at 0.1M glycin (Glycin) damping fluid, the 0.2%AZCL-polygalactomannan (Megazyme, Australia) that obtains by the angle beans among the pH10.0.Test is stirred and temperature is controlled on 40 ℃ the hot mixing tank to manage among the 1.5ml at Eppendorf Micro and carries out having.Cultivated the 0.750ml substrate 20 minutes with the 0.05ml enzyme, by stopping in centrifugal 4 minutes with 15000rpm.In the 1cm cuvette, under 600nm, measure the color of supernatant liquor.A ManU (mannosans unit of enzyme) obtains 0.24 (absolute value) in 1cm.Obtain BACILLUS AGARADHERENS mannase NCIMB40482 bacterial strain

Bacillus agaradherens NCIMB40482 contains the mannase of DNA sequences encoding.

Coli strain: prepare intestinal bacteria SJ2 cell (Diderichsen, B., Wedsted, U., Hedegaard, L., Jensen, B.R., Sjoholm, C. (1990) clone aldB, its alpha-acetolactate decarboxylase of encoding, a kind of extracellular enzyme from bacillus brevis, J.Bacteriol., 172,4315-4321), use the Gene Pulser that obtains by BIO-RAD ^TMThe electroporation device transforms by electroporation as described in supplier.

This bacterial strain of subtilis PL2306. is subtilis DN 1885 (Diderichsen, B., the Wedsted that has break apr and npr gene, U., Hedegaard, L., Jensen, B.R., Sjoholm, C. (1990) clone aldB, its alpha-acetolactate decarboxylase of encoding, a kind of extracellular enzyme from bacillus brevis, J.Bacteriol., 172,4315-4321), it breaks in the transcription unit of known subtilis cellulose enzyme gene, produces the cellulase negative cells.Break basically as Eds.A.L.Sonenshein, J.A.Hoch and RichardLosick (1993), " subtilis and other gram positive bacterium ", AmericanSociety for microbiology carries out described in the 618th page.

As Yasbin, R.E., Wilson, G.A. and Young, F.E. (1975) " conversion in the lysogenic strain of subtilis and transfection: the proof of in competent cell, selecting to introduce prophage ", prepare competent cell described in the J.Bacteriol.121:296-304, and transform.Plasmid

PSJ1678 (in WO94/19454, describe in detail, classify this paper reference as).

PMOL944: this plasmid is mainly to contain preparation subtilis, the element of fertile plasmid and have strong promoter and in the kalamycin resistance gene by the pUB110 derivative of the signal peptide of the amyL gene clone of Bacillus licheniformis ATCC14580.Signal peptide contains the Sacll position, makes its DNA of the protein mutant body portion that merges of clones coding and signal peptide easily.This causes preceding protein expression, and it points to the outside of cell.

Make up plasmid by the conventional genetic engineering technique that is summarized as follows.The structure of pMOL944:

PUB110 plasmid (McKenzie, T. etc., 1986, " plasmid " 15:93-103) digests with single restriction enzyme Ncil.The PCR fragment (P.L.Jorgensen etc., 1990, " gene ", 96,37-41 page or leaf) of being amplified by the amyL promotor that is encoded on plasmid pDN1981 digests with Ncil, and obtains plasmid pSJ2624 among the pUB110 of insertion Ncil digestion.

Employed two kinds of PCR primers have following sequence: #LWN5494 5 '-GTCGCCGGGGCGGCCGCTATCAATTGGTAACTGTATCTCAGC-3 ' #LWN5495 5 '-GTCGCCCGGGAGCTCTGATCAGGTACCAAGCTTGTCGACCTGCAGAATGAGGCAGC AAGAAGAT-3 '

Primer #LWN5494 inserts the Notl position in the plasmid.

Plasmid pSJ2624 uses Sacl and Notl digestion subsequently, and the new PCR fragment of being amplified by the amyL promotor that is encoded on pDN1981 digests with Sacl and Notl, obtains plasmid pSJ2670 among the pSJ2624 with this dna fragmentation insertion Sacl-Notl digestion.

This clones an amyL promotor that replaces using identical promoters but in the opposite direction clone.Two kinds of primers that are used for the PCR amplification have following sequence: #LWN5938 5 ｀-GTCGGCGGCCGCTGATCACGTACCAAGCTTGTCGACCTGCAGAATGAGGCAGCAAG AAGAT-3 ' #LWN5939,5 ｀-GTCGGAGCTCTATCAATTGGTAACTGTATCTCAGC-3 '

Plasmid pSJ2670 digests with restriction enzyme Pstl and Bcll, SP722 is (open in the open WO95/26397 of international patent application by coding alkali starch enzyme, classify this paper reference as) the cloned dna sequence PCR fragment of amplifying with Pstl and Bcll digestion, and insert and obtain plasmid pMOL944.Two kinds of primers that are used for the PCR amplification have following sequence: #LWN7864 5 ｀-AACAGCTGATCACGACTGATCTTTTAGCTTGGCAC-3 ' #LWN7901 5 ｀-AACTGCAGCCGCGGCACATCATAATGGGACAAATGGG-3 '

Primer #LWN7901 inserts the Sacll position in the plasmid.Cloned genomic dna preparation from the mannase gene of Bacillus agaradherens:

In liquid medium, breed described in bacterial strain Bacillus agaradherensNCIMB40482 such as the WO94/01532.After 30 ℃ and 300rpm cultivate 16 hours, harvested cell, by (Pitcher such as Pitcher, D.G., Saunders, N.A.Owen, R.J. (1989) " with guanidine thiocyanate rapid extraction bacterial genomes DNA ", Lett.Appl.Microbiol., 8,151-156) the method isolation of genomic DNA of Miao Shuing.Genomic library construction:

Genomic dna partly digests with restriction enzyme Sau3A, carries out the size classification by electrophoretic method on 0.7% sepharose.Size is separated (Dretzen by electrophoretic method in the fragment between the 2-7kb on the DEAE-cellulose paper, G.Bellard, M., Sassone-Corsi, P., Chambon, P. (1981) " reliable method of recovery dna fragmentation from agarose and acrylamide gel " Anal.Biochem., 112,295-298).

The separated DNA fragment is connected to the pSJ1678 plasmid DNA that BamHI digests, connects mixture and be used for transformed into escherichia coli SJ2.The identification of positive colony:

The e. coli dna library of Gou Jianing is being contained 0.2%AZCL-polygalactomannan (Megazyme) and 9 μ g/ml paraxin and is being screened on the LB of 37 ℃ of overnight incubation agar plate as mentioned above.Express the active clone of mannase and show blue diffusion haloing.Separate by Qiagen plasmid spin preps in the meat soup of 1ml incubated overnight (cell is containing among the TY of 9 μ g/ml paraxin and cultivates down at 37 ℃, and with the 250rpm vibration) by one of these clones plasmid DNA that obtains.

This clone (MB525) further characterizes with the determined dna sequence of the Sau3A dna fragmentation of cloning.Determined dna sequence uses the terminal cyclic sequence metering equipment of Taq deoxidation (Perkin-Elmer, USA) terminator of fluorescent agent sign and undertaken by the primer walking as the suitable oligonucleotide of primer.

The analysis of sequence data is according to (1984) " nucleic acids research " such as Devereux, and 12, carry out described in the 387-395.The sequence of coding mannase is shown in the SEQ ID No1.The deutero-protein sequence is shown in the SEQ ID No.2.

The subclone of mannase and expression in subtilis:

The mannase of dna sequence dna of the present invention of encoding is the PCR that uses the PCR primer sets be made up of following two kinds of oligonucleotide to amplify:

Mannase, last Sacll5 '-CAT TCT GCA GCC GCG GCA GCA AGT ACA GGC TTT TAT GTT GAT GG-3 '

Mannase, following Notl5 '-GAC GAC GTA CAA GCG GCC GCG CTA TTT CCC TAA CAT GAT GATATT TTC G-3 '

Underlined is agretope Sacll and Notll.

Be used as template by the guidance according to manufacturers in the PCR reaction of using Amplitaq archaeal dna polymerase (Perkin Elmer) of the isolating chromosomal DNA of B.agaradherens NCIMB40482 as mentioned above.PCR be reflected at each dNTP of containing 200 μ M, 2.5 units the AmpliTaq polysaccharase (Perkin-Elmer, Cetus, USA) and PCR damping fluid (the 10mM Tris-HCl of each primer of 100pmol, pH8.3,50mM Repone K, 1.5mM magnesium chloride, 0.01% (w/v) gelatin) middle foundation.

(Landgraf Germany) carries out with the DNA thermo cycler in the PCR reaction.Cultivated 1 minute at 94 ℃, use subsequently, carry out 30 PCR circulations 60 ℃ of annealing 1 minute with 72 ℃ of Recycle design of extending 2 minutes 94 ℃ of sex change 30 seconds.In 0.7% sepharose (NuSieve, the 5 μ l aliquots containigs of amplifying product with the electrophoretic method analysis in FMC).The outward appearance of dna fragmentation size 1.4kb is represented the suitable amplification of gene fragment.

The segmental subclone of PCR

45 μ l aliquots containigs of the PCR product of above-mentioned generation are according to the guidance of manufacturers QlAquick PCR purifier apparatus (Qiagen, USA) purifying.The DNA of purifying is with 50 μ l 10mMTris-HCl, pH8.5 wash-out.

The PCR fragment of 5 μ g pMOL944 and 25 μ l purifying digests with Sacll and Notl, agarose (SeaPlaque GTG at 0.8% low gelation temperature, FMC) electrophoresis in the gel, the relevant fragment of excision from gel, according to the guidance of manufacturers QlAquick gel extraction equipment (Qiagen, USA) purifying.Isolating PCR dna fragmentation is connected in the pMOL944 of Sacll-Notl digestion and purifying subsequently.Connect that (Boehringer Mannheim Germany) spends the night at 16 ℃ with the T4DNA ligase enzyme of 0.5 each dna fragmentation of μ g, 1U and T4 ligase enzyme damping fluid.

Connect mixture and be used for transformed competence colibacillus subtilis PL2306.Cell transformed is carried out plating on LBPG-10 μ g/ml kantlex flat board.After 18 hours, on flat board, see bacterium colony 37 ℃ of cultivations.By analyzing some clones by incubated overnight meat soup isolated plasmid dna.

This positive colony is rule (restreak) several times again on above-mentioned used agar plate, this clone is called MB594.37 ℃ of grow overnight, the instruction that was used for the subtilis process for preparing plasmid in second day according to manufacturers is used therefrom separation quality grain of 1ml cell with QiaprepSpin Plasmid Miniprep Kit#27106 to clone MB594 at TY-10 μ g/ml kantlex.This DNA is sequencing and the maturing part that shows corresponding to mannase, the DNA of the dna sequence dna of the position 94-1404 of promptly appended SEQ ID NO:3.The deutero-mature protein shows in SEQ ID NO:4.It shows by 3 ' end of the mannase of the sequence encoding of SEQ ID NO:1 changes into the sequence shown in the SEQ ID NO:3 owing to be used for the low primer design of PCR.The aminoacid sequence that obtains is shown among the SEQ ID NO:4, and obviously the C of SEQ ID NO:2 end (SHHVREIGVQFSAADNS SGQTALYVDNVTLR) is changed into the C end (IIMLGK) of SEQ ID NO:4.

Substratum:

TY (as Ausubel, F.M. etc. (eds.) " current programme in the molecular biology (Currentprotocols in Molecular Biology) " .John Wiley and Sons are described in 1995).

LB agar (as Ausubel, F.M. etc. (eds.) " current programme in the molecular biology (Current protocols in Molecular Biology) " .John Wiley and Sons are described in 1995).

LBPG is with 0.5% glucose and 0.05M potassiumphosphate, the LB agar (as mentioned above) that pH7.0 replenishes.

The BPX substratum is described in EP0506780 (WO91/09129).Expression, purifying and the sign of the mannase that obtains by Bacillus agaradherens

The clone MB594 that obtains described in above-mentioned Materials and Methods was containing in 25 * 200mlBPX substratum of 10 μ g/ml kantlex under 37 ℃ and 300rpm growth 5 days in the two baffle plates vibration of 500ml flask.

Collect the vibration flask of 6500ml clone MB594 and cultivate fluid (batch of material #9813), pH regulator to 5.5.Adding 146ml cationoid reagent (C521) and 292ml reagents for anion (A130) flocculate in whipping process.By separating the materials that flocculate at 6 ℃ in centrifugal 20 minutes with 9000rpm with Sorval RC 3B sedimentator.Supernatant liquor finally cuts 10kDa with filtron and concentrates with Whatman glass filter GF/D and C clarification.With sodium hydroxide this enriched material of 750ml is adjusted to pH7.5.Settled solution is used for anion-exchange chromatography, uses by 50mmolTrispH7.5 equilibrated 900ml Q-Sepharose post.With sodium-chlor gradient elution mannosans enzymic activity binding substances.

Pure enzyme obtains single band in SDS-PAGE, molecular weight is 38kDa.The aminoacid sequence of mannase, promptly Fan Yi dna sequence dna is shown among the SEQ ID No.2.

Kinetic constant is measured:

Substrate: carob bean gum (carob) and go back raw sugar analysis (PHBAH).

The carob bean gum (G-0753) that obtains by Sigma.

Kinetic determination obtained in the pH10 cultivation at 40 ℃ with the carob bean gum of different concns in 20 minutes

Kcat: per second 467

Km：0.08g/l

MW：38kDa

Pl (iso-electric point): 4.2

The temperature optimum value of mannase is 60 ℃.

The pH activity curve shows that maximum activity is between pH8-10.

It is 77 ℃ that the DSC differential scanning calorimeter obtains at the fusing point of pH7.5 in the Tris damping fluid, shows that this enzyme is very heat-staple.

Use the 0.2%AZCL-polygalactomannan that obtains by carob bean gum as substrate with as mentioned above 40 ℃ of compatible abilities demonstrations of washing composition and the outstanding consistency of conventional liq washing composition and the consistency good of cultivating mensuration down with conventional powder detergent.The acquisition of subtilis mannase 168

Following sign and purifying subtilis 'beta '-mannase:

With known bacillus beta-mannase gene sequence (Mendoza etc., Biochemicaet Biophysica Acta 1243:552-554,1995) the genomic homology of retrieval subtilis, product are that the coding region of the ydhT of the unknown shows that 58% is similar to known genus bacillus 'beta '-mannase.Design the sequence that following oligonucleotide is used to amplify the maturing part of the 'beta '-mannase that coding infers: 5 '-GCT CAA TTG GCG CAT ACT GTG TCG CCT GTG-3 ' and 5 '-GAC GGA TCC CGG ATT CAC TCA ACG ATT GGC G-3 '.The total genomic dna that is obtained by bacillus subtilis strain 1A95 uses above-mentioned primer to amplify the ripe zone of ydhT as template.(Foster City CA) carries out PCR for PerkinElmer, Applied Biosystems with the AMPLITAQ archaeal dna polymerase with GENE-AMP PCR Kit.At first, carry out 25 following programs of round-robin subsequently:,, extended 2 minutes at 72 ℃ 55 ℃ of annealing 2 minutes 95 ℃ of fusings 1 minute 95 ℃ of fusings 5 minutes.In the end after the circulation, be reflected at 72 ℃ and keep 10 minutes to finish extension.PCR product QlAquick PCR purifier apparatus (Qiagen, Chatsworth, CA) purifying.

Insert as follows among the expression vector pPG1524 (the previous description) by the ripe zone of ydhT that bacillus subtilis strain 1A95 amplifies.The 1028bp fragment of amplifying digests with Mfe I and BamH I.Expression vector pPG1527 digests with EcoR I and BamH I.Restriction product QlAquickPCR purifier apparatus (Qiagen, Chatsworth, CA) purifying.Two fragments connect (13 hours, 16 ℃) with the T4 dna ligase, are used for transformed competence colibacillus coli strain DH5-α.DNA cultivates the amicillin resistance bacterium colony for preparation.DNA characterizes with restriction analysis subsequently.Plasmid pPG3200 contains the ripe zone of ydhT gene.Plasmid pPG3200 is used for transformed competence colibacillus bacillus subtilis strain PG632 (Saunders etc., 1992) subsequently.

Select 7 kalamycin resistance subtilis clones and 1 PG632 contrast clone, growth in 20ml 20/20/5 substratum (20g/l tryptone, 20g/l yeast extract and 5g/l sodium-chlor) that replenishes with 1ml25%maltrin, 120 μ l 10mM manganous chloride and 20 μ l 50mg/ml kantlex.Be cloned in 250ml with in the baffle plate flask of 250rpm vibration 37 ℃ of following grow overnight with marking protein.Cell was with 14000rpm spin 15 minutes.1 each supernatant liquor of μ l dilutes with the 50mM sodium acetate (pH6.0) of 99 μ l.1 this diluent of μ l is according to the guidance inscribe-1 of manufacturers, and (Megazyme Ireland) analyzes 4-'beta '-mannase β-Mannazyme Tabs.Measure absorbancy at Beckman DU640 spectrophotometer at 590nm.Clone 7 shows 1.67 high absorbance.PG632 does not show absorbancy to impinging upon 590nm.

(Novex, San Diego analyze to confirm the desired protein size of 38kDa by SDS-PAGE in Ca) supernatant liquor in the 10-20%Tris-glycine gels.Specimen preparation is as follows.500 μ l samples of ydhT clone 7 and PG632 supernatant liquor, are suspended in the 50 μ l Tris-glycine SDS sample damping fluids (Novex) with the washing of 100 μ l, 5% trichoroacetic acid(TCA) again with 55.5 μ l, 100% trichoroacetic acid(TCA)s (Sigma) precipitation, seethe with excitement 5 minutes.1 μ l per sample (p.s.) in gel under 30mA electrophoresis 90 minutes.Observe proteinic big band explanation ydhT clone 7 and be 38kDa.

Subtilis ydhT clone 7 10l fermentation is carried out in B.Braun Biostat C fermentation container.Fermentation condition is as follows.Cell in being similar to 20/20/5 rich substratum 37 ℃ of growths 18 hours down.When fermentation test finishes, take out cell, use tangential flow filtration system concentrated supernatant to 1l.The ultimate yield of the 'beta '-mannase in concentrated supernatant is determined as 3g/1.

Be performed as follows by fermented supernatant fluid purifying 'beta '-mannase: at 4 ℃ with 500ml supernatant liquor centrifugal 10 minutes at 10000rpm.The centrifugal supernatant liquor cuts off film (Spectrum) dialysed overnight by Spectrapor 12000-14000mol.wt. at 4 ℃ then in two 4 liters 10mM potassiumphosphates (pH7.2) change.The supernatant liquor of dialysis 4 ℃ under 10000rpm centrifugal 10 minutes.200mlQ Sepharose flow fast (Pharmacia) anion-exchange column with 1 liter of 10mM potassiumphosphate (pH7.2) 20 ℃ of following balances, load 300ml supernatant liquor in post.Collect two and flow through cut 210ml (Sample A) and 175ml (sample B).Two cuts are as above analyzed, and just sample dilutes with 199 μ l 50mM sodium acetates (pH6.0), and they show the absorbancy of .38 and .52 respectively.2 μ l per sample (p.s.)s add 8 μ l Tris-glycine SDS sample damping fluids (Novex, CA) in, seethed with excitement 5 minutes.The sample that obtains the 10-20%Tris-glycine gels (Novex, Ca) under 30mA electrophoresis 90 minutes.In per sample (p.s.), have main band corresponding to 38kDa, account for gross protein more than 95%.Guidance according to manufacturers is carried out BCA protein test (Pierce) as standard to two kinds of samples with bovine serum albumin.Sample A and sample B contain 1.3mg/ml and 1.6mg/ml 'beta '-mannase respectively.Proteinic identity is by ionspray mass spectrum and aminoterminal amino acid sequence analysis.

The 'beta '-mannase sample of purifying is following to be used to characterize enzymic activity.Above-mentioned inscribe-1,4-'beta '-mannase β-Mannazyme Tabs (Megazyme Ireland) are used in all tests.Activity at pH scope 3.0-9.0 is carried out in 50mM Citrate trianion phosphate buffered saline buffer, for the determination of activity of pH9.5, adopts 50mM CAPSO (Sigma), and for the pH10.0-11.0 scope, then adopts 50mM CAPS damping fluid.The best pH of subtilis 'beta '-mannase is pH6.0-6.5.The temperature activity curve carries out in 50mM Citrate trianion phosphoric acid salt (pH6.5).This enzyme shows optimum activity at 40-45 ℃.Be lower than 15 ℃ and when being higher than 80 ℃ the subtilis 'beta '-mannase keep significantly active.According to the guidance of manufacturers, with inscribe-1,4-'beta '-mannase β-Mannazyme Tabs (Megazyme Ireland) measure with respect to β-1, the ratio work of 4-polygalactomannan is 160,000 μ mol/min.mg 'beta '-mannases.The Nucleotide of subtilis 'beta '-mannase and aminoacid sequence are shown in SEQ ID No.5 and 6.

Mannase is preferably to press composition weight meter 0.0001%-2%, more preferably 0.0005%-0.1%, and most preferably the content of the pure enzyme of 0.001%-0.02% adds in the composition of the present invention.

Enzyme of the present invention except the enzyme nuclear that contains catalyst structure domain, also contains cellulose binding domain (CBD), and the cellulose binding domain of enzyme and enzyme nuclear (catalytic activity structural domain) are operably connected.The integral part that cellulose binding domain (CBD) can be used as codase exists, thereby or can introduce enzyme from the CBD in other source and form the enzyme hybrid.In this article, term " cellulose binding domain " can be regarded as by Peter Tomme etc., " cellulose binding domain: classification and character ", at " enzyme liberating of insoluble carbohydrate ", John N.Saddler and Michael H.Penner (Eds), ACS Symposium Series, No.618, in 1996 define.This definition will be divided into 10 families (I-X) above 120 kinds of cellulose binding domains, illustrate that CBD is present in various enzymes, for example among cellulase, zytase, mannase, arabinofuranosidase, acetyl esterase and the chitinase.CBD for example finds among the red algae Porphyra purpurea as non-Polysaccharides conjugated protein also in algae, referring to the document of quoting as proof more than Tomme etc.Yet most of CBD are from cellulase and zytase, and CBD is at proteinic N and C end or in the centre.The enzyme hybrid is known in the prior art, for example referring to WO90/00609 and WO95/16782, can be by DNA structure being transformed into host cell and growth host cell expressing the fusion gene preparation, described DNA structure contain at least one coding by or be not connected in the dna fragmentation of cellulose binding domain of the dna sequence dna of coding mannase by joint.The enzyme hybrid can be described by following formula:

CBD-MR-X wherein CBD is N-end or a C-end regions corresponding to the aminoacid sequence of cellulose binding domain at least; MR is region intermediate (joint), and can be key, or about 100 carbon atoms of preferably about 2-, the more preferably short linking group of 2-40 carbon atom; Or about 100 amino acid of preferably about 2-, more preferably 2-40 amino acid; With X be the N-end or the C-end regions of enzyme of the present invention.

Above-mentioned enzyme can be any suitable source, for example plant, animal, bacterium, fungi and yeast source.The source can also be have a liking for temperature or have a liking for limiting condition (extremophilic) (have a liking for cold, psychrotrophic, thermophilic, have a liking for pressure, have a liking for alkali, have a liking for acid, have a liking for halogen etc.).Pure or the impure form of these enzymes can both be used.At present, common practice is with their effectiveness of performance in cleaning composition of the present invention of optimizing through protein/genetic engineering technique modification agriotype enzyme.For example but design variable is to increase the consistency of the component that runs into usually in enzyme and the said composition.In addition, but design variable makes best pH, SYNTHETIC OPTICAL WHITNER or sequestrant stability, the catalytic activity etc. of enzyme variants can adapt to specific washing uses.

Under the situation of bleach stability, especially should note to note surface charge to the amino acid of oxidation-sensitive with for surfactant compatibility.The iso-electric point of this kind of enzyme can be passed through some charged amino acid whose displacement modification, for example increases iso-electric point and can help to improve consistency with anion surfactant.The stability of enzyme can further be improved by producing for example additional salt bridge, and the reinforcement metal binding site is to increase sequestrant stability.Soil release polymer

Laundry detergent composition of the present invention contains 0.0001%-20% by weight usually, preferred 0.001-15%, more preferably the cotton goods polymine soil release polymer of 0.01-10%.Preferred cotton goods polymine soil release polymer is water-soluble or dispersible modified polyamine cotton goods stain remover, and it contains corresponding to by Procter ﹠amp; The polyamine formula V that describes among the WO97/42288 that Gamble1997 applied at April 25 with modification _(n+1)W _mY _nThe polyamine backbone of the following formula of Z: Or has a polyamine formula V of modification _(n-k+1)W _mY _nY ' _kThe polyamine backbone of Z corresponding to following formula:

Wherein k is less than or equal to n, and before modification, described polyamine backbone has greater than about 200 daltonian molecular weight, wherein

I) the V unit is the terminal units with following formula:

Or

Or

Ii) the W unit is the skeleton unit with following formula:

Or Or

Iii) the Y unit is the chain unit with following formula:

Or

Or

With

Iv) the Z unit is the terminal units with following formula:

Or

Or The R unit that wherein connects skeleton is selected from C ₂-C ₁₂Alkylidene group, C ₄-C ₁₂Alkenylene, C ₃-C ₁₂Hydroxy alkylidene, C ₄-C ₁₂Alkyl sub-dihydroxy, C ₈-C ₁₂The dialkyl group arylidene ,-(R ¹O) _xR ¹-,-(R ¹O) _xR ⁵(OR ¹) _x-,-(CH ₂CH (OR ²) CH ₂O) _z-(R ¹O) _yR ¹(OCH ₂CH (OR ²) CH ₂) _w-,-C (O) (R ⁴) _rC (O)-,-CH ₂CH (OR ²) CH ₂-and their group of mixture; R wherein ¹Be C ₂-C ₆Alkylidene group and their mixture; R ₂Be hydrogen ,-(R ¹O) _xB and their mixture; R ³Be C ₁-C ₁₈Alkyl, C ₇-C ₁₂Arylalkyl, C ₇-C ₁₂Aryl, C that alkyl replaces ₆-C ₁₂Aryl and their mixture; R ⁴Be C ₁-C ₁₂Alkylidene group, C ₄-C ₁₂Alkenylene, C ₈-C ₁₂Aryl alkylene, C ₆-C ₁₀Arylidene and their mixture; R ⁵Be C ₁-C ₁₂Alkylidene group, C ₃-C ₁₂Hydroxy alkylidene, C ₄-C ₁₂Alkyl sub-dihydroxy, C ₈-C ₁₂The dialkyl group arylidene ,-C (O)-, C (O) NHR ⁶NHC (O)-,-R ¹(OR ¹)-,-C (O) (R ⁴) _rC (O)-,-CH ₂CH (OH) CH ₂-, CH ₂CH (OH) CH ₂O (R ¹O) _yR ¹-OCH ₂CH (OH) CH ₂-and their mixture; R ⁶Be C ₂-C ₁₂Alkylidene group or C ₆-C ₁₂Arylidene; The E unit is selected from hydrogen, C ₁-C ₂₂Alkyl, C ₃-C ₂₂Thiazolinyl, C ₇-C ₂₂Arylalkyl, C ₂-C ₂₂Hydroxyalkyl ,-(CH ₂) _pCO ₂M-,-(CH ₂) _qSO ₃M-,-CH (CH ₂CO ₂M) CO ₂M ,-(CH ₂) _pPO ₃M ,-(R ¹O) _xB ,-C (O) R ³With their group of mixture; Its prerequisite is when any E unit of nitrogen is hydrogen, and described nitrogen neither the N-oxide compound; B is hydrogen, C ₁-C ₆Alkyl ,-(CH ₂) _qSO ₃M-,-(CH ₂) _pCO ₂M-,-(CH ₂) _q(CHSO ₃M)-CH ₂SO ₃M ,-(CH ₂) _q(CHSO ₂M)-CH ₂SO ₃M ,-(CH ₂) _pPO ₃M ,-PO ₃M and their mixture; M is hydrogen or the water-soluble cationic that presents in an amount at least sufficient to satisfy charge balance; X is a water soluble anion;

K and k ' are 1-about 15; M is 4-about 400; N is 0-about 200; P is 1-6, and q is 0-6; R is 0 or 1; W is 0 or 1; X is 1-100; Y is 0-100; Z is 0 or 1.

It can be straight chain or cyclic skeleton that these polyamine contain.Polyamine backbone can also contain the polyamine side chain of bigger or less degree.Usually, polyamine backbone described herein modification as follows makes that each nitrogen of polyamine chain is described to replace, quaternized, oxidation or their bonded unit.

Being used for hydrogen atom (replacement), quaternized skeleton nitrogen (quaternized) or oxidation skeleton nitrogen that term of the present invention " modification " is defined as replacing with the E unit skeleton-NH is N-oxide compound (oxidation).Replace when being connected in the hydrogen atom of skeleton nitrogen when relating to the E unit, term " modification " and " replacement " are used interchangeably.Quaternized or oxidation can be carried out under some occasion that does not have to replace, but replaces the oxidation of preferably following at least one skeleton nitrogen or quaternized.

The straight chain or the non-annularity polyamine backbone that constitute cotton goods stain remover of the present invention have following general formula: Before modification subsequently described skeleton contain by R " connection " unit connect primary, the second month in a season and tertiary amine nitrogen.The cyclic polyamines skeleton that constitutes cotton goods stain remover of the present invention has following general formula: Before modification subsequently described skeleton contain by R " connection " unit connect primary, the second month in a season and tertiary amine nitrogen.

In case be used for of the present inventionly containing the skeleton of modification or the primary amine nitrogen of side chain is defined as V or Z " end " unit.For example, when the primary amine part with following structure that is positioned at a main polyamine backbone or a link ends is carried out modification according to the present invention:

H ₂N-R]-it is defined as V " end " unit subsequently, or abbreviate the V unit as.Yet, for the purpose of the present invention, being subjected to the following restriction that further describes, some or all primary amine parts can keep unmodified.Consider its position in skeletal chain, these unmodified primary amine parts still are " end " unit.Equally, when the primary amine part with following structure that is positioned at main polyamine backbone end is carried out modification according to the present invention:

-NH ₂It is defined as Z " end " unit subsequently, or abbreviates the Z unit as.Be subjected to the following restriction that further describes, it is unmodified that this unit can keep.

Similarly, in case contain the skeleton of modification or the secondary amine nitrogen of side chain is defined as W " skeleton " unit.For example, when the secondary amine part, when the major portion of skeleton with following structure of the present invention or side chain is carried out modification according to the present invention:

It is defined as W " skeleton " unit subsequently, or abbreviates the W unit as.Yet for the purpose of the present invention, partly or entirely the secondary amine part can keep unmodified.Consider its position in skeletal chain, these unmodified secondary amine parts still are " skeleton " unit.

Also similarly, in case contain the skeleton of modification or the tertiary amine nitrogen of side chain also is called Y " side chain " unit.For example, when having following structure, when carrying out modification according to the present invention for the tertiary amine part of the chain branching point of polyamine backbone or other side chain or ring: It is defined as Y " side chain " unit subsequently, or abbreviates the Y unit as.Yet for the purpose of the present invention, partly or entirely the tertiary amine part can keep unmodified.Consider its position in skeletal chain, these unmodified tertiary amine parts still are " side chain " unit.The R unit that following description and the V that is used to be connected polyamine nitrogen, W link to each other with the Y unit.

Therefore, the final modified structure of polyamine of the present invention can be represented with following general formula for straight-chain polyamine cotton goods soil release polymer:

V _(n+1)W _mY _nZ and can represent with following general formula for cyclic polyamines cotton goods soil release polymer:

V _(n-k+1)W _mY _nY ' _kZ is to the situation of the polyamine that contains ring, the Y ' unit of following formula:

Branch point as a skeleton or a chain link.For each Y ' unit, there is the Y unit of following formula: It will form the tie point of ring and host polymer chain or side chain.Skeleton is that polyamine backbone has following formula under the single situation of complete ring therein:

Thereby do not contain the Z terminal units, and have following formula:

V _N-kW _mY _nY ' _kWherein k is the quantity that forms the unitary ring of side chain.Polyamine backbone of the present invention does not preferably contain ring.

Under the situation of acyclic polyamine, subscript n is called relative degree of branching with the ratio of subscript m.Complete non-branching straight chain modified polyamine of the present invention has following formula:

VW _mZ is that n equals 0.N value big more (ratio of m and n is more little), degree of branching is big more in the molecule.The scope of m value usually from minimum value 4 to about 400, yet bigger m value also is preferred, especially in the value of subscript n very little or near 0 in.

Each polyamine nitrogen, no matter it be primary, the second month in a season or uncle's nitrogen, in case carry out modification, also be defined as a kind of in three kinds of common kinds: simple that replace, quaternised or oxidation according to the present invention.Those unmodified polyamine nitrogen unit according to its whether be primary, the second month in a season or uncle's nitrogen, be categorized as V, W, Y or Z unit.Promptly unmodified for the purpose of the present invention primary amine nitrogen is V or Z unit, and unmodified secondary amine nitrogen is that W unit and unmodified tertiary amine nitrogen are the Y unit.

The modification primary amine partly is defined as V " end " unit with one of following three kinds of forms:

A) have the unit of the simple replacement of following structure:

B) have the quaternized unit of following structure:

Wherein X provides the suitable counter ion of charge balance; With

C) have the oxidation unit of following structure:

Modification secondary amine partly is defined as W " skeleton " unit with one of following three kinds of forms:

A) have the unit of the simple replacement of following structure:

B) have the quaternized unit of following structure:

Wherein X provides the suitable counter ion of charge balance; With

C) have the oxidation unit of following structure:

Enhanced tertiary amine partly is defined as Y " side chain " unit with one of following three kinds of forms:

A) have the unmodified unit of following structure:

B) have the quaternized unit of following structure: Wherein X provides the suitable counter ion of charge balance; With

C) have the oxidation unit of following structure:

Some modification primary amine partly is defined as Z " end " unit with one of following three kinds of forms:

A) have the unit of the simple replacement of following structure:

B) have the quaternized unit of following structure:

Wherein X provides the suitable counter ion of charge balance; With

C) have the oxidation unit of following structure:

When the position on any nitrogen is not replace or when unmodified, should understand hydrogen and will replace E.The primary amine unit that for example contains a unitary hydroxyethyl part of E is to have formula (HOCH ₂CH ₂) the V terminal units of HN-.

There is two types chain end unit for the purpose of the present invention, V and Z unit.Z " end " unit is by structure-NH ₂The amino part of terminal primary obtain.Non-annularity polyamine backbone of the present invention only comprises a Z unit, thereby cyclic polyamines can not comprise the Z unit.Except when outside the Z unit was modified when forming the N-oxide compound, Z " end " unit can replace with any E as described below unit.Z unit nitrogen is oxidized under the situation of N-oxide compound therein, and nitrogen must be modified, thereby E can not be a hydrogen.

Polyamine of the present invention comprises skeleton R " connection " unit, and it is used to connect the nitrogen-atoms of skeleton.The R unit comprises for the purpose of the present invention and is called " alkyl R " unit and " oxygen base R " unitary unit." alkyl " R unit is C ₂-C ₁₂Alkylidene group, C ₄-C ₁₂Alkenylene, C ₃-C ₁₂Hydroxy alkylidene, wherein except the carbon atom that is directly connected in polyamine backbone nitrogen, any position, C that hydroxylic moiety can be on the R cellular chain ₄-C ₁₂Alkyl sub-dihydroxy, wherein except the carbon atom that is directly connected in polyamine backbone nitrogen, hydroxylic moiety can connect any two carbon atoms, the C on the R cellular chain ₈-C ₁₂The dialkyl group arylidene is the arylidene part that contains as two alkyl substituents of connection chain part in the present invention.For example, the dialkyl group arylene units has following formula:

Though the unit needs not to be 1,4-replaces, and also can be 1,2 or 1,3 C that replaces ₂-C ₁₂Alkylidene group, preferred ethylidene, propylene and their mixture, more preferably ethylidene." oxygen base " R unit comprises-(R ¹O) _xR ⁵(OR ¹) _x-,-(CH ₂CH (OR ²) CH ₂O) _z(R ¹O) _yR ¹(OCH ₂CH (OR ²) CH ₂) _w-,-CH ₂CH (OR ²) CH ₂-,-(R ¹O) _xR ¹-and their mixture.The R unit is C preferably ₂-C ₁₂Alkylidene group, C ₃-C ₁₂Hydroxy alkylidene, C ₄-C ₁₂Alkyl sub-dihydroxy, C ₈-C ₁₂The dialkyl group arylidene ,-(R ¹O) _xR ¹-,-CH ₂CH (OR ²) CH ₂-,-(CH ₂CH (OH) CH ₂O) _z(R ¹O) _yR ¹(OCH ₂CH (OH) CH ₂) _w-,-(R ¹O) _xR ⁵(OR ¹) _x-; The R unit is more preferably C ₂-C ₁₂Alkylidene group, C ₃-C ₁₂Hydroxy alkylidene, C ₄-C ₁₂Alkyl sub-dihydroxy ,-(R ¹O) _xR ¹-,-(CH ₂CH (OH) CH ₂O) _z(R ¹O) _yR ¹(OCH ₂CH (OH) CH ₂) _w-,-(R ¹O) _xR ⁵(OR ¹) _x-and their mixture; The R unit is C preferably also ₂-C ₁₂Alkylidene group, C ₃Hydroxy alkylidene and their mixture; C most preferably ₂-C ₆Alkylidene group.Most preferred skeleton of the present invention contains at least 50% and is the R unit of ethylidene.

R ¹Be C ₂-C ₆Alkylidene group and their mixture, preferred ethylidene;

R ₂Be hydrogen and-(R ¹O) _xB, preferred hydrogen.

R ³Be C ₁-C ₁₈Alkyl, C ₇-C ₁₂Arylalkyl, C ₇-C ₁₂Aryl, C that alkyl replaces ₆-C ₁₂Aryl and their mixture, preferred C ₁-C ₁₂Alkyl, C ₇-C ₁₂Aryl alkylene, most preferably C ₁-C ₁₂Alkyl, most preferable.R ³The unit is as the unitary part of E described below.

R ⁴Be C ₁-C ₁₂Alkylidene group, C ₄-C ₁₂Alkenylene, C ₈-C ₁₂Aryl alkylene, C ₆-C ₁₀Arylidene, preferred C ₁-C ₁₂Alkylidene group, C ₈-C ₁₂Aryl alkylene, more preferably C ₂-C ₈Alkylidene group, most preferably ethylidene or butylidene.

R ⁵Be C ₁-C ₁₂Alkylidene group, C ₃-C ₁₂Hydroxy alkylidene, C ₄-C ₁₂Alkyl sub-dihydroxy, C ₈-C ₁₂The dialkyl group arylidene ,-C (O)-, C (O) NHR ⁶NHC (O)-,-C (O) (R ⁴) _rC (O)-,-R ¹(OR ¹)-, CH ₂CH (OH) CH ₂O (R ¹O) _yR ¹OCH ₂CH (OH) CH ₂-,-C (O) (R ⁴) _rC (O)-,-CH ₂CH (OH) CH ₂-, R ⁵Preferably ethylidene ,-C (O)-, C (O) NHR ⁶NHC (O)-,-R ¹(OR ¹)-,-CH ₂CH (OH) CH ₂-, CH ₂CH (OH) CH ₂O (R ¹O) _yR ¹OCH ₂CH (OH) CH ₂-, be more preferably-CH ₂CH (OH) CH ₂-.

R ⁶Be C ₂-C ₁₂Alkylidene group or C ₆-C ₁₂Arylidene.

Preferably " oxygen base " R unit is at R ¹, R ²And R ⁵Further definition in the unit.Preferably " oxygen base " R unit comprises preferred R ¹, R ²And R ⁵The unit.Preferred cotton goods stain remover of the present invention contains at least 50% and is the R of ethylidene ¹The unit.Preferred R ¹, R ²And R ⁵The unit combines as follows with " oxygen base " R unit and obtains preferred " oxygen base " R unit.

I) at-(CH ₂CH ₂O) _xR ⁵(OCH ₂CH ₂) _xThe preferred R of-middle replacement ⁵Obtain-(CH ₂CH ₂O) _xCH ₂CH OHCH ₂(OCH ₂CH ₂) _x-.

Ii) at-(CH ₂CH (OR ²) CH ₂O) _z(R ¹O) _yR ¹O (CH ₂CH (OR ²) CH ₂) _wThe preferred R of-middle replacement ¹And R ²Obtain-(CH ₂CH (OH) CH ₂O) _z(CH ₂CH ₂O) _yCH ₂CH ₂O (CH ₂CH (OH) CH ₂) _w-.

Iii) at-CH ₂CH (OR ²) CH ₂The preferred R of-middle replacement ²Mention-CH ₂CH (OH) CH ₂-.

The E unit is selected from hydrogen, C ₁-C ₂₂Alkyl, C ₃-C ₂₂Thiazolinyl, C ₇-C ₂₂Arylalkyl, C ₂-C ₂₂Hydroxyalkyl ,-(CH ₂) _pCO ₂M-,-(CH ₂) _qSO ₃M-,-CH (CH ₂CO ₂M) CO ₂M ,-(CH ₂) _pPO ₃M ,-(R ¹O) _mB ,-C (O) R ³, preferred hydrogen, C ₂-C ₂₂Hydroxy alkylidene, benzyl, C ₁-C ₂₂Alkylidene group ,-(R ¹O) _mB ,-C (O) R ³,-(CH ₂) _pCO ₂M-,-(CH ₂) _qSO ₃M-,-CH (CH ₂CO ₂M) CO ₂M, more preferably C ₁-C ₂₂Alkylidene group ,-(R ¹O) _xB ,-C (O) R ³,-(CH ₂) _pCO ₂M-,-(CH ₂) _qSO ₃M-,-CH (CH ₂CO ₂M) CO ₂M, most preferably C ₁-C ₂₂Alkylidene group ,-(R ¹O) _xB and-C (O) R ³When not carrying out modification or replace on nitrogen, then hydrogen atom keeps the part represented as E.

Oxidized when V, W or Z unit, when promptly nitrogen was the N-oxide compound, the E unit did not contain hydrogen atom.For example skeletal chain or side chain do not comprise the unit of following structure:

Or

Or

In addition, oxidized when V, W or Z unit, when promptly nitrogen was the N-oxide compound, the E unit did not comprise the carbonyl moiety that is directly connected in nitrogen-atoms.According to the present invention, E unit-C (O) R ³Part is not bonded in the nitrogen of N-oxide modifying, does not promptly have the N-oxide compound acid amides with following structure: Or

Or Or their combination.

B is hydrogen, C ₁-C ₆Alkyl ,-(CH ₂) _qSO ₃M-,-(CH ₂) _pCO ₂M-,-(CH ₂) _q(CHSO ₃M) CH ₂SO ₃M ,-(CH ₂) _q(CHSO ₂M) CH ₂SO ₃M ,-(CH ₂) _pPO ₃M ,-PO ₃M, preferred hydrogen ,-(CH ₂) _qSO ₃M-,-(CH ₂) _q(CHSO ₃M) CH ₂SO ₃M ,-(CH ₂) _q(CHSO ₂M) CH ₂SO ₃M, more preferably hydrogen or-(CH ₂) _qSO ₃M.

M is hydrogen or the water-soluble cationic that presents in an amount at least sufficient to satisfy charge balance.For example, sodium cation just in time satisfies-(CH ₂) _pCO ₂M and-(CH ₂) _qSO ₃M, thus obtain-(CH ₂) _pCO ₂Na and-(CH ₂) _qSO ₃The Na part.Can be in conjunction with to satisfy required chemical charge balance more than a kind of univalent cation (sodium, potassium etc.).Yet, surpass an anionic group and can use the divalent cation balancing charge, or must be more than one univalent cation to satisfy the electric charge needs of polyanion group.For example with sodium atom replace-(CH ₂) _qSO ₃M partly has formula-(CH ₂) _qSO ₃Na ₃Divalent cation, for example calcium (Ca ²⁺) or magnesium (Mg ²⁺) be used to replace or combine with other suitable unit price water-soluble cationic and be used for replacing.Preferred cation is sodium and potassium, more preferably sodium.

X is a water soluble anion, for example chlorine (Cl), bromine (Br ^-) and iodine (I ^-) or X can be any group that has negative charge, for example sulfate radical (SO ₄ ^2-) and methylsulfate (CH ₃SO ₃ ^-).

It is 1-6 that the general formula subscript has following value: p, and q is 0-6; R is 0 or 1; W is 0 or 1; X is 1-100; Y is 0-100; Z is 0 or 1; K is less than or equal to the value of n; M is 4-about 400; N is 0-about 200; M+n is at least 5.

Preferred cotton goods stain remover of the present invention contains and wherein is less than about 50% R group and comprises the unitary polyamine backbone of " oxygen base " R, preferably is less than approximately 20%, and more preferably less than 5%, most preferably the R unit does not comprise " oxygen base " R unit.

Not comprising the unitary most preferred cotton goods stain remover of " oxygen base " R contains and wherein is less than 50% R group and comprises the polyamine backbone that surpasses 3 carbon atoms.For example comprise 3 or carbon atom still less, for example ethylidene, propylene and trimethylene are preferred " alkyl " R unit.Promptly working as skeleton R unit is C ₂-C ₁₂During alkylidene group, preferred C ₂-C ₃Alkylidene group, most preferably ethylidene.

Cotton goods stain remover of the present invention contains all even non-homogeneous polyamine backbone of modification, wherein 100% or less-NH unit be modified.Be used for term of the present invention " evenly polyamine backbone " and be defined as the polyamine backbone that contains identical R unit (for example whole ethylidene).Yet this identity definition is not got rid of and is contained other external unitary polyamine that contains polymer backbone, and described polymer backbone is owing to the artifact of the method for selected chemosynthesis exists.For example, the known thanomin of those skilled in the art can be used as " initiator " in polymine synthetic, the polymine sample that therefore contains a hydroxyethyl part that is produced by polymerization " initiator " will be considered to contain even polyamine backbone in the present invention.Comprising and wherein having the unitary polyamine backbone of the unitary whole ethylidene R of non-side chain Y is even skeleton.Comprising the unitary polyamine backbone of all ethylidene R is and existing degree of branching or the irrelevant even skeleton of ring-type side chain number.

Be used for term of the present invention " non-homogeneous polymer backbone " and be meant polyamine backbone into the mixture of various R element lengths and R cell type.For example, non-homogeneous skeleton contains the R unit, and it is the unitary mixture of ethylidene and propylene." alkyl " and the unitary mixture of " oxygen base " R needn't provide non-homogeneous skeleton in the present invention.The suitable manipulation of these " R unit chain lengths " provides the ability of the water-soluble and fabric affinity of modification cotton goods stain remover of the present invention to the makers-up.

Preferred cotton goods soil release polymer of the present invention contains even polyamine backbone, it all or part of by polyethyleneoxy partly replace, all or part of quaternized amine, all or part of N-of the being oxidized to oxide compound of nitrogen and its mixture.Yet, the modification in an identical manner of not all skeleton amine nitrogen, the selection of modification is according to makers-up's concrete needs decision.Degree of ethoxylation also by the makers-up specifically need the decision.

The preferred polyamine normally polyalkylene amine (PAA), the polyalkyleneimine (PAI) that contain the skeleton of The compounds of this invention, preferably polyethylene amine (PEA), polymine (PEI), or by having PEA or the PEI that the R unit longer than parent PAA, PAI, PEA or PEI connects.Usually polyalkylene amine (PAA) is four butylidenes, five amine.PEA obtains with aftercut by comprising the reaction of ammonia and ethylene dichloride.Usually the PEA that obtains is Triethylenetetramine (TETA) (TETA) and tetren (TEPA).Surpass five amine, i.e. hexamine, seven amine, eight amine and nine possible amine, generally the mixture that obtains jointly shows and can not pass through fractionation by distillation, can comprise other material, for example cyclammonium, especially piperazine.The cyclammonium that can also have the side chain of being with nitrogen atom.Referring to the US2792372 of the Dickinson that issues May 14 nineteen fifty-seven, it has described the preparation method of PEA.

Preferred amine polymer skeleton is included as C ₂The unitary R of alkylidene group (ethylidene) unit also is called polymine (PEI).Preferred PEI has medium at least side chain, and promptly the ratio of m and n is less than 4: 1, yet the ratio that most preferably has m and n is about 2: 1 PEI.Preferred skeleton has following general formula before modification: Wherein the definition of m and n as mentioned above.Preferred PEI has the about 200 daltonian molecular weight of surpassing before modification.

In polyamine backbone, especially under the situation of PEI, primary, the second month in a season and the unitary relative proportion of tertiary amine will change according to the preparation method.Each hydrogen atom that connects each nitrogen-atoms of polyamine backbone chain represents to be used for to replace subsequently, the potential site of quaternized or oxidation.

These polyamine can be for example by at catalyzer, carbonic acid gas for example, polymerising ethylene imines preparation under the existence of sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetate etc.The concrete grammar for preparing these polyamine backbone is all classified this paper reference as at the US2553696 of the Wilson of the US2806839 of the Crowther of the US2208095 of US3033746, the Esselmann of promulgation on July 16th, 1940 etc. of US2182306, the Mayle of promulgation on May 8th, 1962 etc. of the Urich of promulgation on December 5 nineteen thirty-nine etc., promulgation on September 17 nineteen fifty-seven and promulgation on May 21 nineteen fifty-one.

The example that contains the modification cotton goods soil release polymer of the present invention of PEI illustrates with formula I-V:

Formula I has narrated the preferred cotton goods soil release polymer that contains the PEI skeleton, and wherein all commutable nitrogen are by using polyoxyalkylene oxygen base unit ,-(CH ₂CH ₂O) ₂₀H replaces the hydrogen modification, and it has following formula:

Formula I

Formula II has narrated the cotton goods soil release polymer that contains the PEI skeleton, and wherein all commutable nitrogen are by using polyoxyalkylene oxygen base unit ,-(CH ₂CH ₂O) ₇H replaces the hydrogen modification, has following formula:

Formula II

This is all with the example of one type group modified cotton goods soil release polymer.

Formula III has been narrated the cotton goods soil release polymer that contains the PEI skeleton, and wherein all commutable primary amine nitrogen are by using polyoxyalkylene oxygen base unit ,-(CH ₂CH ₂O) ₇H replaces the hydrogen modification, and by all oxidable primary and secondary nitrogen are oxidized to the N-oxide modifying, described cotton goods stain remover has following formula to molecule subsequently:

Formula III

Formula IV has narrated the cotton goods soil release polymer that contains the PEI skeleton, and wherein all skeleton hydrogen atoms are substituted, and part skeleton amine unit is by quaternized.Substituting group is polyoxyalkylene oxygen base unit ,-(CH ₂CH ₂O) ₇H or methyl.The PEI cotton goods soil release polymer of modification has following formula:

Formula IV

Formula V has narrated the cotton goods soil release polymer that contains the PEI skeleton, and wherein skeleton nitrogen is by replacing (i.e. quilt-(CH ₂CH ₂O) ₇H or methyl), quaternized, be oxidized to the N-oxide compound or it is in conjunction with modification.The cotton goods soil release polymer that obtains has following formula:

Formula V

In as above example, the nitrogen of not all unit kind comprises identical modification.The present invention allows the makers-up to contain the secondary amine nitrogen of some ethoxylation, contains other secondary amine nitrogen that is oxidized to the N-oxide compound simultaneously.This can also be used for primary amine nitrogen because, the makers-up can be chosen in oxidation or quaternized before with one or more substituting group modifications all or a part of primary amine nitrogen.Any possible combination of E group can be substituted on the primary and secondary amine nitrogen, except above-mentioned restriction.

The makers-up can utilize the possibility of polyamine backbone of the present invention with the mode modification that only obtains minimum oxidation matrix skeleton, and for example bleaching " mediations " can be finished before or after preparing.In the present invention, term " bleaching be in harmonious proportion " is defined as with the polyamine of enough SYNTHETIC OPTICAL WHITNER processing modifications with according to preparation condition oxidation skeleton.As an illustration, polyamine backbone needn't need by quaternized or chlorination modification to bleach stable.When the polyamine backbone sample of modification was exposed to suitable bleach system (for example nonanoly acyloxy benzene sulfonate/perborate), oxidable any skeleton nitrogen was with oxidized under this condition.Yet because the precision architecture character of skeleton, nitrogen part or all of or that the pre-bleaching agent is handled can keep not carrying out.Took place in case should be in harmonious proportion, the makers-up can guarantee that polyamine will not consume a large amount of SYNTHETIC OPTICAL WHITNER in conjunction with the polyamine and the bleach system of modification.

The technician of SYNTHETIC OPTICAL WHITNER preparation will understand the bleaching mediation will have its limitation, and more weak mediation bleaching can not be used for replacing the prescription SYNTHETIC OPTICAL WHITNER.

Alternatively, the makers-up wishes in process for preparation to add excessive SYNTHETIC OPTICAL WHITNER in laundry detergent composition so that carry out suitable bleaching on the spot " mediation " in the storage of preparation with in handling.

The preferred embodiments of the invention comprise uses polyhydroxy fatty acid amide surfactant to combine with modified polyamine described herein.This nonionogenic tenside is particularly useful for low pH prescription with combining of modified polyamine, promptly is lower than about 10 pH.Be applicable to low pH embodiment of the present invention polyhydroxy fatty acid amide can with other suitable detergent surfactant, for example nonionic, both sexes, zwitterionics and their mixture combination.

Be used for preferred cotton goods polymine soil release polymer of the present invention and be selected from polymine 1800E7 described in the embodiment 1-4 of WO97/42288 and its amine oxide derivative, polymine 1200E7 and its oxidation and/or quaternary ammonium derivative, polymine 600E20 and/or their mixture.Detergent component

Laundry detergent composition of the present invention must contain at least a other detergent component.The specific nature of these annexing ingredients and their add-on will be according to the physical form of composition and the character decisions of employed washing operation.

Laundry detergent composition of the present invention preferably also contains and is selected from washing assistant, especially zeolite, tripoly phosphate sodium STPP and/or layered silicate, tensio-active agent, preferred nonionic surfactants, for example other detergent component of alkylethoxylate or alkyl methyl glucamide, conventional soil release polymer and/or their mixture.

Laundry detergent composition of the present invention can be liquid, paste, gel, piece, sheet, sprays, foams, powder or particle.Particulate composition can also be " densification " form, and liquid composition can be " concentrating " form.

Composition of the present invention for example can be mixed with craft and machine laundry cleaning composition, and it comprises laundry additive composition and is applicable to the immersion of dirty fabric and/or pretreated composition and the fabric softener composition that adds when being applicable to rinsing.

When being formulated as the composition of the clothes washing method that is used to machine-wash, composition of the present invention preferably contains tensio-active agent and washing-aid compound and additional one or more detergent components simultaneously, and it is preferably selected from organic polymer, SYNTHETIC OPTICAL WHITNER, additional enzyme, suds suppressor, dispersion agent, lime soap dispersing agent, dirt suspension and anti redeposition agent and corrosion inhibitor.Laundry composition also can contain the softening agent as additional detergent components.When being formulated as laundry detergent composition, the said composition that contains mannase and cotton goods soil release polymer can provide fabric washing, decontamination, whiteness to keep and the color outward appearance.

Composition of the present invention also can be used as the detergent additives product of solid or liquid form.This additive product is used for replenishing or strengthening the performance of conventional detergent composition, and can add in any stage of washing process.

As required, the density of laundry detergent composition of the present invention is for being determined as the 400-1200 grams per liter, preferred 500-950 grams per liter composition under 20 ℃.

" densification " form of the present composition by density and, for composition, reflect best by the amount of mineral filler salt; Mineral filler salt is the conventional component of the laundry detergent composition of powder type; In conventional detergent composition, filling salt is generally by general composition weight meter 17-35% to exist in a large number.

In compact composition, filling salt preferably is no more than 10% to be no more than 15% of total composition by composition weight meter, is most preferably not exceeding 5% amount existence.Mineral filler salt such as indication in the present composition those, is selected from the vitriol and the muriate of basic metal and alkaline-earth metal.Preferred filling salt is a sodium sulfate.

Liquid detergent composition of the present invention also can be " conc forms ", in this case, compares with the conventional liq washing composition, and liquid detergent composition of the present invention will contain the water of low amount.The water content of concentrated liquid detergent is generally by detergent composition weight and is lower than 40%, more preferably less than 30%, most preferably is lower than 20%.

Be used for suitable detergent compound of the present invention and be selected from compound as described below.Surfactant system

Laundry detergent composition of the present invention preferably also can contain surfactant system, and wherein tensio-active agent can be selected from nonionic and/or negatively charged ion and/or positively charged ion and/or both sexes and/or zwitter-ion and/or semi-polarity tensio-active agent.Except mannase and cotton goods soil release polymer, laundry detergent composition of the present invention especially will contain nonionogenic tenside, preferably have the C8-C20 chain length, preferred C12-C16, with degree of ethoxylation be 2-9, alkyl ethoxylated nonionogenic tenside or the alkyl chain length of preferred 3-7 are C8-C20, the alkyl methyl glycosamine tensio-active agent of preferred C12-C18.We are surprised to find said composition scourability preferably are provided, especially for makeup and food stain and clean effect preferably.

Other tensio-active agent exists with the amount of 0.1%-60% by weight usually.In laundry detergent composition of the present invention, more preferably add-on is 1%-35% by weight, most preferably 1%-30% by weight.

Tensio-active agent preferably be mixed with composition in the enzyme component compatibility that exists.In liquid or gelatinous composition, tensio-active agent most preferably is mixed with it is promoted, or does not destroy the stability of any enzyme in these compositions at least.

The polyoxyethylene of alkylphenol, polyoxypropylene and polyoxy croton condensation thing are suitable as the nonionogenic tenside of surfactant system of the present invention, wherein preferred polyoxyethylene condenses.These compounds comprise having and contain about 14 carbon atoms of about 6-, the alkylphenol of the alkyl of the straight or branched configuration of about 14 carbon atoms of preferably about 8-and the condensation product of alkylene oxide.In preferred embodiments, oxyethane equals about 25 moles of about 2-with every mole of alkylphenol, and more preferably from about the amount of about 15 moles of ethylene oxide of 3-exists.Commercial available such ionic surfactant pack is drawn together the Igepal that is sold by GAF company ^TMCO-630 is by Rohm ﹠amp; The Triton that Haas company sells ^TMX-45, X-114, X-100 and X-102.These tensio-active agents are commonly referred to alkylphenol alcoxylates (for example alkyl phenol ethoxylate).

The condensation product of the oxyethane that primary and secondary fatty alcohol and about 1-are about 25 moles is suitable as the nonionogenic tenside of nonionic surfactant system of the present invention.The alkyl chain of fatty alcohol can be a straight or branched, and uncle or secondary contains about 22 carbon atoms of the 8-that has an appointment usually.Preferably have and contain about 20 carbon atoms of about 8-, more preferably contain the alcohol of alkyl of about 18 carbon atoms of about 10-and the condensation product of about 10 moles of ethylene oxide of the about 2-of every mol of alcohol.Every mol of alcohol exists about 7 moles of ethylene oxide of about 2-, most preferably 2-5 moles of ethylene oxide in described condensation product.The example of commercial available such nonionogenic tenside comprises Tergitol ^TM15-S-9 (C ₁₁-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Tergitol ^TM24-L-6NMW (C with narrow molecular weight distributions ₁₂-C ₁₄The condensation product of primary alconol and 6 moles of ethylene oxide), sell by Union Carbide Corp; Neodol ^TM45-9 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Neodol ^TM23-3 (C ₁₂-C ₁₃The condensation product of straight chain alcohol and 3.0 moles of ethylene oxide), Neodol ^TM45-7 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 7 moles of ethylene oxide), Neodol ^TM45-5 (C ₁₄-C ₁₅The condensation product of straight chain alcohol and 5 moles of ethylene oxide), by the sale of shell chemical company, Kyro ^TMEOB (C ₁₃-C ₁₅The condensation product of alcohol and 9 moles of ethylene oxide), by Procter ﹠amp; Gamble sells; With Genapol LA 030 or 050 (C ₁₂-C ₁₄The condensation product of alcohol and 3 or 5 moles of ethylene oxide), sell by Hoechst.The preferred HLB scope of these products is 8-11, most preferably 8-10.

The nonionogenic tenside that also can be used as surfactant system of the present invention is a disclosed alkyl polysaccharide in the US4565647 of the Llenado of promulgation on January 21st, 1986, it contains about 30 carbon atoms of the 6-that has an appointment, the hydrophobic grouping of preferred about 16 carbon atoms of about 10-with contain the 1.3-that has an appointment about 10, preferred about 1.3-about 3, the most preferably from about polysaccharide of about 2.7 sugar units of 1.3-, for example polysaccharide glycosides hydrophilic radical.Can use any recuding sugars that contains 5 or 6 carbon atoms, glucose for example, semi-lactosi and galactosyl can be used for substituting glucosyl (hydrophobic group optionally is connected positions such as 2-, 3-, 4-, thereby obtains glucose or semi-lactosi with respect to glucoside or galactoside).Key can be between 2-, 3-, 4-and/or the 6-position of position of the sugar unit that for example adds and previous sugar unit between sugar.

Preferred APG has following formula:

R ²O (C _nH _2nO) _t(glycosyl) _xR wherein ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, wherein to contain the 10-that has an appointment about 18 for alkyl, about 14 carbon atoms of preferably about 12-; N is 2 or 3, preferred 2; T is 0-about 10, preferred 0; X is that about 1.3-is about 10, and preferably about 1.3-is about 3, and most preferably from about 1.3-about 2.7.Glycosyl is preferably obtained by glucose.For preparing these compounds, at first form alcohol or alkyl polyethoxye alcohol, form glucoside (being connected the 1-position) with glucose or source of glucose reaction subsequently.Other glycosyl can be connected between its 1-position and previous glycosyl units 2-, 3-, 4-and/or the 6-position, preferably mainly in the 2-position subsequently.

Oxyethane also is suitable as additional nonionic surfactant system of the present invention with the condensation product of the hydrophobic grouping that forms by condensed epoxy propane and propylene glycol.The hydrophobic part of these compounds preferably has about 1500 to about 1800 molecular weight, and shows the water insoluble.Adding polyoxyethylene group in this hydrophobic part will increase the water-soluble of branch subpopulation, and it is the about 50% of condensation product gross weight that the fluid characteristics of product is retained to polyoxyethylene content, about 40 moles oxyethane more than this is equivalent to be condensed to.Such examples for compounds comprises some commercially available Plurafac ^TMLF404 and Pluronic ^TMTensio-active agent is sold by BASF.

The nonionogenic tenside that is suitable as nonionic surfactant system of the present invention equally is an oxyethane and the condensation product of the product that obtains by propylene oxide and reacting ethylenediamine.The hydrophobic grouping of these products is made up of the reaction product of quadrol and excessive propylene oxide, 2500 to about 3000 the molecular weight of having an appointment usually.This hydrophobic grouping and ethylene oxide condensation are to making condensation product contain the polyoxyethylene of about by weight 40%-about 80% and having the degree of the molecular weight of about 5000-about 11000.The example of such nonionogenic tenside comprises some commercially available Tetronic ^TMCompound is sold by BASF.

The nonionogenic tenside that is preferably used as surfactant system of the present invention is the polyethylene oxide condensation compound of alkylphenol, condensation product, alkyl polysaccharide and their mixture of primary and secondary fatty alcohol and about 25 moles of ethylene oxide of about 1-.The C that most preferably contains 3-15 oxyethyl group ₈-C ₁₄Alkyl phenol ethoxylate and the C that contains 2-10 oxyethyl group ₈-C ₁₈Alcohol ethoxylate (preferred average C ₁₀) and their mixture.

Highly preferred nonionogenic tenside is the following formula polyhydroxy fatty acid amide surfactant:

R ²-C (O)-N (R ¹)-Z is R wherein ¹Be H, or R ¹Be C _1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R ²Be C _5-31Alkyl and Z are the polyhydroxy alkyls with the straight-chain alkyl chain that is connected directly to few 3 hydroxyls, or their alkoxy derivative.Preferred R ¹Be methyl, R ²It is straight chain C _11-15Alkyl or C _16-18The alkyl or alkenyl chain, for example Oleum Cocois alkyl or their mixture and Z by in reductive amination process by reducing sugar, for example glucose, fructose, maltose, lactose obtain.

Spendable suitable anion surfactant is linear alkylbenzene sulfonate, alkyl sulfonate surfactants, and it comprises C ₈-C ₂₀The linear ester of carboxylic acid (being lipid acid), it is according to " american petroleum chemistry meeting will ", the method gaseous sulfur trioxide sulfonation in 52 (1975) the 323-329 pages or leaves.Proper raw material will comprise the natural fat material that is obtained by Tallow, beef, palm wet goods.

The preferred alkyl sulfonate surfactants that is particularly useful for laundry applications comprises the alkyl sulfonate surfactants that structural formula is following:

R ³-CH (SO ₃M)-C (O)-OR ⁴R wherein ³Be C ₈-C ₂₀Alkyl, preferred alkyl or their combination, R ⁴Be C ₁-C ₆Alkyl, preferred alkyl or their combination, M is a positively charged ion, it and alkyl ester sulfonic acid form water-soluble salt.Suitable salt-forming cation comprises metal, for example sodium, potassium and lithium and replacement or unsubstituted ammonium cation, for example monoethanolamine, diethanolamine and trolamine.Preferred R ³Be C ₁₀-C ₁₆Alkyl, and R ⁴Be methyl, ethyl or sec.-propyl.Especially preferred is R wherein ³Be C ₁₀-C ₁₆The methyl ester sulfonate of alkyl.

Other suitable anion surfactant comprises alkyl sulfate surfactant, and it is formula ROSO ₃The water-soluble salt of M or acid, wherein R C preferably ₁₀-C ₂₄Alkyl preferably contains C ₁₀-C ₂₀The alkyl of moieties or hydroxyalkyl, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl, M is H or positively charged ion, for example the ammonium of alkali metal cation (for example sodium, potassium, lithium) or ammonium or replacement (methyl-, dimethyl-and trimethylammonium-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine positively charged ion and, for example quaternary ammonium cation that obtains of ethamine, diethylamine, triethylamine and their mixture etc.) by alkylamine.For low wash temperature (for example being lower than about 50 ℃), usually preferred C ₁₂-C ₁₆Alkyl chain, for the preferred C of higher wash temperature (for example being higher than about 50 ℃) _16-18Alkyl chain.

Other anion surfactant that is applicable to the washing purposes also can be included in the laundry detergent composition of the present invention.They can comprise soap salt (comprise, the ammonium salt of sodium, potassium, ammonium and replacement for example, for example single-, two-and triethanolamine salt), C ₈-C ₂₂Uncle or secondary paraffin sulfonate, C ₈-C ₂₄Sulfonation poly carboxylic acid, the C of alkene sulfonate, the pyrolysis product preparation of passing through the sulfonation alkaline earth metal citrate in GB1082179 for example, described ₈-C ₂₄Alkyl polyglycol ether sulfate (containing 10 moles of ethylene oxide at the most); Alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol vitriol, alkylphenol oxyethane ether sulfate, paraffin sulfonate, alkylphosphonic, isethionate; for example, acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinate monoesters (especially saturated and unsaturated C ₁₂-C ₁₈Monoesters) and sulfosuccinate diester (especially saturated and unsaturated C ₆-C ₁₂Diester), the vitriol of acyl sarcosinate, alkyl polysaccharide, alkyl polyglucoside vitriol (the not Sulfated compound of nonionic described below) for example, chain primary alkyl sulfate and alkyl polyethoxye carboxylate salt, for example formula RO (CH ₂CH ₂O) _k-CH ₂COO ^-M ⁺, wherein, R is C ₈-C ₂₂Alkyl, k are the integers of 1-10, and M is the positively charged ion that forms soluble salt.Resinous acid and hydrogenated resin acid also are suitable, for example rosin, staybelite and the resinous acid and the hydrogenated resin acid that are present in or are obtained by Yatall MA.

Other example is described in " tensio-active agent and washing composition " (I and II volume, Schwartz, Perry and Berch).Various these class tensio-active agents also usually are described in the US3929678 of the Laughlin of on December 30th, 1975 promulgation etc., and the 23rd hurdle the 58th walks in the 29th hurdle the 23rd row (classifying this paper reference as).

If comprise, it is about 40% that laundry laundry detergent composition of the present invention contains about by weight 1%-usually, preferably about 3%-about 20% this analog anion surfactants.

The ten minutes preferred anionic surfactants tensio-active agent that comprises alkyl alkoxylated sulfate surfactant is formula RO (A) _mSO ₃The water-soluble salt of M or acid, wherein R is unsubstituted C ₁₀-C ₂₄Alkyl or contain C ₁₀-C ₂₄The hydroxyalkyl of moieties, preferred C ₁₂-C ₂₀Alkyl or hydroxyalkyl, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than zero, usually between about 0.5 to about 6, more preferably from about between 0.5 to about 3, M is H or positively charged ion, and it can be the ammonium cation of metallic cation (for example sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement for example.The present invention thinks over alkyl ethoxylated sulfate and alkyl propoxylated sulphates.The specific examples of the ammonium cation that replaces comprise methyl-, dimethyl-, trimethylammonium-ammonium cation and quaternary ammonium cation, for example tetramethyl-ammonium and lupetidine positively charged ion and by alkylamine, for example ethamine, diethylamine, triethylamine, the positively charged ion that their mixture obtains etc.The tensio-active agent of illustrative is C ₁₂-C ₁₈Alkyl polyethoxylated (1.0) vitriol (C ₁₂-C ₁₈E (1.0) M), C ₁₂-C ₁₈Alkyl polyethoxylated (2.25) vitriol (C ₁₂-C ₁₈E (2.25) M), C ₁₂-C ₁₈Alkyl polyethoxylated (3.0) vitriol (C ₁₂-C ₁₈E (3.0) M) and C ₁₂-C ₁₈Alkyl polyethoxylated (4.0) vitriol (C ₁₂-C ₁₈E (4.0) M), wherein M is selected from sodium and potassium usually.

The cationic detersive tensio-active agent that is applicable to laundry detergent composition of the present invention is the material that contains a long chain hydrocarbon groups.The example of this cats product comprises ammonium surfactant, for example alkyl trimethyl ammonium halogenide and have the tensio-active agent of following formula:

[R ²(OR ³) _y] [R ⁴(OR ³) _y] ₂R ⁵N ⁺X ^-R wherein ²Be alkyl or the alkyl benzyl that in alkyl chain, contains about 18 carbon atoms of the 8-that has an appointment, each R ³Be selected from-CH ₂CH ₂-,-CH ₂CH (CH ₃)-,-CH ₂CH (CH ₂OH)-,-CH ₂CH ₂CH ₂-and their mixture; Each R ⁴Be selected from C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, by connecting two R ⁴The benzyl rings structure that group forms ,-CH ₂CHOH-CHOHCOR ⁶CHOHCH ₂OH, wherein R ⁶Be that any hexose or molecular weight are lower than about 1000 hexose polymkeric substance and when y is not 0, are hydrogen; R ⁵With R ⁴Identical or alkyl chain, wherein R ²Add R ⁵The total number of carbon atoms be no more than about 18; Each y is that 0-is about 10, and the summation of y value is 0-about 15; With X be any compatible negatively charged ion.

Be applicable to that quaternary ammonium surfactant of the present invention has as shown in the formula (I):

Formula I wherein R1 is a short-chain alkyl (C6-C10) or as shown in the formula the alkyl amido alkyl of (II):

Formula II

Y is 2-4, and is preferred 3,

Wherein R2 is H or C1-C3 alkyl,

Wherein x is 0-4, preferred 0-2, and most preferably 0,

Wherein R3, R4 and R5 are identical or different, can be the alkoxylated alkyl of short-chain alkyl (C1-C3) or following formula III,

X wherein ^-Be counter ion, preferred halogenide, for example muriate or methylsulfate,

Formula III

R6 is C ₁-C ₄With z be 1 or 2.

Preferred quaternary ammonium surfactant is the compound by formula I definition, wherein

R ₁Be C ₈, C ₁₀Or their mixture, x=0,

R ₃, R ₄=CH ₃And R ₅=CH ₂CH ₂OH.

Highly preferred cats product is the water-soluble quaternary ammonium compound with following formula that is used for the present composition:

R ₁R ₂R ₃R ₄N ⁺X ^-(i) R wherein ₁Be C ₈-C ₁₆Alkyl, each R ₂, R ₃And R ₄Be respectively C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, benzyl and-(C ₂H ₄O) _xH, wherein x is 2-5, X is a negatively charged ion.R ₂, R ₃Or R ₄In to be no more than one should be benzyl.

R ₁The preferred alkyl chain length be C ₁₂-C ₁₅, especially wherein alkyl be the mixture of the chain length that obtains by Oleum Cocois or palm nuclear fat or by alkene the synthetic or pure synthetic method of OXO obtains.R ₂, R ₃And R ₄Preferred group be methyl and hydroxyethyl, negatively charged ion X can be selected from halogenide, methylsulfate, acetate moiety and phosphate anion.

The example that is used for suitable formula (i) quaternary ammonium compound of the present invention comprises:

Oleum Cocois trimethyl ammonium muriate or bromide;

Oleum Cocois methyl dihydroxy ethyl ammonium muriate or bromide;

Decyl triethyl ammonium muriate;

Decyl dimethyl hydroxyl ethyl ammonium muriate or bromide;

C _12-15Dimethyl hydroxyl ethyl ammonium muriate or bromide;

Oleum Cocois dimethyl hydroxyl ethyl ammonium muriate or bromide;

Tetradecyl trimethyl ammonium Methylsulfate;

Dodecyl dimethyl hexadecyldimethyl benzyl ammonium muriate or bromide;

Dodecyl dimethyl (oxyethylene group) ₄Ammonium muriate or bromide;

Cholinesterase (formula (i) compound, wherein R ₁Be CH ₂-CH ₂-O-C (O)-C _12-14Alkyl and R ₂, R ₃And R ₄Be methyl);

Dialkylimidazolium quinoline [formula (i) compound].

Be used for US4228044 and EP000224 that other cats product of the present invention also is described in the Cambre of promulgation on October 14th, 1980.

The soft component of typical cationic fabric comprises the soft active substance of water-insoluble quaternary ammonium fabric or their corresponding amine precursors, and the most frequently used is ammonium chloride or the Methylsulfate that contains two chain alkyl chains.

Wherein the preferred cation softening agent comprises as follows:

1) two Tallow, beef alkyl dimethyl ammonium chlorides (DTDMAC);

2) dihydro Tallow, beef alkyl dimethyl ammonium chloride;

3) dihydro Tallow, beef dimethyl methyl ammonium sulfate;

4) VARISOFT TA100;

5) two oil base alkyl dimethyl ammonium chlorides;

6) two palmityl hydroxyethyl ammonio methacrylates;

7) stearyl benzyl dimethyl ammonium chloride;

8) Tallow, beef base trimethyl ammonium chloride;

9) hydrogenated tallow base trimethyl ammonium chloride;

10) C _12-14Alkyl hydroxy ethyl alkyl dimethyl ammonium chloride;

11) C _12-18Alkyl dihydroxy ethyl ammonio methacrylate;

12) two (stearoyl-oxy ethyl) alkyl dimethyl ammonium chlorides (DSOEDMAC);

13) two (Tallow, beef oxygen base ethyl) alkyl dimethyl ammonium chloride;

14) two Tallow, beef base imidazoles Methylsulfates;

15) 1-(2-Tallow, beef amido ethyl)-2-Tallow, beef base imidazoles Methylsulfate.

Biodegradable quaternary ammonium compound exists as two long alkyl chain ammonium chloride and the Methylsulfate surrogate that tradition is used.This quaternary ammonium compound contains by functional group, for example long-chain alkane (alkene) base of carboxyl interruption.Described material and the fabric sofetening composition that contains them are at many publications, and be for example open among EP-A-0040562 and the EP-A-0239910.

Quaternary ammonium compound of the present invention and amine precursor have as shown in the formula (I) or (II): Wherein Q be selected from-O-C (O)-,-C (O)-O-,-O-C (O)-O-,-NR ⁴-C (O)-,-C (O)-NR ⁴-;

R ¹Be (CH ₂) _n-Q-T ²Or T ³

R ²Be (CH ₂) _m-Q-T ⁴Or T ⁵Or R ³

R ³Be C ₁-C ₄Alkyl or C ₁-C ₄Hydroxyalkyl or H;

R ⁴Be H or C ₁-C ₄Alkyl or C ₁-C ₄Hydroxyalkyl;

T ¹, T ², T ³, T ⁴And T ⁵Be C independently ₁₁-C ₂₂Alkyl or alkenyl;

N and m are the integers of 1-4; With

X ^-It is the compatible negatively charged ion of softening agent.The anionic unrestricted example compatible with softening agent comprises chlorion or methylsulfate.

Alkyl or alkenyl chain T ¹, T ², T ³, T ⁴And T ⁵Must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.Chain can be a straight or branched.Tallow, beef is the convenience and the cheap source of chain alkyl and thiazolinyl material.T wherein ¹, T ², T ³, T ⁴And T ⁵The compound of representing the long-chain substance mixture of common Tallow, beef is especially preferred.

The specific examples that is applicable to the quaternary ammonium compound of aqueous fabric soft compound of the present invention comprises:

1) N, N-two (Tallow, beef base oxygen base ethyl)-N, N-alkyl dimethyl ammonium chloride;

2) N, N-two (Tallow, beef base oxygen base ethyl)-N-methyl, N-(2-hydroxyethyl) methylsulfuric acid ammonium;

3) N, N-two (2-Tallow, beef base oxygen base-2-oxoethyl)-N, N-alkyl dimethyl ammonium chloride;

4) N, N-two (2-Tallow, beef base oxygen base-ethyl carbonyl-oxygen base ethyl)-N, N-alkyl dimethyl ammonium chloride;

5) N-(2-Tallow, beef base oxygen base-2-ethyl)-N-(2-Tallow, beef base oxygen base-2-oxoethyl)-N, the N-alkyl dimethyl ammonium chloride;

6) N, N, N-three (Tallow, beef base-oxygen base-ethyl)-N-ammonio methacrylate;

7) N-(2-Tallow, beef base-amino-2-oxoethyl)-N-(Tallow, beef base)-N, the N-alkyl dimethyl ammonium chloride; With

8) 1,2-two Tallow, beef base oxygen base-3-trimethyl ammonium propane chloride;

Mixture with any above-mentioned substance.

If comprise, it is about 25% that laundry detergent composition of the present invention contains by weight 0.2%-usually, preferably about 1%-about 8% this cats product.

Laundry detergent composition of the present invention also can contain nonionic and/or the anion surfactant outside both sexes, zwitter-ion and semi-polarity tensio-active agent and the above-mentioned material of having described.

Amphoterics also is applicable in the laundry detergent composition of the present invention.These tensio-active agents can broadly be described as the aliphatic derivatives of the second month in a season or tertiary amine or heterocycle is secondary and the aliphatic derivatives of tertiary amine, and wherein aliphatic group can be a straight or branched.One of aliphatic series substituting group contains at least about 8 carbon atoms, and about 18 carbon atoms of about usually 8-and at least one aliphatic substituting group contain the anionic water solubilizing group, for example carboxyl, sulfonate radical, sulfate radical.Referring to the US3929678 at the Laughlin of on December 30th, 1975 promulgation etc., the amphoterics of the capable illustrated of the 19th hurdle 18-35.

If comprise, it is about 15% that laundry detergent composition of the present invention contains by weight 0.2%-usually, preferably about 1%-about 10% this amphoterics.

Zwitterionics also is applicable in the laundry detergent composition.These tensio-active agents can broadly be described as the derivative of secondary and tertiary amine or heterocycle is secondary and the derivative of tertiary amine, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Referring to the US3929678 at the Laughlin of on December 30th, 1975 promulgation etc., the zwitterionics of 38 row-22 hurdles, the 19th hurdle, 48 row illustrated.

If comprise, it is about 15% that laundry detergent composition of the present invention contains by weight 0.2%-usually, preferably about 1%-about 10% this zwitterionics.

Semi-polar nonionic surfactants is the nonionogenic tenside of particular variety, and it comprises that the alkyl that contains about 18 carbon atoms of about 10-and two are selected from the water-soluble amine oxides of the part of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl; Contain the water soluble oxidized phosphine that the moieties of about 18 carbon atoms of about 10-and two are selected from the part of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl; Be selected from the water-soluble sulfoxide of the part of the alkyl that contains about 3 carbon atoms of the 1-that has an appointment and hydroxyalkyl with the moieties that contains about 18 carbon atoms of about 10-and one.

Semi-polarity nonionic detergent tensio-active agent comprises the amine oxide surfactant with following formula:

R wherein ³Be alkyl, hydroxyalkyl or the alkyl phenyl that contains about 22 carbon atoms of the 8-that has an appointment; R ⁴Be alkylidene group or hydroxy alkylidene or their mixture that contains about 3 carbon atoms of the 2-that has an appointment; X is 0-about 3; Each R ⁵It is the polyoxyethylene group that contains the alkyl or the hydroxyalkyl of about 3 carbon atoms of the 1-that has an appointment or contain about 3 ethylene oxide groups of the 1-that has an appointment.R ⁵Group can for example be interconnected to form ring structure by oxygen or nitrogen-atoms.

These amine oxide surfactants especially comprise C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₈-C ₁₂Alkoxyethyl dihydroxy ethyl amine oxide.

If comprise, it is about 15% that cleaning composition of the present invention contains by weight 0.2%-usually, about 10% semi-polar nonionic surfactants of preferably about 1%-.

Laundry detergent composition of the present invention also can contain the cosurfactant that is selected from uncle or tertiary amine.

Be used for suitable primary amine of the present invention and comprise formula R ₁NH ₂Amine, R wherein ₁Be C ₆-C ₁₂, preferred C ₆-C ₁₀Alkyl chain or R ₄X (CH ₂) _n, X is-O-,-C (O) NH-or-NH-, R ₄Be C ₆-C ₁₂Alkyl chain, n are 1 to 5, preferred 3.R ₁Alkyl chain can be a straight or branched, can preferably be less than 5 ethylene oxide moieties and be interrupted by 12 at the most.

The preferred amines of following formula of the present invention is positive alkylamine.Be used for suitable amine of the present invention and be selected from 1-hexylamine, 1-octylame, 1-decane and lauryl amine.Other preferred primary amine comprises C ₈-C ₁₀Oxygen base propylamine, octyloxy propylamine, 2-ethyl hexyl oxy propylamine, lauryl amido propylamine and amido propylamine.

Be used for suitable tertiary amine of the present invention and comprise having formula R ₁R ₂R ₃The tertiary amine of N, wherein R ₁And R ₂Be C ₁-C ₈Alkyl chain or

R ₃Be C ₆-C ₁₂, preferred C ₆-C ₁₀Alkyl chain or R ₃Be R ₄X (CH ₂) _n, and X is-O-,-C (O) NH-or-NH-, R ₄Be C ₄-C ₁₂, n is 1 to 5, preferably 2-3.R ₅Be H or C ₁-C ₂Alkyl and x are 1-6.

R ₃And R ₄It can be straight or branched; R ₃Alkyl chain can preferably be less than 5 ethylene oxide moieties and be interrupted by 12 at the most.

Preferred tertiary amine is R ₁R ₂R ₃N, wherein R ₁Be C ₆-C ₁₂Alkyl chain, R ₂And R ₃Be C ₁-C ₃Alkyl or

R wherein ₅Be H or methyl and x=1-2.

The amidoamines of following formula equally preferably: R wherein ₁Be C ₆-C ₁₂Alkyl; N is 2-4, and preferred n is 3; R ₂And R ₃Be C ₁-C ₄

The most preferred amine of the present invention comprises 1-octylame, 1-hexylamine, 1-decyl amine, 1-lauryl amine, C ₈-C ₁₀Oxygen base propylamine, N-Oleum Cocois 1,3 diaminopropanes, Oleum Cocois alkyl dimethyl amine, lauryl dimethyl amine, lauryl two (hydroxyethyl) amine, Oleum Cocois two (hydroxyethyl) amine, 2 moles of propenoxylated lauryl amines, 2 moles of propenoxylated octylames, lauryl amido propyl-dimethyl amine, C ₈-C ₁₀Amido propyl-dimethyl amine and C ₁₀The amido propyl-dimethyl amine.

The most preferred amine that is used for the present composition is 1-hexylamine, 1-octylame, 1-decyl amine, 1-lauryl amine.Especially suitable is oleyl amine, lauryl amido propylamine and the Oleum Cocois amido propylamine of dodecyl dimethyl amine and dihydroxy ethyl Oleum Cocois alkylamine and 7 times of ethoxylations.SYNTHETIC OPTICAL WHITNER

Laundry detergent composition of the present invention also can comprise SYNTHETIC OPTICAL WHITNER, hydrogen peroxide for example, and particle size is PB1, PB4 and the percarbonate of 400-800 micron.These bleaching components can comprise one or more oxygen bleaching agents and, according to selected SYNTHETIC OPTICAL WHITNER, one or more bleach-activating agents.If exist, the oxygen bleaching compound exists with the content of about 1%-about 25% usually.

Being used for SYNTHETIC OPTICAL WHITNER of the present invention can be any SYNTHETIC OPTICAL WHITNER that is used for laundry detergent composition, comprises oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER well known in the prior art.Be applicable to that SYNTHETIC OPTICAL WHITNER of the present invention is activation or non-activated SYNTHETIC OPTICAL WHITNER.

Spendable a kind of oxygen bleaching agent comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class SYNTHETIC OPTICAL WHITNER comprises monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid magnesium salts, 4-amino in the ninth of the ten Heavenly Stems-4-oxo Perbutyric Acid and diperoxy 12 carbon docosandioic acids.This SYNTHETIC OPTICAL WHITNER is open in US4483781, US patent application 740446, EP0133354 and US4412934.Highly preferred SYNTHETIC OPTICAL WHITNER also is included in 6-amino in the ninth of the ten Heavenly Stems-6-oxo of describing among the US4634551 and crosses oxy hexanoic acid.

Operable another kind of SYNTHETIC OPTICAL WHITNER comprises halogen bleaching agent.The example of hypohalite SYNTHETIC OPTICAL WHITNER for example comprises TCCA (Trichloroisocyanuric acid) and dichloroisocyanuric acid sodium and potassium and N-chlorine and N-bromoalkane sulphonamide.This material is usually in the weight 0.5-10% by final product, and preferably 1-5% adds by weight.

The hydrogen peroxide releasing agent can with bleach-activating agent; for example tetra acetyl ethylene diamine (TAED), nonanoly acyloxy benzene sulfonate (NOBS; in US4412934, describe), 3; 5;-trimethyl acetyl oxygen base benzene sulfonate (ISONOBS; in EP120591, describe) or penta-acetyl glucose (PAG) or N-nonanoyl-6-aminocaprolc acid sulfophenylate (NACA-OBS; in WO 94/28106, describe) be used in combination; they are crossed hydrolysis to form the peracid as active albic material, improved bleaching effect.Same suitable bleach-activating agent is the acylations citrate, and is for example open in the european patent application of not examining 91870207.7, at Procter ﹠amp; The asymmetric acyclic imide bleach activators of disclosed following formula among the patent application US № 60/022786 (application on July 30th, 1996) that does not examine of Gamble and the № 60/028122 (asking in 15 days October in 1996):

R wherein ₁Be C ₇-C ₁₃Saturated or the unsaturated alkyl of straight or branched, R ₂Be C ₁-C ₈Straight or branched saturated or unsaturated alkyl and R ₃Be C ₁-C ₄Saturated or the unsaturated alkyl of straight or branched.

Be used for the useful SYNTHETIC OPTICAL WHITNER of detergent composition of the present invention, the bleach system that comprises peroxy acid and contain bleach-activating agent and peroxy bleaching compound is described in application USSN08/136626, PCT/US95/07823, WO95/27772, WO95/27773, WO95/27774 and WO95/27775 that we examine.

Hydrogen peroxide can also exist by adding enzyme system (being enzyme and its substrate), it can washing and/or rinse cycle begins or process in produce hydrogen peroxide.This enzyme system is open in the EP patent application 91202655.6 of application on October 9th, 1991.

The containing metal catalyzer that is used for whitener composition comprises cobalt-containing catalyst, five amine cobaltous acetate (III) salt and contain Mn catalyst, for example compound of in EPA549271, EPA549272, EPA458397, US5246621, EPA458398, US5194416 and US5114611, describing for example.The bleaching composition that contain peralcohol, contains manganese bleach catalysts and sequestrant is described in patent application № 94870206.3.

SYNTHETIC OPTICAL WHITNER except that oxygen bleaching agent also is known in the prior art, can be used for the present invention.A kind of non-oxygen bleaching agent that cherishes a special interest comprises the photoactivation SYNTHETIC OPTICAL WHITNER, for example sulfonated zinc and/or aluminium phthalocyanine.These materials can be deposited on the dirt-carrying body in washing process.Under rayed and in the presence of oxygen, for example by clothes being hung in the daylight when dry, sulfonation zinc phthalocyanine phthalocyanine is activated, and the dirt-carrying body is bleached subsequently.Preferred zinc phthalocyanine and photoactivation bleaching process are described in US4033718.Detergent composition will contain about 1.25% sulfonation zinc phthalocyanine phthalocyanine of about by weight 0.025%-usually.Builder system

Laundry detergent composition of the present invention preferably also can contain washing assistant, more preferably zeolite, tripoly phosphate sodium STPP and/or layered silicate.We are surprised to find said composition scourability preferably are provided, especially for makeup and food stain and clean effect preferably.

The builder system of any routine is applicable to the present invention, it comprises silico-aluminate material, silicate, multi-carboxylate, alkyl or alkenyl succsinic acid and lipid acid, material, for example edetate, diethylenetriamine pentamethylene acetate, metal ion chelation agent, for example amino polyphosphonate, especially ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylenophosphonic acid(DTPP).Phosphate builders also can be used among the present invention.

Suitable washing assistant can be a mineral ion exchange material, normally inorganic hydrated aluminosilicate material, more particularly hydration synthetic zeolite, for example hydrated zeolite A, X, B, HS or MAP.

Other suitable inorganic builders material is a layered silicate, for example SKS-6 (Hoechst).SKS-6 is by water glass (Na ₂Si ₂O ₅) crystalline layered silicate formed.

The suitable multi-carboxylate of containing a carboxyl is included in disclosed lactic acid, oxyacetic acid and their ether derivant in belgian patent 831368,821369 and 821370.The multi-carboxylate of containing two carboxyls comprise succsinic acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid water-soluble salt and DE2446686 and 2446687 and US3935257 in the ether carboxylate described and the sulfinyl carboxylate salt of in belgian patent 840623, describing.The multi-carboxylate of containing three carboxyls especially comprises water-soluble citrate, aconitate and citraconate and succinate derivative, the carboxyl methoxy succinate of for example in GB1379241, describing, the newborn oxygen base succinate of in Holland's application 7205873, describing and the oxygen multi-carboxylate material of in GB1387447, describing, 2-oxa--1 for example, 1,3-tricarballylic acid salt.

The multi-carboxylate of containing four carboxyls is included in disclosed oxygen di-succinate, 1,1,2 among the GB1261829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group be included in GB1398421 and 1398422 and US3936448 in disclosed sulfo-succinic acid salt derivative and the sulfonation pyrolysis Citrate trianion in GB1082179, described, and it is open in GB1439000 to contain the substituent multi-carboxylate of phosphine.

Alicyclic ring and heterocycle multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene (cyclopentadienide) pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF) tetracarboxylic acid hydrochlorate, 1,2,3,4,5,6-hexane hexacarboxylic acid salt and polyhydroxy-alcohol, for example carboxymethyl derivant of Sorbitol Powder, mannitol and Xylitol.Aromatic multi-carboxy acid's salt is included in disclosed mellitic acid among the GB1425343, pyromellitic acid and phthalic acid derivative.

Wherein, preferred multi-carboxylate is that per molecule contains the hydroxycarboxylate of three carboxyls, more particularly Citrate trianion at the most.

The preferred builder system that is used for the present composition comprises water-insoluble silico-aluminate washing assistant, for example zeolite A or layered silicate (SKS-6) and water-soluble carboxylate sequestrant, for example mixture of citric acid.Other preferred builder system comprises water-insoluble silico-aluminate washing assistant, for example zeolite A and water-soluble carboxylate sequestrant, for example mixture of citric acid.The preferred builder system that is used for liquid detergent composition of the present invention comprises soap and multi-carboxylate.

But component part is used for other builder material of the builder system of particulate composition and comprises inorganic substance, for example alkaline carbonate, supercarbonate, silicate and organic substance, for example organic phosphonate, amino polyalkylene phosphonate and aminopolycanboxylic acid's salt.

Other suitable water-soluble organic salt is all or co-polymeric acids or their salt, and wherein poly carboxylic acid contains and is no more than at least two carboxyls that two carbon atoms are separated from each other.Such polymkeric substance is open in GB-A-1596756.The example of this salt is the multipolymer of the polyacrylate of MW2000-5000 and they and maleic anhydride, and this multipolymer has 20000-70000, especially about 40000 molecular weight.

Detergent builders salt is usually pressing composition weight meter 5%-80%, preferred 10%-70%, and the most common be the amount existence of 30%-60% by weight.Conventional detergent enzyme

Except mannase, laundry detergent composition also can contain one or more enzymes, and it provides scourability, fabric nursing and/or hygiene effect.

Described enzyme comprises the enzyme that is selected from cellulase, hemicellulase, peroxidase, proteolytic enzyme, glucoamylase, amylase, zytase, lipase, phosphide enzyme, esterase, at, polygalacturonase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase, malic enzyme, beta-glucanase, arabinofuranosidase/xylosidase, hyaluronic enzyme, chondroitinase, laccase or their mixture.

Preferably combination contains the conventional enzyme that is suitable for, as the laundry detergent composition of proteolytic enzyme, amylase, lipase, at and/or cellulase and one or more plant cell-wall degrading enzymes bonded mixtures.

Suitable proteolytic enzyme is the subtilysin (subtilysin BPN and BPN ') that the special bacterial strain by subtilis and Bacillus licheniformis obtains.A kind of suitable proteolytic enzyme is obtained by the special bacterial strain that the whole pH scope at 8-12 has the bacillus of maximum activity, and it is developed by NovoIndustries A/S (Denmark), and sells with ESPERASE , hereinafter referred to as " Novo ".The preparation of this kind of enzyme and similar enzyme is described in the GB1243784 of Novo.Other suitable proteolytic enzyme comprises ALCALASE , DURAZYM  and SAVINASE  and the MAXATASE  that is obtained by Gist-Brocades, MAXACAL , PROPERASE  and the MAXAPEM  (Maxacal of protein engineering) that is obtained by Novo.Protease also comprises the modified bacteria serine protease, the proteolytic enzyme of description in the european patent application 87303761.8 (especially 17,24 and 98 pages) of on April 28th, 1987 application for example, it is referred to herein as " proteolytic enzyme B " and the proteolytic enzyme in the EP199404 of disclosed Venegas on the 29th October in 1986, it relates to the bacterial serine protease of modification, and it is referred to herein as " protease A ".Suitable is the proteolytic enzyme that is referred to herein as " proteolytic enzyme C ", it is the mutation of the alkaline serine protease that obtained by bacillus, wherein replace arginine with Methionin at 27, replace Xie Ansuan at 104 with tyrosine, replace l-asparagine and replace Threonine with L-Ala with Serine at 274 at 123.Proteolytic enzyme C is disclosed EP90915958.4 in 16 days Mays in 1991, corresponding to describing among the WO91/06637.The mutation of gene modification, especially the mutation of proteolytic enzyme C is also included among the present invention.

The preferred protease that is called " proteolytic enzyme D " is the carbonylic hydrolase mutation that has at the undiscovered aminoacid sequence of occurring in nature, be called as the name of the C.Ghosh of WO95/10591 and on October 13rd, 1994 application etc. described in the patent application of " bleaching composition that contains proteolytic enzyme " (US series number № 08/322677), it by in above-mentioned carbonylic hydrolase, be equivalent to+replace various amino-acid residues with different aminoacids on 76 positions, and preferred also in conjunction with replacing numbering+99 that are equivalent to be selected from according to the bacillus amyloliquefaciens subtilysin, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206, + 210, + 216, + 217, + 218, + 222, + 260, + 265 and/or+one or more amino-acid residues of 274 obtain by the precursor carbonylic hydrolase.Same suitable be carbonylic hydrolase mutation at the proteolytic enzyme described in the WO95/10591, it has by substituted various amino-acid residues on being equivalent to of pre-enzyme+210 positions and in conjunction with one or more following residues :+33, + 62, + 67, + 76, + 100, + 101, + 103, + 104, + 107, + 128, + 129, + 130, + 132, + 135, + 156, + 158, + 164, + 166, + 167, + 170, + 209, + 215, + 217, the aminoacid sequence that+218 and+222 replacement obtains, wherein Bian Hao position is equivalent to from the subtilysin of the natural generation of bacillus amyloliquefaciens or is equivalent at other carbonylic hydrolase or subtilysin, for example the slow suitable amino-acid residue in the genus bacillus subtilysin (application on June 4th, 1997 examine patent application US series number 60/048550).

Being equally applicable to of the present invention is the proteolytic enzyme of describing in EP251446 and WO91/06637, the proteolytic enzyme BLAP  that describes in WO91/02792 and their mutation described in WO95/23221.

Also can be referring to the high pH proteolytic enzyme that obtains by bacillus NCIMB40338 described in the WO93/18140A of Novo.The enzyme-containing detergent that comprises proteolytic enzyme, one or more other enzymes and a kind of reversible protease inhibitors has been described among the WO92/03529A of Novo.If desired, can be as Procter ﹠amp; The WO95/07791 of Gamble is described to obtain having the absorptivity of reduction and the water-disintegrable proteolytic enzyme of improvement.A kind of recombinant trypsin shape proteolytic enzyme that is applicable to washing composition of the present invention has been described among the WO94/25583 of Novo.Other suitable proteolytic enzyme is described in the EP516200 of Unilever.

Protease to be pressing composition weight meter 0.0001%-2%, preferred 0.001%-0.2%, and more preferably the content of the pure enzyme of 0.005%-0.1% adds in the laundry detergent composition of the present invention.

Be used for cellulase of the present invention and comprise bacterium or fungal cellulase.They preferably have the pH optimum value between the 5-12 and surpass the ratio work of 50CEVU/mg (Mierocrystalline cellulose viscosity unit).Suitable cellulase is described in US4435307, the J61078384 of Barbesgoard etc. and WO96/02653, and they disclose the fungal cellulase that is produced by Humicola insolens, Trichoderma (Trichoderma), careless Rhizopus (Thielavia) and Sporothrix (Sporotrichum) respectively.EP739982 has described by the new isolating cellulase of genus bacillus kind.Suitable cellulase also is disclosed among GB-A-2075028, GB-A-2095275, DE-OS-2247832 and the WO95/26398.

The example of this cellulase is the bacterial strain by Humicola insolens (Humicola grisea var.thermoidea), especially the cellulase of humicola lanuginosa strain DSM 1800 generations.

Other suitable cellulase is that the molecular weight that has that is obtained by Humicola insolens is about 50kDa, iso-electric point 5.5 and contain 415 amino acid whose cellulases; With the plain enzymic activity of the display fibers that obtains by Humicolainsolens DSM 1800 ^～The 43kD endoglucanase; Preferred endoglucanase component has disclosed aminoacid sequence among the PCT patent application WO91/17243.It is same that what be fit to is the EGIII cellulase of describing in the WO94/21801 of disclosed Genencor on the 29th September in 1994 that is obtained by Trichoderma longibrachiatum.Especially suitable cellulase is the cellulase with color nursing efficacy.The example of this cellulase is the cellulase of describing in the EP patent application № 91202879.2 (Novo) of application on November 6th, 1991.Carezyme and Celluzyme (NovoNordisk A/S) are particularly useful.Also referring to WO91/17244 and WO91/21801.Other plain enzyme of suitable fibers that is used for fabric nursing and/or scourability is described at WO96/34092, WO96/17994 and WO95/24471.

Described cellulase adds in the laundry detergent composition in the content by the pure enzyme of laundry detergent composition weight 0.0001%-2% usually.

Peroxidase and oxygen source, for example percarbonate, perborate, persulphate, hydrogen peroxide etc. and be used in combination as the phenols substrate of SYNTHETIC OPTICAL WHITNER synergy molecule.They are used for " solution bleaching ", promptly avoid the dyestuff removed by the dirt-carrying body in washing operation or pigment to be transferred in other dirt-carrying body in washing soln.Peroxidase is known in the prior art, and it comprises, for example horseradish peroxidase, lignoenzyme and halo peroxidase, for example chlorine and bromoperoxidase.The detergent composition that contains peroxidase is open in the EP № 96870013.8 of the European patent application EP 91202882.6 of for example PCT International Application No. WO 89/099813, WO89/09813 and application on November 6th, 1991 and application on February 20th, 1996.Same suitable is laccase.

Synergistic agent exists with the content by general composition weight meter 0.1%-5% usually.The thiodiphenylamine that preferred synergistic agent is replacement and phenoxazine, lysivane propionic acid (PPT), 10-ethyl thiodiphenylamine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP) and 10-first base phenoxazine (in WO94/12621, describing) and the cloves acid esters (the alkyl cloves acid esters that C3-C5 replaces) and the phenol that replace.SPC-D or Sodium peroxoborate are preferred hydrogen peroxide cources.

Above-mentioned peroxidase adds in the laundry detergent composition in the content by the pure enzyme of laundry detergent composition weight 0.0001%-2% usually.

Other preferred enzyme that can be included in the laundry detergent composition of the present invention comprises lipase.The suitable lipase that is used for the washing composition purposes comprises the microorganism by Rhodopseudomonas, the lipase that Situ Ci Shi aeruginosa atcc 19.154 disclosed in GB1372034 obtains.Suitable lipase comprises the lipase that shows positive immunological cross-reaction with lipase antibody, and it is produced by microorganism Pseudomonas fluorescens IAM1057.This lipase can be obtained by Amano Pharmaceutical Co.Ltd. (Nagoya, Japan), and commodity are called lipase P " Amano ", hereinafter referred to as " Amano-P ".Other suitable commercial lipases comprises Amano-CES, from the Chromobacter viscosum lipase of the Chromobacter viscosum var.lipolyticumNRRLB 3673 of ToyoJozo Co. (Tagata, Japan) for example; The Chromobacter viscosum lipase that obtains by U.S.Biochemical Corp. (US) and Disoynth (Holland); And the lipase that obtains by the gladiolus pseudomonas.Especially suitable lipase is lipase, for example M1 Lipase ^RAnd Lipomax ^R(Gist-Broxades) and Lipolase ^RWith Lipolase Ultra ^RWhen (Novo), they are found in and are used in combination with composition of the present invention is very effective.Same suitable be the lipolytic enzyme of in WO94/03578, the WO95/35381 of EP258068, the WO92/05249 of Novo Nordisk and WO95/22615 and Unilever and WO96/00292, describing.

That same suitable is at [EC 3.1.1.50], and it is considered to the lipase of particular variety, does not promptly need the lipase of interface activation.In laundry detergent composition, add at for example WO-A-88/09367 (Genencor); Describe among WO90/09446 (Plant Genentic System) and WO94/14963 and the WO94/14964 (Unilever).

Lipase and/or at add in the laundry detergent composition in the content by the pure enzyme of laundry detergent composition weight 0.0001%-2% usually.

Can comprise that amylase (α and/or β) is to remove the spot of carbohydrate-based.On February 3rd, 1994, the WO94/02597 of disclosed Novo Nordisk A/S described the diastatic laundry detergent composition of adding mutant.Same WO95/10603 referring to disclosed Novo NordiskA/S on the 20th in April nineteen ninety-five.Other amylase that becomes known for detergent composition comprises α-and beta-amylase.α-Dian Fenmei is known in the prior art, is included in the amylase of describing among US5003257, EP252666, WO91/00353, FR2676456, EP285123, EP525610, EP368341 and the GB1296839 (Novo).Other suitable amylase is the amylase of the improved stability described among the disclosed WO96/05295 in 18 days Augusts in 1994 of Genencor disclosed WO94/18314 and on February 22nd, 1996 and as in the amylase mutation that has additional modification in direct parent of being obtained by Novo Nordisk A/S of describing among the disclosed WO95/10603 of in April, 95.Same suitable amylase is described in EP277216, WO95/26397 and WO96/23873 (all belonging to Novo Nordisk).

The example of commercial α-Dian Fenmei product is Purafect Ox Am  and Termamyl , BAN , Fungamyl  and the Duramyl  that is obtained by Genencor, obtains by Novo Nordisk A/S Denmark.WO95/26397 has described other suitable amylase: α-Dian Fenmei, it is characterized in that, by the test determination of Phadebas  alpha-amylase activity, have under its pH in 25 ℃-55 ℃ temperature range and at 8-10 than the ratio of Termamyl  high at least 25% ratio alive and live.Suitable is the above-mentioned diastatic mutation of describing in WO96/23873 (Novo Nordisk).In WO95/35382, describe having other amylolytic enzyme that improves character aspect activity level and thermostability and the greater activity horizontal integration.

Amylolytic enzyme to be pressing composition weight meter 0.0001%-2%, preferred 0.00018%-0.06%, and more preferably the content of the pure enzyme of 0.00024%-0.048% adds in the laundry detergent composition of the present invention.

Above-mentioned enzyme can be any suitable source, for example plant, animal, bacterium, fungi and yeast source.The source can also be have a liking for temperature or have a liking for limiting condition (have a liking for cold, psychrotrophic, thermophilic, have a liking for pressure, have a liking for alkali, have a liking for acid, have a liking for halogen etc.).Pure or the impure form of these enzymes can both be used.At present, common practice is that enzyme through protein/group engineering modification agriotype is with their effectiveness of performance in laundry detergent composition of the present invention of optimizing.For example but design variable is to increase the consistency of the component that runs into usually in enzyme and the said composition.In addition, but design variable makes best pH, SYNTHETIC OPTICAL WHITNER or sequestrant stability, the catalytic activity etc. of enzyme variants can adapt to specific washing uses.

Under the situation of bleach stability, especially should note the amino acid of oxidation-sensitive and should note surface charge for surfactant compatibility.The iso-electric point of this kind of enzyme can be passed through some charged amino acid whose displacement modification, for example increases iso-electric point and can help to improve consistency with anion surfactant.The stability of enzyme can further be improved by producing for example additional salt bridge, and strengthens the calcium binding site to increase sequestrant stability.Must note cellulase especially, because most of cellulase has combination separately in conjunction with territory (CBS).The character of this kind of enzyme can change in conjunction with the modification in the territory by these.

Described enzyme adds in the laundry detergent composition of the present invention in the content by the pure enzyme of laundry detergent composition weight 0.0001%-2%.Enzyme can be used as independent component (containing a kind of bead, particle, stabilising liq of enzyme etc.) or adds as the mixture (for example composite particles (cogranulate)) of two or more enzymes.

Other suitable detergent component that can add is the oxydasis scavenging agent, and it is described not examining in the european patent application 92870048.6 of application on January 31st, 1992.The example of this oxydasis scavenging agent is ethoxylation four ethylidene polyamine.

The WO9307263A of Genencor International and WO9307260A, the US3553139 of the McCarty of the WO8908694A of Novo and promulgation on January 5th, 1971 etc. has also described the method in various enzyme materials and their the adding synthetic detergent compositions.The US4507219 of the US4101457 of the Place of promulgation on July 18th, 1978 etc. and the Hughes of promulgation on March 26th, 1985 further discloses enzyme.The US4261868 of the Hora of on April 14th, 1981 promulgation etc. has disclosed the proenzyme material that is used for the liquid scrubbing prescription and they and has added method in this prescription.The enzyme that is used for washing composition can in all sorts of ways and be stablized.The US3600319 of the Gedge of on August 17th, 1971 promulgation etc. and October in 1986 Venegas on the 29th EP199405 and EP200586 the enzyme stabilization technique is disclosed and enumerates.The enzyme stabilising system is also for example described in US3519570.The WO9401532A of Novo has described the useful bacillus AC13 that can access proteolytic enzyme, zytase and cellulase.Color nursing and fabric nursing effect

Also can comprise the technology that color nursing efficacy type is provided.The example of these technology is the organo-metallic catalysts that are used for the color protection.This organo-metallic catalyst is described in the european patent application of not examining 92870181.2.Dye-fixing agent, be used for crease-resistant and improve polyolefine dispersion agent, the spices of water adsorptive power and be used for that color nursing is handled and the polymkeric substance (PCT/US97/16546) of the amido functional group of spices affinity is other example of color nursing/fabric nursing technology, and examine description among the patent application № 96870140.9 in application on November 7th, 1996.

Fabric softener also can add in the laundry detergent composition of the present invention.These materials can be inorganic or organic types.Inorganic softening agent is the terre verte of for example describing in GB-A-1400898 and US5019292.The organic fabric softening agent comprises the water-insoluble tertiary amine as describing among GB-A1514276 and the EP-B0011340, the mixture of they and single C12-C14 quaternary ammonium salt in EP-B-0026527 and EP-B-0026528 open and as EP-B0242919 in disclosed two long-chain acid amides.Other useful organic constituent of fabric softener system is included in disclosed high molecular weight polyethylene oxide material in EP-A0299575 and 0313146.

The consumption of terre verte is usually at 2%-20% by weight, and more preferably in the scope of 5%-15%, this material mixes in the rest part that component adds prescription as doing.The organic fabric softening agent, for example water-insoluble tertiary amine or two long-chain acid amides materials are with 0.5%-5% by weight, usually the consumption of 1%-3% adds, and high molecular weight polyethylene oxide material and water-soluble cationic material be with 0.1%-2% by weight, and the consumption of 0.15%-1.5% adds usually.These materials add the spraying drying part of composition usually, though they can be more easily as doing mixed particle adding or being sprayed at as melt liquid on other solid ingredient of composition in some cases.Sequestrant

Laundry detergent composition of the present invention also optionally contains one or more iron and/or manganese sequestrant.This sequestrant can be selected from aminocarboxylate, amino phosphonates do, and aromatic chelator that polyfunctional group replaces and composition thereof hereinafter will define them.Although do not want to be limited by theory, we think that the effect of these materials is in part because they remove the excellent ability of iron and mn ion by forming the soluble chelating thing from washings.

The aminocarboxylate of the sequestrant of useful as selective comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their basic metal, ammonium and substituted ammonium salt and composition thereof.When allowing to use the total phosphorus of minimum content at least in laundry detergent composition, amino phosphonates do also is adapted at being used as in the present composition sequestrant, and it comprises ethylenediamine tetraacetic (methylene phosphonic acid salt), is DEQUEST.These amino phosphonates do preferably do not comprise the alkyl or alkenyl more than about 6 carbon atoms.The aromatic chelator that polyfunctional group replaces also is suitable for the present composition.US3812044 referring to the Connor of on May 21st, 1974 promulgation etc.This compounds of preferred sour attitude is the dihydroxyl disulfobenzene, as 1, and 2-dihydroxyl-3,5-disulfobenzene.

Being used for preferred biodegradable cheating agent of the present invention is ethylenediamine disuccinate (" EDDS "), [S, S] isomer particularly, and this is open in the US4704233 of the Hartman of promulgation on November 3rd, 1987 and Perkins.

Composition of the present invention can also contain and for example insoluble washing assistant, water-soluble methylglycine oxalic acid (MGDA) salt (or acid) that is used as sequestrant or auxiliary washing assistant that for example zeolite, layered silicate etc. use together.

If use, these sequestrants generally account for about 0.1%-about 15% of laundry detergent composition weight of the present invention.More preferably, if use, these sequestrants are about 0.1%-about 3.0% of said composition weight.Suds suppressor

The component of another selection is a suds suppressor, for example polysiloxane and silicon dioxide-poly-mixture of siloxanes.Polysiloxane can be expressed as alkylating polysiloxane material usually, and silicon-dioxide uses with the broken form of fine powder usually, for example various types of silicon-dioxide aerosols, xerogel and water drain silica.These materials can be used as particle and add, and wherein suds suppressor advantageously water-soluble or water is dispersible, go up substantially and discharge the ground adding in the impermeable carrier by the nonsurfactant washing composition.In addition, suds suppressor solubilized or be dispersed in the liquid vehicle adds by being sprayed on one or more other components.

Preferred polysiloxane Foam Control is open in the US3933672 of Bartollota etc.Other suds suppressor that especially is suitable for is the self-emulsifying polysiloxane suds suppressor of describing among the disclosed German patent application DTOS2646126 on April 28th, 1977.This examples for compounds is DC-544, is commercially obtained by Dow Corning, and it is polysiloxane-glycol copolymer.Especially preferred Foam Control is the suds suppressor system that contains the mixture of polysiloxane oil and 2-alkyl chain triacontanol.Suitable 2-alkyl-alkanol is a 2-butyl octanol, and it obtains with trade(brand)name Isofol12R commercial.

This suds suppressor system is described not examining in the european patent application 92870174.7 of application on November 10th, 1992.

Especially preferred polysiloxane Foam Control is described in the european patent application of not examining 92201649.8.Described composition can contain and forge system atresia silicon-dioxide, for example Aerosil ^RBonded polysiloxane/silica mixture.

Usually to press composition weight meter 0.001%-2%, the content of preferred 0.01%-1% by weight uses above-mentioned suds suppressor.Other

Can use other component that is used for laundry detergent composition, for example soil-suspending agent, stain remover, white dyes, abrasive material, sterilant, tarnish inhibitor, tinting material and/or encapsulate capsule or do not wrap capsular spices.

Especially suitable encapsulate capsule material is a water-soluble capsule, and described in GB1464616, it is made up of the matrix of polysaccharide and polyol.Other suitable water-soluble encapsulate capsule material comprises the dextrin that the starch acid esters by the not gelationization of the dicarboxylic acid that replaces described in US3455838 obtains.These acid esters dextrin are preferably by starch, and for example nephrite rice, soft Chinese sorghum, sago, tapioca (flour) and potato prepare.The suitable example of described encapsulate capsule material comprises the N-Lok by National Starch preparation.N-Lok encapsulate capsule material is made up of modified corn starch and glucose.Starch is by adding simple function group substituted radical, for example octenyl succinic acid anhydride modification.

Antiredeposition and soil-suspending agent that the present invention is suitable comprise derivatived cellulose, for example methylcellulose gum, carboxymethyl cellulose and Natvosol and poly carboxylic acid or its salt all or multipolymer.Such polymkeric substance comprises previously mentioned as the polyacrylate of washing assistant and the multipolymer of maleic anhydride-acrylic copolymer and maleic anhydride and ethene, methyl ethylene salt or methacrylic acid, and maleic anhydride accounts at least 20 moles of % of multipolymer.These materials are usually with 0.5%-10% by weight, and more preferably 0.75%-8% most preferably presses the amount of composition weight meter 1%-6% and uses.

Preferred white dyes is the negatively charged ion feature, the example is 4,4 '-two-(2-alcohol amido-4-anilino-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2-morpholino-4-anilino-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4 '; 4 "-two-(2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2:2 ' disulfonate sodium, 4,4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethyl amino)-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(4-phenyl-2,1,3-triazole-2-yl) stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two-(2-anilino-4-(1-methyl-2-hydroxyethyl amino)-s-triazine-6-base is amino) stilbene-2:2 ' disulfonic acid disodium, 2-(stilbene radicals-4 "-(naphtho--1 '; 2 ': 4; 5)-1; 2; 3-triazole-2 "-sodium sulfonate and 4,4 '-two (2-sulfo group styryl) biphenyl.Highly preferred whitening agent is a disclosed concrete whitening agent among the EP753567.

Other useful polymkeric substance is a polyoxyethylene glycol, and especially molecular weight is 1000-10000, more preferably 2000-8000, most preferably from about 4000 polymkeric substance.They are with 0.20%-5% by weight, and more preferably the amount of 0.25%-2.5% is used.The multi-carboxylate of these polymkeric substance and homopolymerization mentioned above or copolymerization is improving whiteness maintenance, fabric dust deposit and is being valuable aspect the scourability of earth, protein and oxidable dirt in the presence of transition metal impurity.Conventional soil release polymer

Laundry detergent composition of the present invention preferably will contain other conventional soil release polymer.Said composition provides washing and detergency ability preferably.Suitable soil release polymer is the end capped polyester of negatively charged ion and the conventional terephthalic acid and ethylene glycol and/or the unitary multipolymer of propylene glycol or the terpolymer of different arrangement modes.The example of this polymkeric substance the common US4116885 that transfers the possession of and 4711730 and EP0272033 in describe.According to EP-A-0272033, especially preferred polymkeric substance has following formula: (CH ₃(PEG) ₄₃) _0.75(POH) _0.25[T-PO) _2.8(T-PEG) _0.4] T (POH) _0.25((PEG) ₄₃CH ₃) _0.75Wherein PEG is-(OC ₂H ₄) O-, PO is (OC ₃H ₆O) and T be (pcOC ₆H ₄CO).

Equally of great use be modified poly ester, the random copolymers of dimethyl terephthalate (DMT), sulfoisophthalic acid dimethyl ester, ethylene glycol and 1-2 propylene glycol for example, end group mainly are made up of sulfosalicylic acid ester and less important monoesters by ethylene glycol and/or propylene glycol.Target is to obtain at two ends by the end capped polymkeric substance of sulfosalicylic acid ester, and in the present invention, most of above-mentioned multipolymer of the present invention " mainly " is by sulfosalicylic acid ester end-blocking.Yet some multipolymer will not be end capped fully, thereby their end group can be made up of the monoesters of the ethylene glycol and/or the third 1-2 glycol, and its " inferior strategic point " forms this material.

The polyester that the present invention selects contains about by weight 46% dimethyl terephthalate (DMT), by weight about 16% the third-1,2 glycol, about 10% ethylene glycol, about 13% sulfosalicylic acid dimethyl ester and about by weight 15% sulfoisophthalic acid by weight by weight, its molecular weight is about 3000.Polyester and their preparation method describe in detail in EPA311342.

The enzyme that promptly exists in the inactivation detergent composition of the known free chlorine that in tap water, exists of people in the prior art.Therefore, use chlorine scavenger to press the content of general composition weight meter more than 0.1% in prescription, for example perborate, ammonium sulfate, S-WAT or polymine will provide the improvement stability of detergent enzyme in washing process.The composition that contains chlorine scavenger is described in the european patent application 92870018.6 of application on January 31st, 1992.

Oxyalkylated multi-carboxylate by the polyacrylate preparation is used for the present invention so that additional degrease performance to be provided.This material is classified this paper reference as in WO91/08281 and PCT90/01815 page 4 and hereinafter description.Comprise that at these materials chemically every 7-8 acrylate unit has the polyacrylate of an oxyethyl group side chain.Side chain has formula-(CH ₂CH ₂O) _m(CH ₂) _nCH ₃, wherein m is 2-3, n is 6-12.The side chain ester is connected in polyacrylate " skeleton " so that " comb shape " polymer-type structure to be provided.Molecular weight can change, but is generally about 2000-about 50000.This alkoxylate multi-carboxylate can account for about 0.05%-about 10% of present composition weight.Dispersion agent

Laundry detergent composition of the present invention also can contain dispersion agent: suitable water-soluble organic salt is all or co-polymeric acids or its salt, and wherein poly carboxylic acid contains and is no more than at least two carboxyls that two carbon atoms are separated from each other.Such polymkeric substance is open in GB-A-1596756.The example of this salt is the multipolymer of the polyacrylate of MW 2000-5000 and they and maleic anhydride, and this multipolymer has the molecular weight of 1000-100000.

Especially the multipolymer of acrylate and methacrylate, for example molecular weight is that 4000 480N can add by the content of composition weight meter 0.5-20% in the laundry detergent composition of the present invention.

Composition of the present invention can contain calcium soap peptizing agent compound, and it has as what give a definition and is no more than 8, preferably is no more than 7, is most preferably not exceeding 6 lime soap dispersing power (LSDP).Calcium soap peptizing agent compound preferably exists with the amount of 0%-20% by weight.

The various measuring results of calcium soap peptizing agent effect provide by calcium soap peptizing agent ability (LSDP), it is by using at article H.C.Borghetty and C.A.Bergman, and the calcium soap distributed test of describing in the 88-90 page or leaf of J.Am.Oil.Chem.Soc. the 27th volume is measured.This calcium soap distributed test method is extensive use of by the practitioner in this area, and is relevant with for example following comment; W.N.Linfield, tensio-active agent science book series (Surfactant science Series), the 7th volume, page 3; W.N.Linfield, Tenside surf.det. the 27th volume, 159-163 page or leaf (1990) and M.K.Nagarajan, W.F.Masler, Cosmetics andToiletries, the 104th volume, 71-73 page or leaf (1989).LSDP is at 30ml 333ppm lime carbonate (calcium: magnesium=3: 2) disperse the required dispersion agent of the calcium soap precipitates that formed by the 0.025g sodium oleate and the % weight ratio of sodium oleate in the water of equivalent hardness.

Tensio-active agent with good calcium soap peptizing agent ability comprises some amine oxide, trimethyl-glycine, sultaine, alkyl ethoxy sulfate and ethoxylated alcohol.

Having LSDP is no more than 8 the example that is used for tensio-active agent of the present invention and comprises C ₁₆-C ₁₈Dimethyl oxidation amine, average degree of ethoxylation are the C of 1-5 ₁₂-C ₁₈Alkyl ethoxy sulfate, especially average degree of ethoxylation are 3 C ₁₂-C ₁₅Alkyl ethoxy sulfate surfactant (LSDP=4) and average degree of ethoxylation are the C of 12 (LSDP=6) or 30 ₁₄-C ₁₅Ethoxylated alcohol is sold with trade(brand)name Lutensol A012 and Lutensol A030 respectively by BASF GmbH.

Be applicable to polymerization calcium soap peptizing agent of the present invention at M.K.Nagarajan, W.F.Masler at Cosmetics and Toiletries, the 104th the volume, describe in the article in the 71-73 page or leaf (1989).

The hydrophobic bleach agent is the amino caproyl of 4-[N-capryloyl-6-for example] benzene sulfonate; the amino caproyl of 4-[N-nonanoyl-6-] benzene sulfonate, the amino caproyl of 4-[N-decanoyl-6-] benzene sulfonate and their mixture and nonanoly acyloxy benzene sulfonate also can be used as calcium soap peptizing agent compound with hydrophilic/hydrophobic SYNTHETIC OPTICAL WHITNER preparation.Dye transfer suppresses

Laundry detergent composition of the present invention also contains and is suppressed at the dyestuff that comprises the dissolving that runs in the band yarn dyed fabric washing operation and suspension is transferred to another kind of fabric from a kind of fabric compound.The polymeric dye transfer inhibitor

Laundry detergent composition of the present invention contains 0.001%-10% by weight usually, preferred 0.01%-2%, more preferably 0.05%-1% polymeric dye transfer inhibitor.In laundry detergent composition, add described polymeric dye transfer inhibitor usually and carry the dye transfer of yarn dyed fabric to other fabric that therewith washs so that suppress.In washing process, before the fugitive dye that DYED FABRICS washes out had an opportunity to contact other article, this polymkeric substance had complexing or adsorbs the ability of this dyestuff.

Especially suitable polymeric dye transfer inhibitor is multipolymer, polyvinylpyrrolidonepolymers polymers, Ju Yi Xi oxazolidinone and the polyvinyl imidazol or their mixture of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.

Add this polymkeric substance and improved the performance of enzyme of the present invention.

A) polyamine N-oxide pllymers

The polyamine N-oxide pllymers that is suitable for contains the unit with following structural formula:

Wherein P is polymerisable unit, and the R-N-O group can the coupled or wherein polymerisable unit of R-N-O group component part or both combinations.A is

-O-,-S-,-N-; X is 0 or 1;

R is aliphatic series, aliphatic, the aromatic series of ethoxylation, heterocycle or alicyclic group or its any combination, the part that the nitrogen of N-O group can nitrogen coupled or wherein N-O group is these groups.

The N-O group can be represented by following general structural formula:

Wherein R1, R2 and R3 are aliphatic group, aromatic series, heterocycle or alicyclic group or their combination, x or/and y or/and z is 0 or 1, the part that the nitrogen of N-O group can be connected with it or wherein the nitrogen of N-O group constitutes these groups wherein.

The N-O group can be the part of polymerizable unit (P) or can link to each other with polymeric skeleton or both combination.

Wherein the suitable polyamine N-oxide of the part of N-O group formation polymerizable unit comprises polyamine N-oxide, and wherein R is selected from aliphatic series, aromatic series, alicyclic ring or heterocyclic group.

The above-mentioned polyamine N-oxide of one class comprises one group of polyamine N-oxide, and wherein the nitrogen of N-O group constitutes the part of R-group.Preferred polyamine N-oxide compound is that wherein R is a heterocyclic group, for example the compound of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and their derivative.

Another kind of above-mentioned polyamine N-oxide comprises one group of polyamine N-oxide, and wherein the nitrogen of N-O group is connected in the R group.

Other suitable polyamine N-oxide is the polyamine oxide compound that is connected with polymerizable unit of N-O group wherein.

These polyamine N-oxide of preferred class are the polyamine N-oxide with general formula (I), and wherein R is aromatic series, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is the part of described R group.

The example of this compounds is the polyamine oxide compound, and wherein R is a heterogeneous ring compound, for example pyridine, pyrroles, imidazoles and their derivative.

The polyamine N-oxide of another preferred class is the polyamine oxide compound with general formula (I), and wherein R is aromatic series, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is connected in described R group.

The example of this compounds is the polyamine oxide compound, and wherein the R group can be aromatics, for example phenyl.

Can use any polymer backbone as long as the amine oxide polymers that forms is water miscible and has the dye transfer inhibition activity.The example of suitable polymeric skeleton is polyethylene, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and their mixture.

The ratio that common amine n-oxide polymkeric substance of the present invention has amine and amine n-oxide is 10: 1-1: 1000000.Yet the amount of the amine oxide group that exists in the polyamine oxide polymer can change by suitable copolymerization or by suitable N-degree of oxidation.The ratio of amine and amine n-oxide is preferably 2: 3-1: 1000000, more preferably 1: 4-1: 1000000, most preferably be 1: 7-1: 1000000.In fact polymkeric substance of the present invention comprises random or segmented copolymer, and one of them monomer type is an amine n-oxide, and other monomer type is amine n-oxide or is not.The unitary PKa of the amine oxide of polyamine N-oxide＜10, preferred PKa＜7, more preferably PKa＜6.

The polyamine oxide compound can obtain by almost any extent of polymerization.Extent of polymerization is not crucial, as long as material has required water-soluble and dye suspension ability.

Molecular-weight average is generally 500-1000000; Preferred 1000-50000, more preferably 2000-30000, most preferably 3000-20000.

B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole

Be used for N-vinyl imidazole N-vinyl pyrrolidone polymer of the present invention and have 5000-1000000, the molecular-weight average of preferred 5000-200000.

The highly preferred polymkeric substance that is used for laundry detergent composition of the present invention comprises the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, wherein said polymkeric substance has 5000-50000, more preferably 8000-30000, the most preferably molecular-weight average of 10000-20000.

Average molecular weight range passes through determination of light scattering by as Barth H.G. and Mays J.W. " chemical analysis " 113 volumes described in " modernism of polymer characterization ".

Highly preferred N-vinyl imidazole N-nvp copolymer has 5000-50000; More preferably 8000-30000; The molecular-weight average of 10000-20000 most preferably.

With above-mentioned molecular-weight average is that the N-vinyl imidazole N-vinylpyrrolidone copolymer of feature provides fabulous dye transfer inhibition activity, and does not influence the scourability with the detergent composition of its preparation unfriendly.

The mol ratio that N-vinyl imidazole N-vinylpyrrolidone copolymer of the present invention has N-vinyl imidazole and N-vinyl pyrrolidone is 1-0.2, more preferably 0.8-0.3, most preferably 0.6-0.4.

C) Polyvinylpyrolidone (PVP)

Laundry detergent composition of the present invention can also use molecular-weight average to be about 2500-about 400000, preferred about 5000-about 200000, more preferably from about 5000-is about 50000, most preferably from about the Polyvinylpyrolidone (PVP) of the molecular-weight average of 5000-about 15000 (" PVP ").Suitable Polyvinylpyrolidone (PVP) commercial by ISP Corporation, New York, NY and Montreal, Canadian with ProductName PVP K-15 (viscosity molecular weight is 10000), PVP K-30 (molecular-weight average 40000), PVP K-60 (molecular-weight average 160000) and PVP K-90 (molecular-weight average 360000).Can comprise Sokalan HP 165 and Sokalan HP 12 by other suitable Polyvinylpyrolidone (PVP) that BASF Cooperation obtains commercial; Polyvinylpyrolidone (PVP) known to the skilled in detergent applications (referring to for example EP-A-262897 and EP-A-256696).

D) Ju Yi Xi oxazolidinone:

Laundry detergent composition of the present invention also can use Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.It is about 400000 that described Ju Yi Xi oxazolidinone has about 2500-, and preferably about 5000-is about 200000, and more preferably from about 5000-is about 50000, most preferably from about the molecular-weight average of 5000-about 15000.

E) polyvinyl imidazol:

Laundry detergent composition of the present invention also can use polyvinyl imidazol as the polymeric dye transfer inhibitor.It is about 400000 that described polyvinyl imidazol has about 2500-, and preferably about 5000-is about 200000, and more preferably from about 5000-is about 50000, most preferably from about the molecular-weight average of 5000-about 15000.

F) cross-linked polymer:

Cross-linked polymer is that its skeleton is interconnected to polymkeric substance to a certain degree; These connections can be chemistry or physical properties, may have active group on skeleton or side chain; Cross-linked polymer is described in the 1035-1039 page or leaf at " polymer science magazine " 22 volumes.

In one embodiment, prepare cross-linked polymer by this way and make them form three-dimensional rigid structure, it can catch dyestuff in the hole that is formed by three-dimensional structure.In another embodiment, cross-linked polymer is caught dyestuff by swelling.This cross-linked polymer is described in the patent application of not examining 94870213.9.Washing methods

Composition of the present invention can be used for any washing or cleaning method basically, the method that it comprises immersion process, pretreatment process and can add the rinse step of independent rinse aid composition.

The method that the present invention describes comprises fabric to contact with washing soln with mode hereinafter described usually.Method of the present invention is carried out in washing process usually.Washing methods especially carries out between 10 ℃-60 ℃ preferably at 5 ℃-95 ℃.The pH of treatment soln is preferably 7-12.

Following embodiment is used to illustrate composition of the present invention, rather than limits or define in addition scope of the present invention.In laundry detergent composition, the content of enzyme represents that with the pure enzyme of general composition weight meter except as otherwise noted, detergent component is to represent by general composition weight meter.The component symbol of abbreviation has following implication: LAS: straight chain C _11-13Sodium alkyl benzene sulfonate TAS: Tallow, beef sodium alkyl sulfate CxyAS: C _1x-C _1ySodium alkyl sulfate CxySAS: C _1x-C _1ySecondary (2,3) sodium alkyl sulfate CxyEz: with the C of average z moles of ethylene oxide condensation _1x-C _1yBe mainly the primary alconol CxyEzS of straight chain: with the C of average z moles of ethylene oxide condensation _1x-C _1ySodium alkyl sulfate QAS: R ₂.N ⁺(CH ₃) ₂(C ₂H ₄OH), R ₂=C ₁₂-C ₁₄QAS1: R ₂.N ⁺(CH ₃) ₂(C ₂H ₄OH), R ₂=C ₈-C ₁₁APA: C _8-10Amido propyl-dimethyl amine soap: the straight-chain alkyl carboxylic acid's sodium nonionogenic tenside that obtains by 80/20 mixture of Tallow, beef and coco-nut oil fatty acid: C ₁₃-C ₁₅Mixed ethoxylated/propoxylated fatty alcohol, average degree of ethoxylation 3.8, average

Degree of propoxylation 4.5Neodol 45-13: C ₁₄-C ₁₅The straight chain primary alcohol ethoxylate is sold STS by Shell Chemical CO: toluenesulfonic acid sodium salt CFAA: C ₁₂-C ₁₄Alkyl N-methyl glucose amide TFAA: C ₁₆-C ₁₈Alkyl N methyl glucose amide TPKFA: C ₁₂-C ₁₄The full cut lipid acid of topping silicate: amorphous sodium silicate (SiO ₂: Na ₂The metasilicate of O ratio=1.6-3.2): Starso (SiO ₂: Na ₂O ratio=1.0) zeolite A: formula Na ₁₂(AlO ₂SiO ₂) ₁₂.27H ₂The hydrated sodium aluminosilicate of O, primary particle size are that 0.1-10 is little

Rice (weight of representing based on anhydrous benchmark) NaSKS-6: formula δ-Na ₂Si ₂O ₅The crystalline layered silicate Citrate trianion: citrate trisodium dihydrate, active 86.4%, particle size distribution 425-850 micron citric acid: Citric Acid, usp, Anhydrous Powder borate: Sodium Tetraborate carbonate: anhydrous sodium carbonate, particle size 200-900 micron supercarbonate: anhydrous sodium bicarbonate, particle size distribution is a 400-1200 micron vitriol: anhydrous sodium sulphate sal epsom: anhydrous magnesium sulfate STPP: tripoly phosphate sodium STPP TSPP: tetrasodium pyrophosphate MA/AA: 4: 1 acrylate/maleate random copolymerss, the about 70000-80000MA/AA1 of molecular-weight average: 6: 4 acrylate/maleate random copolymerss, the about 10000AA of molecular-weight average: molecular-weight average is 4500 sodium polyacrylate polymer P A30: molecular-weight average is the polyacrylic acid 480N of about 4500-8000: 7: 3 acrylate/methacrylate random copolymerss, the about 3500Polygel/carbopol of molecular-weight average: high molecular weight crosslinked polyacrylate PB1: anhydrous sodium perborate monohydrate, nominal formula: NaBO ₂.H ₂O ₂PB4: sodium perborate tetrahydrate, nominal formula: NaBO ₂.3H ₂O.H ₂O ₂Percarbonate: anhydrous SPC-D, nominal formula: 2Na ₂CO ₃.3H ₂O ₂NaDCC: dichloroisocyanuric acid sodium TAED: tetra acetyl ethylene diamine NOBS: nonanoly acyloxy benzene sulfonate; sodium-salt form NACA-OBS: (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate DTPA: diethylene triaminepentaacetic acid(DTPA) HEDP: 1; 1-hydroxyl ethane di 2 ethylhexyl phosphonic acid DETPMP: diethyl triamine five (methylene phosphonic acid salt); all sell EDDS: quadrol-N by Meng Shan with trade(brand)name Dequest 2060; N '-disuccinic acid; (S; S) isomer; its sodium-salt form MnTACN: 1; 4; 7 trimethylammoniums 1; 4; 7 7-triazacyclononanes close manganese photoactivation SYNTHETIC OPTICAL WHITNER: use the capsular sulfonation zinc phthalocyanine phthalocyanine photoactivation of dextrin polymer soluble bag SYNTHETIC OPTICAL WHITNER 1: use the capsular sulphonation aluminum phthalocyanine PAAC of dextrin polymer soluble bag: five amine cobaltous acetate (III) salt paraffin: by the paraffin oil NaBz of Wintershall with trade mark Winog 70 sales: Sodium Benzoate BzP: benzoyl peroxide mannase: from Bacillus agaradherens; the mannosans protease enzyme of MCIMB40482: with trade(brand)name Savinase; Alcalase; Durazym (Novo Nordisk A/S); Maxacal

The protease that Maxapem (Gist-Brocades) sells and patent WO91/06637 and/

Or the proteolytic enzyme amylase of describing among WO95/10591 and/or the EP251446: at WO94/18314, describe among the WO96/05295 by Genencor with trade(brand)name Purafact Ox

The amylolytic enzyme that Am  sells, the Termamyl  that obtains by Novo Nordisk A/S,

Fungamyl  and Duramyl  and those amylolytic enzyme lipase of in WO95/26397, describing: by Novo Nordisk A/S with trade(brand)name Lipolase, Lipolase Ultra and by

The lipolytic enzyme cellulase that Gist-Brocades sells with Lipomax: by Novo Nordisk A/S with trade(brand)name Carezyme, Celluzyme and/or Endolase

The cellulolytic enzyme CMC that sells: Xylo-Mucine PVP: polyethylene polymer, molecular-weight average is 60000PVNO: polyvinylpyridine-N-oxide compound, molecular-weight average is 50000 PVPVI: vinyl imidazole and vinylpyrrolidone copolymer, molecular-weight average is 20000 whitening agent 1: 4,4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 2: 4,4 '-two (4-anilinos-6-morpholino-1,3,5 triazines-2-yl) stilbene-2:2 '-disulfonic acid disodium polysiloxane defoamers: contain the polydimethylsiloxane Foam Control of siloxanes oxyalkylene copolymers as dispersion agent

The ratio of described Foam Control and described dispersion agent is 10: 1-100: 1 suds suppressor: 12% polysiloxane/silicon-dioxide, 18% stearyl alcohol, 70% starch, the particle form opalizer: water base single styrene latex mixture, by BASF Aktiengesellschaft with trade(brand)name

Lytron 621 sells SRP1: the end capped polyester SRP2 of negatively charged ion: the short block polymer QEA of diethoxyization poly-(terephthalic acid 1,2 propylidene ester): two ((C ₂H ₅O) (C ₂H ₄O) _n) (CH ₃)-N ⁺-C ₆H ₁₂-N ⁺-(CH ₃) two ((C ₂H ₅O)-(C ₂H ₄O)) _n, its

Middle n=20-30PEI: polymine, PEI 1800 E described in WO97/42288 ₇, PEI 1200 E ₇, season

PEI 1200 E of ammoniumization ₇, PEI 600 E ₂₀SCS: cumene sodium sulfonate HMWPEO: high molecular weight polyethylene oxide PEGx: polyoxyethylene glycol, molecular weight xPEO: polyethylene oxide, molecular-weight average 5000

Embodiment 1

Be prepared as follows high-density laundry detergent composition of the present invention:

Schedule: Nano Tea Application List 1, the West Lake Longjing tea 26 nano, nano Spring Ridge hui white tea 2, Hui Ming Tea 27 nano, nano eyebrow tea 3, nano Dongting Biluochun tea 28, nano Anji white tea tablets 4, nano Guzhu purple tea 29 tea Nano Nanjing rain 5, sub-nanometer afternoon tea 30 cents cents, nano Jingtingshan Green Ice Tea 6, nano Huangshan Mao Feng tea 31, nano revere tribute bud 7, nano Xinyangmaojian 32, nano Beach Tea 8, the nano level drops tea 33, nano silver needle tea Ssangyong 9, nano-Po Hung Tea 34 Tea nano Monkey Chief Peace 10, nano-browed Shangrao tea 35 tea Nano source 11, 36 nanometer Camellia Drive, nano Gap State Bifeng tea 12, nano Emei Trimeresurus tea 37 cents nano mist tea QinBa 13, Nami Nan An Danting green tea 38, nano Kai-top tea 14, 39 nanometer sky snow tea, nano Lushan fragrant 15, Nami Meng top tea 40, Na Mian of pine needle tea 16, nano Bay Creek fire Qingcha 41, nano Sunforge snow bud 17, 42 nanometer cactus tea, nano Ziyang Mao Jian tea 18, 43 nanometer Tianshan green tea, Green Peony Tea nano country 19, nano Yongchuan show bud 44, nano Tea Tea Product 20, nano Hugh Ningsong Luo tea 45 tea Nano Silver Peak Takahashi 21, nano Enshi Yulu Tea 46 Tea nano Yunfeng Pan cents 22, nano Duyun Tippy Tea 47 Tea nano Han mercury shuttle 23, nano Jiukeng Tippy Tea 48, nano Pekoe tea in Yunnan 24, nano Guiping Xishan tea 49, nano Zunyi Mao Feng Tea 25, nano-old bamboo tea generous 50 nm Jiuhua Shan Mao Feng Tea 51, nano Wang Gai Shan rice tea 76 tea new nano down the river 52, nano-hillock emerald green 77, nano Goldwater Verde Tea 53, Cha 78 nanometer Shaofeng, nano-gold altar Buxus tea 54, Namigulao tea 79 tea Nano Guzhang Tippy 55, Na Mishu City orchid tea 80 tea nano shuangjing 56, nano Pik tea 81 tea blacksmith nano weeks 57, nano small cloth yancha 82, nano Wenjun tender green tea 58, 83 nanometer Chinese top fragrant, nano lotus tea before the peak 59, 84 nanometer Tianshan white hair bud, bud nano silver lions 60, Cha 85 nanometer Tianzhu sword cents, nano Wild Goose Mao Feng Tea 61 Wong Chuk pekoe tea 86 nano, nano Kowloon Tea 62, 87 nano-Ma mushroom tea, nano Crescent Mao Feng Tea 63, nano car Yunshan Tippy Tea 88 Tea nano Nanshan Shoumei 64, 89 nanometer Guilin Mao Jian tea, green tea Namixiangbo 65, 90 nanometer Jiande tea bud, nano drying green tea 66, Nami Rui Huang Bo spent 91 states, nano rocks emerald green 67, nano Shuangqiaoshan Tippy Tea 92, Nami Meng top nectar tea 68, nano qintang Tippy Tea 93, Nami Rui grass Kui Tea 69, 94 nanometer Donghu Yin Hao tea, tea garden nano Hexi 70, nano Ganghwa Tippy Tea 95 nm Putuo Buddhist tea 71, Cha 96 nanometer dragon dance, nano Xuefeng Tippy Tea 72, Green 97 nanometer Turtle Rock, nano Qingcheng snow bud 73, Cha 98 cents Wuxi Nano, nano-ding tea 74, nano Guidong Delicate tea 99, Nami Long in tea 75, nano-top tea 100 Tian Mu Qing, nano silver monkey tea Songyang 101, 126 nm Longyan hatchback tea, nano Nanyue fragrant 102, Nami Mei tea 127 nanometer mark Greenwood Tea 103, 128 nm Lanxi Mao Feng Tea, Tea nano Mekong emerald tablets 104, 129 nm guanzhuang Tippy Tea, Tea Lo nano Chui 105, 130 nm clouds pekoe tea, tea Nano nest pit 106, 131 nm lotus tea, tea Nano Yuyao Falls 107, Jinshan Tsui bud 132 nanometers, nm Snow Mountain Green Tea 108 nm Mindanao Camellia 133 nm Chess fragrant 109, 134 nm cow tea arrived, nano-fragrant huaguoshan 110, 135 nano Buddhist tea, tea uniform nano Narcissus Velvet 111, 136 nm Guiding fragrant, nano silver monkey tea Suichang 112, 137 nm Tianchi name milli tea, nano ink Jiang Yun needle tea 113 nm Babel yancha 138 nm green tea 114, 139 nm Lingyun white tea, oolong nano 115 nm steamed green sencha 140 nm Wuyi 116, 141 nm Yunlin tea, nano Wuyi cinnamon tea 117 Nanodisks An Yunfeng Tea 142 nanometers in northern Fujian Narcissus tea 118 nm Green Jade Green Tea 143 Ma, Nano Iron Goddess of Mercy tea 119 East White Green bud 144 nm, nano white hair monkey tea 120, 145 nm Taebaek parietal tea, nano octagonal Herb Tea 121, 146 nm Kuril tea leaves, tea nanometer gold Gui 122, 147 nm Cheonggyecheon jade bud, nano Yongqing bergamot tea 123, Chan Lin tea 148 nanometers, nm Anxi tea-colored bell 124, green 149 nm blue fairy king, nano Phoenix Narcissus tea 125, green 150 nm seven Jingtang, nano Taiwan oolong tea 152, 177 nm Da Hong Pao tea, tea Nami Pu bait 153, 178 nm luohan tea, nano tea 154, 179 Nano White-crowned chicken tea, jasmine tea Nano 155, 180 nm water beetles tea, tea nano Zhulan 156, 181 nm tea, nano osmanthus tea 157, 182 nm white tea, honeysuckle tea Nano 158, 183 Nano Silver Needle Pekoe tea, scented tea nano Prynne 159, 184 nm white peony tea, tea roses nano 160, Nami Gong eyebrow tea 185 tea Nano Toi Toi 161, 186 nm yellow tea, tea nano nest 162, 187 Nano Silver Needle tea, ginseng tea Nano 163, Nami Meng top yellow bud 188 nm ginger tea 164, 189 nm Pak tippy tea, jujube tea Nano 165, 190 nm deer park Tippy Tea, Tea nano tonkinensis 166, Nami Huo Shan Huang Ya Cha 191 nm dogwood Yu Tea 167 nm Wei River White Tippy Tea 192 nm hawthorn tea 168 nm Wenzhou Huang Tang Tea 193 nm patchouli tea 169 nm Anhui states large yellow tea 194 nm Fennel tea 170, 195 nm Guangdong Dahua Yeh tea, tea nano Schisandra 171, 196 nm hippocampus Palace tea, licorice tea Nano 172, nano black tea 197 nm calamus tea 173, 198 nm Hunan black tea, nano Salvia tea 174, 199 nano-old green tea, nano ebony tea 175, 200 nm Sichuan brick tea, white tea Nano 176, 201 nanometer six Fort tea powder, nano Cordyceps tea 202, 227 nm lobelia tea, tea Nano sarmentosum 203, 228 nm Patriarch God tea, tea nano Citrus aurantium 204, Nami Xi red tea 229 nm Amomum tea 205, 230 nm lotus tea, tea Nano Elsholtzia 206, 231 nm ginseng tea, tea Nano Panda Hai 207, 232 nm lily tea, lotus leaf tea Nano 208, Nami Chuan Fritillaria tea 233 nm lotus tea 209, 234 nm red ginseng tea, lotus tea Nano 210, 235 nm cocklebur tea, nano Motherwort tea 211, 236 nm nitidum tea, tea nano Beiqi 212, 237 nm Radix tea, ginkgo leaf tea Nano 213, Nami Xin weed tea 238 nanometers bell sheep silk and tea 214, 239 nm tea incense, nano mulberry tea 215, 240 nm tea fungus, nano mistletoe tea 216, 241 nm orange peel tea, chrysanthemum tea Nano 217, 242 nm JGC tea, Chrysanthemum tea Nano 218, 243 nm Artemisia annua tea, nano Epimedium leaf tea 219, 244 nm capillaris tea, nano bamboo tea 220, 245 nm loquat tea, Nami Su leaf tea 221, 246 nm Acanthopanax tea, tea nano thistles 222, 247 nm diffusa tea, tea nano Shegan 223, 248 nm loosestrife tea, tea nano Dendrobium 224, 249 nm cardamom tea, tea nanometer British public 225, 250 nano-grass tea, tea nano Zaoren 226, 251 nm Mangosteen tea, mountain tea Nano 252, 278 nm barley tea, Nami Ding tea 253, 279 nm sandalwood tea, tea Nano Guri 254, 280 nm Gynostemma tea, tea nano thirty-seven 256, 281 nm mint tea, tea Nano Smilax 257, 282 nm senna tea, rhubarb tea Nano 258 nm Eucommia 283 nm betel tea 259, 284 nm Uncaria tea, betel nano skin tea 260, 285 nm Chine tea, tea nano woody 261, 286 nm Pulsatilla tea, tea Nano Euonymus alatus 262, 287 nm Cassia tea, Nami Yi leaf tea 263, 288 nm cinnamon tea, Nami Chuan Yun Tea 264, 289 nm Morinda tea, tea nano Araceae 265, 290 nm cynomorium tea, tea nano bezoar 266, 291 nm Ban Langen tea, tea nano Heiyi 267, 292 nm Poria tea, tea nano Curculigoside 268 nm Tianma Tea 293 nm Agrimony tea 269, 294 nanometer propolis tea, tea nano Angelica 270, 295 nm spores tea, tea Nano Gualou 271, 296 nm gentian tea, fruit tea Nano Mallow 272, 297 nm Bupleurum tea, nano earthworm tea 273, 298 nm Gui tea, tea satisfied Digupi 274, 299 nm ephedra tea, yellow tea nano ground 275, 300 nm kudzu tea, tea nano Burnet 276, Nami Su co-tea 301 nm one hundred tea 277, 302 nm hematoxylin tea, nano angelica tea 303, 328 nm Zhuru tea, tea Nano Quisqualis 304, 329 nano-Yuan Hu tea, tea nano Oriental Arborvitae 305, 330 nanometer Blood tea, tea nano Perrin 306, 331 nm scorpion tea, tea olive nano 307, 332 nm Acacia tea, tea nano Nepeta 308, 333 nm rushes tea, tea nano wind 309, 334 nm benzoin tea, nano comfrey tea 310, 335 nm red tea, tea Nano Gecko 311, Nami Mai bud 336 nm velvet tea 312, 337 nano-pepper tea, nano Huang Jing Tea 313, 338 nm pepper tea, goldenseal tea Nano 314, 339 nm cardamom tea, tea nano seabirds 315, 340 nm turtle shell tea, tea nano Campsis 316, 341 nm turtle tea, tea subtilis nano Ha 317, 342 Gunpowder Shanjia nano, nano summer without tea 318, 343 nm soap thorn tea, tea nano Radish 319, 344 nm Anemarrhena tea, tea nano Cyperus 320, 345 nm Treats tea, scented tea nano Magnolia 321, 346 nm Sophora tea, tea nano Clematis 322, 347 nanometer grass neem tea, tea nanotechnology littoralis 323, 348 nm bitter almond tea, tea Nano Passepartout 324, 349 nm Yuli tea, cotton nano-Lantern Tea 325, 350 nm peel tea, scented tea nano winter 326, 351 nm Millettla tea, nano mulberry leaf tea 327, 352 nm honeysuckle tea, ginger jujube tea Nano 353, 377 nm green beans Coffee, tea vertical nano Lingtoudancong 354, 378 nm corn tea, nano phoenix tea 355, 379 nm Babao tea, black tea nano Mauritius 356, 380 nano-noon tea, nano Indian tea 357 nm Ilex 381 nm highlands of Sri Lanka Tea 358 nm violet tea 382 nm to tea in Sri Lanka 359, Nami Xia Sang Ju tea 383 nm lowlands of Sri Lanka Tea 360, 384 nano-enriched tea, nano Sri Lanka Ceylon 361, 385 nm tea fungus, nano Kenyan tea 362, 386 nm walnut tea, black tea nano Indonesia 363, 387 nm governance and black tea, black tea nano Turkey 364, 388 nm Fujian tea, nano Japanese Gyokuro tea 365, Nami Tan Yang black tea 389 nm covered under the Japanese Tea 366, 390 nm Bai Lin tea, nano Japanese grind tea 367, Na Mining tea 391 nanometers Japanese Sencha 368, 392 nm Keemun, nano Japanese tea 369, 393 nanometer Lake black tea, oolong tea nano Japan 370, 394 nm Yunnan Jiang tea, black tea nano Pakistan 371, 395 nm should be black, nano Malaysia tea 372, 396 nm more tea, black tea nano Vietnam 373, 397 Nami Chuan tea, black tea nano Rwanda 374, 398 nm bergamot tea, black tea nano Tanzania 375, 399 nanometer ancient stone floor oolong tea, black tea nano Argentina 376 nm single longitudinal tea Phoenix 400 nm Brazilian tea Preparation of nano-tea "three-step" as shown in Figure The first step, common ground: It is a traditional mill the material crushed to mm ...

The following granular laundry detergent compositions that preparation the present invention especially uses under European washing machine condition:

I II III IV V VILAS 5.5 7.5 5.0 5.0 6.0 7.0TAS 1.25 1.9-0.8 0.4 0.3C24AS/C25AS-2.2 5.0 5.0 5.0 2.2C25E3S-0.8 1.0 1.5 3.0 1.0C45E7 3.25 ---- 3.0TFAA - 2.0-- C25E5 -5.5---- QAS 0.8 ----- QAS1-0.7 1.0 0.5 1.0 0.7STPP 19.7 ----- zeolite A-16.75 24.0 19.5 20.0 17.0NaSKS-6 / citrate-10.6-10.6-- (79: 21) Na-SKS-6 - 9.0-10.0 10.0 Carbonate 6.1 9.0 10.0 10.0 18.0 21.4 -2.0 7.0 5.0-2.0 bicarbonate silicate 6.8 - 0.3 0.5 - citrate - 4.0 4.0 - sulfuric acid Salt 36.8 - 5.0 - 12.0 Magnesium sulfate - 0.1 0.2 0.2-MA/AA 0.5 1.6 3.0 3.5 1.0 1.0CMC 0.2 0.4 1.0 1.0 0.4 0.4PB4 5.0 12.7 ---- percarbonate ---- 18.0 15.0TAED 0.5 3.1 - 5.0-NACA-OBS 1.0 3.5 --- 2.5DETPMP 0.25 0.2 0.3 0.4-0.2HEDP-0.3-0.3 0.3 0.3QEA - 1.0 1.0 1.0-mannanase 0.001 0.02 0.001 0.03 0.015 0.03 0.009 0.02 0.001 0.05 Protease 0.05 0.02 0.003 0.003 0.006 0.006 0.006 lipase cellulase 0.004 0.0007 0.0006 0.0006 0.0005 0.0005 0.0007 amylase 0.002 0.002 0.006 0.006 0.01 0.003PEI 3.0 1.75 1.0 0.5 0.25 0.25PVNO/PVPVI--0.2 0.2 - PVP 0.9 1.3 --- 0.9 SRP1 - 0.2 0.2 0.2-photoactivated bleaching agents 15 27 - 20 20 (ppm) photoactivated bleaching agents 15 ----- 1 (ppm) Brightener 1 0.08 0.2 - 0.09 0.15 Brightener 2-0.04 ---- Perfume 0.3 0.5 0.4 0.3 0.4 0.3 silicone defoamer 0.5 2.4 0.3 0.5 0.3 2.0 Density, g / l 750 750 750 750 750 750 Trace and a minor component up to 100% Example 3 was prepared as follows the In particular the invention the conditions for the European washing machine detergent composition:...

I II III IV blows powder

LAS????????????????6.0????5.0?????11.0?????6.0

TAS????????????????2.0????-???????-????????2.0

Zeolite A 23.5--19.5

STPP???????????????-??????26.0????21.0?????-

Vitriol 4.0 6.0 13.0-

MA/AA??????????????1.0????4.0?????6.0??????2.0

Silicate 1.0 7.0 3.0 3.0

CMC????????????????1.0????1.0?????0.5??????0.6

Whitening agent 1 0.2 0.2 0.2 0.2

Polysiloxane defoamers 1.0 1.0 1.0 0.3

DTPMP 0.4 0.4 0.2 0.4 spraying liquids

Whitening agent 0.02--0.02

C45E7??????????????-??????-???????-????????5.0

C45E2??????????????2.5????2.5?????2.0??????-

C45E3??????????????2.6????2.5?????2.0??????-

Spices 0.5 0.3 0.5 0.2

Polysiloxane defoamers 0.3 0.3 0.3-dried additive

QEA????????????????-??????-???????-????????1.0

EDDS???????????????0.3????-???????-????????-

Vitriol 2.0 3.0 5.0 10.0

Carbonate 6.0 13.0 15.0 14.0

Citric acid 2.5--2.0

QAS1???????????????0.5????-???????-????????0.5

Na-SKS-6???????????10.0???-???????-????????-

PEI????????????????0.5????1.0?????3.0??????0.5

Percarbonate 18.5---

PB4??????????????-????????18.0?????10.0???21.5

TAED?????????????2.0??????2.0??????-??????2.0

NACA-OBS?????????3.0??????2.0??????4.0????-

Mannase 0.001 0.02 0.01 0.0015

Proteinase-10 .03 0.03 0.03 0.03

Lipase 0.008 0.008 0.008 0.004

Amylase 0.003 0.003 0.003 0.006

Whitening agent 1 0.05--0.05

Trace and a small amount of component are prepared as follows granular detergent composition of the present invention to 100% embodiment 4 at most:

I II III IV V VI blows powder

LAS?????23.0??8.0????7.0?????9.0????7.0???7.0

TAS?????-?????-??????-???????-??????1.0???-

C45AS???6.0???6.0????5.0?????8.0????-?????-

C45AES??-?????1.0????1.0?????1.0????-?????-

C45E35??-?????-??????-???????-??????2.0???4.0

Zeolite A 10.0 18.0 14.0 10.25 10.0 10.0

MA/AA???-?????0.5????-???????-??????-?????2.0

MA/AA1??7.0???-??????-???????-??????-?????-

AA??????-?????3.0????3.0?????2.0????3.0???3.0

Vitriol 5.0 6.3 12.3 11.0 13.0 18.3

Silicate 10.0 1.0 1.0 1.0 1.0 1.0

Carbonate 14.5 19.0 10.0 20.7 8.0 6.0

PEG4000?0.4???1.5????1.5?????1.0????1.0???1.0

DTPA????-?????0.9????0.5?????-??????-?????0.5

Whitening agent 2 0.3 0.2 0.3-0.1 0.3 spraying liquid

C45E7???-?????2.0????-???????-??????2.0???2.0

C25E9????????????3.0?????-??????-??????-??????-??????-

C23E9????????????-???????-??????1.5????2.0????-??????2.0

Spices 0.3 0.3 0.3 2.0 0.3 0.3 agglomerates

C45AS????????????-???????5.0????5.0????2.0????-??????5.0

LAS??????????????-???????2.0????2.0????-??????-??????2.0

Zeolite A-7.5 7.5 8.0-7.5

Carbonate-4.0 4.0 5.0-4.0

PEG4000??????????-???????0.5????0.5????-??????-??????0.5

The dried additive of minor component (water etc.)-2.0 2.0 2.0-2.0

QAS??????????????-???????-??????-??????-??????1.0????-

Citric acid----2.0-

PB4??????????????-???????-??????-??????-??????12.0???1.0

PB1??????????????4.0?????1.0????3.0????2.0????-??????-

Percarbonate----2.0 10.0

Carbonate-5.3 1.8-4.0 4.0

NOBS?????????????4.0?????-??????6.0????-??????-??????0.6

Methylcellulose gum 0.2-----

Na-SKS-6?????????8.0?????-??????-??????-??????-??????-

STS??????????????-???????-??????2.0????-??????1.0????-

Cumene sulfonic acid-1.0---2.0

Mannase 0.001 0.02 0.001 0.015 0.02 0.02

Proteinase-10 .02 0.02 0.02 0.01 0.02 0.02

Lipase 0.004-0.004-0.004 0.008

Amylase 0.003-0.002-0.003-

Cellulase 0.0005 0.0005 0.0005 0.0007 0.0005 0.0005

PVPVI????????????-???????-??????-??????-??????0.5????0.1

PVP??????????????-???????-??????-??????-??????0.5????-

PVNO?????????????-???????-??????0.5????0.3????-??????-

PEI??????????????0.5?????1.0????2.0????1.75???2.0????1.0

QEA??????????????-???????-??????-??????-??????1.0????-

SRP1????????????0.2????0.5?????0.3?????-?????0.2????-

Polysiloxane defoamers 0.2 0.4 0.2 0.4 0.1-

Sal epsom--0.2-0.2-

Trace and a small amount of component are at most to 100 %

Embodiment 5

Be prepared as follows the detergent composition that does not contain SYNTHETIC OPTICAL WHITNER that is particularly useful for washing colored clothes of the present invention:

I II III blows powder

Zeolite A 14.5 14.0-

Vitriol-5.0-

LAS???????????????3.0?????????3.0?????????-

DETPMP????????????0.4?????????0.5?????????-

CMC???????????????0.4?????????0.4?????????-

MA/AA 4.0 4.0-agglomerate

C45AS?????????????-???????????-???????????11.0

LAS???????????????6.0?????????5.0?????????-

TAS???????????????3.0?????????2.0?????????-

PEI???????????????0.5?????????1.0?????????3.0

Silicate 4.0 4.0-

Zeolite A 10.0 15.0 13.0

CMC???????????????-???????????-???????????0.5

MA/AA?????????????-???????????-???????????2.0

Carbonate 9.0 7.0 7.0 spray liquid

Spices 0.3 0.3 0.5

C45E7?????????????4.0?????????4.0?????????4.0

C25E3 2.0 2.0 2.0 dried additives

MA/AA?????????????-???????????-???????????1.0

Na-SKS-6????????-????????-????????11.0

Citrate trianion 10.0-8.0

Supercarbonate 7.0 3.0 5.0

Carbonate 8.0 5.0 7.0

PVPVI/PVNO??????0.5??????0.5??????0.5

Mannase 0.001 0.02 0.015

Proteinase-10 .03 0.02 0.05

Lipase 0.008 0.008 0.008

Amylase 0.01 0.01 0.01

Cellulase 0.001 0.001 0.001

Polysiloxane defoamers 5.0 5.0 5.0

Vitriol-9.0-density (g/l) 700 700 700 minor components and a small amount of component are prepared as follows detergent composition of the present invention to 100% embodiment 6 at most:

I II III IV base-material particle

Zeolite A 29.5 21.0 22.0 10.0

Vitriol 10.0 5.0 10.0 7.0

MA/AA??????3.0?????-????????-?????????-

AA?????????-???????1.6??????2.0???????-

PEI????????0.5?????1.0??????2.0???????3.0

MA/AA1?????-???????12.0?????-?????????6.0

LAS????????14.0????10.0?????9.0???????18.0

C45AS??????8.0?????7.0??????9.0???????7.0

C45AES?????-???????1.0??????1.0???????-

Silicate-1.0 0.5 9.0

Soap-2.0--

Whitening agent 1 0.2 0.2 0.2 0.2

Carbonate 6.0 9.0 10.0 10.0

PEG4000?????????-??????1.0?????1.5?????-

DTPA-0.4--spray liquid

C25E9???????????-??????-???????-???????5.0

C45E7???????????1.0????1.0?????-???????-

C23E9???????????-??????1.0?????2.5?????-

Spices 0.2 0.3 0.3-dried additive

Carbonate 5.0 10.0 18.0 8.0

PVPVI/PVNO??????0.5????-???????0.3?????-

Mannase 0.001 0.02 0.001 0.0015

Proteinase-10 .03 0.03 0.03 0.02

Lipase 0.008--0.008

Amylase 0.002--0.002

Cellulase 0.0002 0.0005 0.0005 0.0002

NOBS????????????-??????4.0?????-???????4.5

PB1?????????????1.0????5.0?????1.5?????6.0

Vitriol 4.0 5.0-5.0

SRP1????????????-??????0.4?????-???????-

Suds suppressor-0.5 0.5-

Trace and a small amount of component are prepared as follows granular detergent composition of the present invention to 100% embodiment 7 at most:

I II III blows powder

Zeolite A 20.0-15.0

STPP???????-?????????20.0??????-

Vitriol--5.0

Carbonate--5.0

TAS????????-?????????-?????????1.0

LAS????????6.0???????6.0???????6.0

C68AS???????????2.0???????2.0???????-

Silicate 3.0 8.0-

MA/AA???????????4.0???????2.0???????2.0

CMC?????????????0.6???????0.6???????0.2

Whitening agent 1 0.2 0.2 0.1

DETPMP??????????0.4???????0.4???????0.1

STS--1.0 spraying liquid

C45E7???????????5.0???????5.0.??????4.0

Polysiloxane defoamers 0.3 0.3 0.1

Spices 0.2 0.2 0.3 dried additives

QEA?????????????-?????????-?????????1.0

Carbonate 14.0 9.0 10.0

PB1?????????????1.5???????2.0???????-

PB4?????????????18.5??????13.0??????13.0

TAED????????????2.0???????2.0???????2.0

QAS?????????????-?????????-?????????1.0

Photoactivation SYNTHETIC OPTICAL WHITNER 15ppm 15ppm 15ppm

Na-SKS-6????????-?????????-?????????3.0

Mannase 0.001 0.02 0.01

Proteinase-10 .03 0.03 0.007

Lipase 0.004 0.004 0.004

Amylase 0.006 0.006 0.003

Cellulase 0.0002 0.0002 0.0005

PEI?????????????1.0???????3.0???????0.5

Vitriol 9.0 17.0 4.5 density (g/l) 700 700 700 trace and a small amount of components are prepared as follows detergent composition of the present invention to 100% embodiment 8 at most:

I II III blows powder

Zeolite A 15.0 15.0 15.0

Vitriol-5.0-

LAS?????????3.0?????3.0????3.0

QAS?????????-???????1.5????1.5

DETPMP??????0.4?????0.2????0.4

EDDS????????-???????0.4????0.2

CMC?????????0.4?????0.4????0.4

MA/AA 4.0 2.0 2.0 agglomerates

LAS?????????5.0?????5.0????5.0

TAS?????????2.0?????2.0????1.0

Silicate 3.0 3.0 4.0

Zeolite A 8.0 8.0 8.0

Carbonate 8.0 8.0 4.0 spray liquid

Spices 0.3 0.3 0.3

C45E7???????2.0?????2.0????2.0

C25E3 2.0 dried additives

Citrate trianion 5.0-2.0

Supercarbonate-3.0-

Carbonate 8.0 14.0 8.0

PEI?????????0.5?????1.0????2.0

TAED????????6.0?????2.0????5.0

PB1?????????13.5????7.0????10.0

PEO?????????-???????-??????0.2

Wilkinite--10.0

Mannase 0.001 0.02 0.01

Proteinase-10 .03 0.03 0.03

Lipase 0.008 0.008 0.008

Cellulase 0.001 0.001 0.001

Amylase 0.01 0.01 0.01

Polysiloxane defoamers 5.0 5.0 5.0

Vitriol-3.0-density (g/l) 850 850 850 minor components and a small amount of component are at most to 100% embodiment, 9 preparations following detergent composition of the present invention:

I, II, III, IVLAS, 18.0, 14.0, 24.0, 20.0QAS, 0.7, 1.0,-, 0.7TFAA,-, 1.0,-,-C23E56.5,-, 1.0,-C45E7,-, 1.0,-,-C45E3S, 1.0, 2.5, 1.0,-STPP, 32.0, 18.0, 30.0, 22.0 silicate, 9.0, 5.0, 9.0, 8.0 Tan hydrochlorate, 11.0, 7.5, 10.0, 5.0 bicarbonate Yan,-, 7.5,-,-PB1, 3.0, 1.0,-,-PB4,-, 1.0,-,-NOBS, 2.0, 1.0,-,-DETPMP,-, 1.0,-,-DTPA, 0.5,-, 0.2, 0.3SRP1, 0.3, 0.2,-, 0.1MA/AA, 1.0, 1.5, 2.0, 0.5CMC, 0.8, 0.4, 0.4, 0.2PEI, 0.4, 0.4, 0.4, 0.4 sulfate, 20.0, 10.0, 20.0, 30.0 magnesium sulfate, 0.2,-, 0.4, 0.9 mannase, 0.001, 0.02, 0.001, 0.01 protease, 0.03, 0.03, 0.02, 0.02 amylase, 0.008, 0.007,-, 0.004 Zhi Mei, 0.004,-, 0.002,-cellulase, 0.0003,-,-, 0.0001 the white agent of photoactivation Piao, 30ppm, 20ppm,-, 10ppm Xiang material, 0.3, 0.3, 0.1, 0.2 the white agent 1/2 of Zeng, 0.05, 0.02, 0.08, 0.1 Wei amount and Shao amount Zu divide, Zui as many as 100%

Embodiment 10

Be prepared as follows liquid detergent preparation of the present invention (content provides with parts by weight, and enzyme is represented with pure enzyme):

Lipase--0.002--

Amylase---0.002-

Cellulase--0.0002 0.0005 0.0001

SRP1?????????????????0.2?????-???????????0.1????????-??????????-

DTPA?????????????????-???????-???????????0.3????????-??????????-

PE1??????????????????0.4?????0.4?????????0.4????????0.4????????0.4

PVNO?????????????????-???????-???????????0.3????????-??????????0.2

Whitening agent 1 0.2 0.07 0.1--

Polysiloxane defoamers 0.04 0.02 0.1 0.1 0.1

The as many as 100% of minor component and water

Embodiment 11

I??????II?????III??????IV

LAS????????????????????????10.0???13.0???9.0??????-

C25AS??????????????????????4.0????1.0????2.0??????10.0

C25E3S?????????????????????1.0????-??????-????????3.0

C25E7??????????????????????6.0????8.0????13.0?????2.5

TFAA???????????????????????-??????-??????-????????4.5

APA????????????????????????-??????1.4????-????????-

TPKFA??????????????????????2.0????-??????13.0?????7.0

Citric acid 2.0 3.0 1.0 1.5

Dodecenyl succinic/tetradecene base amber 12.0 10.0--

Acid

Vegetable seeds lipid acid 4.0 2.0 1.0-

Ethanol 4.0 4.0 7.0 2.0

1,2 propylene glycol 4.0 4.0 2.0 7.0

Monoethanolamine---5.0

Trolamine--8.0-

TEPAE??????????????????????0.5????-??????0.5??????0.2

DETPMP?????????????????????1.0????1.0????0.5??????1.0

Mannase 0.001 0.02 0.001 0.02

Proteinase-10 .02 0.02 0.01 0.008

Lipase-0.002-0.002

Amylase 0.004 0.004 0.01 0.008

Cellulase---0.002

SRP2??????????????????????0.3???????-????????0.3??????0.1

Boric acid 0.1 0.2 1.0 2.0

Calcium chloride-0.02-0.01

Whitening agent 1-0.4--

PEI???????????????????????0.4???????0.4??????0.2??????0.2

Suds suppressor 0.1 0.3-0.1

Opalizer 0.5 0.4-0.3

The as many as pH 8.0 8.0 7.6 7.7 of sodium hydroxide

The as many as 100% of minor component and water

Embodiment 12

Be prepared as follows liquid detergent composition of the present invention (content provides with parts by weight, and enzyme is represented with pure enzyme):

I????????II??????III???????IV

LAS????????????????25.0?????-???????-?????????-

C25AS???????????????????????13.0????18.0??????15.0

C25E3S?????????????-????????2.0?????2.0???????4.0

C25E7??????????????-????????-???????4.0???????4.0

TFAA???????????????-????????6.0?????8.0???????8.0

APA????????????????3.0??????1.0?????2.0???????-

TPKFA??????????????-????????15.0????11.0??????11.0

Citric acid 1.0 1.0 1.0 1.0

Laurylene base/tetradecene base 15.0---

Succsinic acid

Vegetable seed lipid acid 1.0-3.5-

Ethanol 7.0 2.0 3.0 2.0

1,2 propylene glycol 6.0 8.0 10.0 13.0

Monoethanolamine-9.0 9.0

TEPAE??????????????-????????-???????0.4???????0.3

DETPMP??????????????2.0??????1.2??????1.0??????-

Mannase 0.001 0.02 0.001 0.01

Proteinase-10 .08 0.02 0.01 0.02

Lipase--0.003 0.003

Amylase 0.004 0.01 0.01 0.01

Cellulase--0.004 0.003

PEI?????????????????0.2??????0.2??????0.4??????0.4

SRP2????????????????-????????-????????0.2??????0.1

Boric acid 1.0 1.5 2.5 2.5

Wilkinite 4.0 4.0--

Whitening agent 1 0.1 0.2 0.3-

Suds suppressor 0.4---

Opalizer 0.8 0.7--

The as many as pH 8.0 7.5 8.0 8.2 of sodium hydroxide

The as many as 100% of minor component and moisture

Embodiment 13

Prepare following liquid detergent composition of the present invention (content provides with parts by weight, and enzyme is represented with pure enzyme):

I?????????????II

LAS??????????????????????????27.6??????????18.9

C45AS????????????????????????13.8??????????5.9

C13E8????????????????????????3.0???????????3.1

Oleic acid 3.4 2.5

Citric acid 5.4 5.4

Sodium hydroxide 0.4 3.6

Calcium formiate 0.2 0.1

Sodium formiate-0.5

Ethanol 7.0-

Monoethanolamine 16.5 8.0

1,2 propylene glycol 5.9 5.5

Xylene monosulfonic acid-2.4

TEPAE????????????????????????1.5???????????0.8

Proteinase-10 .05 0.002

Mannase 0.001 0.002

PEI??????????????????????0.2???????????0.4

PEG??????????????????????-?????????????0.7

Whitening agent 2 0.4 0.1

Spices 0.5 0.3

The as many as 100% of water and minor component

Embodiment 14

Be prepared as follows particle fabric detergent composition of the present invention, described composition provides the effect of " it is softening to be in the suds ":

I????????II

C45AS????????????????????????????????-????????10.0

LAS??????????????????????????????????7.6??????-

C68AS????????????????????????????????1.3??????-

C45E7????????????????????????????????4.0??????-

C25E3????????????????????????????????-????????5.0

Chlorination coconut alkyl-dimethyl-hydroxyethyl ammonium 1.4 1.0

Citrate trianion 5.0 3.0

NaSKS-6??????????????????????????????-????????11.0

Zeolite A 15.0 15.0

MA/AA????????????????????????????????4.0??????4.0

DETPMP???????????????????????????????0.4??????0.4

PB1??????????????????????????????????15.0?????-

Percarbonate-15.0

TAED?????????????????????????????????5.0??????5.0

Terre verte 10.0 10.0

HMWPEO???????????????????????????????-????????0.1

Mannase 0.001 0.02

Proteinase-10 .02 0.01

Lipase 0.02 0.01

Amylase 0.03 0.005

Cellulase 0.001-

Silicate 3.0 5.0

PEI??????????????????????0.2????????0.4

Carbonate 10.0 10.0

Suds suppressor 1.0 4.0

CMC??????????????????????0.2????????0.1

Trace and a small amount of component are at most to 100%

Embodiment 15

Prepare following laundry detergent bar composition of the present invention (content provides with parts by weight, and enzyme is represented with pure enzyme):

I, II, II1, IV, V, VI, VII, VIIILAS,-,-, 19.0, 15.0, 21.0, 6.75, 8.8,-C28AS, 30.0, 13.5-,-,-, 15.75, 11.2, 22.5 sodium laurate, 2.5, 9.0,-,-,-,-,-,-zeolite A, 2.0, 1.25-,-,-, 1.25, 1.25, 1.25 Tan hydrochlorate, 20.0, 3.0, 13.0, 8.0, 10.0, 15.0, 15.0, 10.0 Tan Suan calcium, 27.5, 39.0, 35.0,-,-, 40.0-, 40.0 sulfate, 5.0, 5.0, 3.0, 5.0, 3.0,-,-, 5.0TSPP, 5.0,-,-,-,-, 5.0, 2.5,-STPP, 5.0, 15.0, 10.0,-,-, 7.0, 8.0, 10.0 swelling Tu,-, 10.0-,-, 5.0,-,-,-DETPMP,-, 0.7, 0.6,-, 0.6, 0.7, 0.7, 0.7CMC,-, 1.0, 1.0, 1.0, 1.0,-,-, 1.0 talcum,-,-, 10.0, 15.0, 10.0-,-,-silicate,-,-, 4.0, 5.0, 3.0,-,-,-PVNO, 0.02, 0.03-, 0.01,-, 0.02-,-MA/AA, 0.4, 1.0,-,-, 0.2, 0.4, 0.5, 0.4SRP1, 0.3, 0.3, 0.3, 0.3, 0.3, 0.3, 0.3, 0.3 mannase, 0.0001, 0.01, 0.001, 0.01, 0.01, 0.001, 0.01, 0.001 amylase,-,-, 0.01,-,-,-, 0.002-protease,-, 0.004-, 0.003, 0.003-,-, 0.003 Zhi Mei,-, 0.002-, 0.002-,-,-,-cellulase,-, .0003-,-, .0003, .0002-,-PEI, 0.2, 0.2, 0.2, 0.2, 0.3, 0.2, 0.2, 0.3 Xiang material, 1.0, 0.5, 0.3, 0.2, 0.4,-,-, 0.4 magnesium sulfate,-,-, 3.0, 3.0, 3.0,-,-, the white agent of-Zeng, 0.15, 0.1, 0.15-,-,-,-, 0.1 the white agent of photoactivation Piao-, 15.0, 15.0, 15.0, 15.0-,-, 15.0, (ppm) Shi Shi example 16 Zhi standby Ru Xia Xi of the present invention wash agent Tian and add agent Zu compound:

I II IIILAS-5.0 5.0PEI 0.5 1.0 3.0STPP 29.5-17.0 zeolite A-34.0 20.0PB1 20.0 15.0-TAED, 10.0 8.0-mannase, 0.001 0.02 0.001 protease-0.3 0.3 amylase-0.06 0.06 Shao amount Zu divide, Shui and the Zui as many as 100% of microcomponent

Sequence Table (A) General information: Applicant: Title: The Procter & Gamble Company Street: One Procter & Gamble Plaza City: Cincinnati, OHIO Country: USA Postal Code: 45202 Invention: mannanase containing soil release polymers and detergent compositions SEQ ID NO: 6 Computer readable form: Media Type: Floppy Disk Computer: IBM PC compatible Operating System: PC-DOS/MS-DOS Software: Patentln Release # 1.0 Version 1.25 (EPO) SEQ ID NO: 1 SEQUENCE CHARACTERISTICS: Length: 1407 base pairs TYPE: nucleic acid Chain Type: Single Topology: straight chain MOLECULE TYPE: genomic DNA Original Source Features: NAME / KEY: CDS Location :1-1482 SEQUENCE DESCRIPTION: SEQ ID NO: 1 ATGAAAAAAAAGTTATCACAGATTTATCATTTAATTATTTGCACACTTATAATA AGTGTGGGAATAATGGGGATTACAACGTCCCCATCAGCAGCAAGTACAGGC TTTTATGTTGATGGCAATACGTTATATGACGCAAATGGGCAGCCATTTGTCAT GAGAGGTATTAACCATGGACATGCTTGGTATAAAGACACCGCTTCAACAGCT ATTCCTGCCATTGCAGAGCAAGGCGCCAACACGATTCGTATTGTTTTATCAG ATGGCGGTCAATGGGAAAAAGACGACATTGACACCATTCGTGAAGTCATTG AGCTTGCGGAGCAAAATAAAATGGTGGCTGTCGTTGAAGTTCATGATGCCA CGGGTCGCGATTCGCGCAGTGATTTAAATCGAGCCGTTGATTATTGGATAG AAATGAAAGATGCGCTTATCGGTAAAGAAGATACGGTTATTATTAACATTGCA AACGAGTGGTATGGGAGTTGGGATGGCTCAGCTTGGGCCGATGGCTATATT GATGTCATTCCGAAGCTTCGCGATGCCGGCTTAACACACACCTTAATGGTTG ATGCAGCAGGATGGGGGCAATATCCGCAATCTATTCATGATTACGGACAAG ATGTGTTTAATGCAGATCCGTTAAAAAATACGATGTTCTCCATCCATATGTAT GAGTATGCTGGTGGTGATGCTAACACTGTTAGATCAAATATTGATAGAGTCA TAGATCAAGACCTTGCTCTCGTAATAGGTGAATTCGGTCATAGACATACTGA TGGTGATGTTGATGAAGATACAATCCTTAGTTATTCTGAAGAAACTGGCACA GGGTGGCTCGCTTGGTCTTGGAAAGGCAACAGTACCGAATGGGACTATTTA GACCTTTCAGAAGACTGGGCTGGTCAACATTTAACTGATTGGGGGAATAGAA TTGTCCACGGGGCCGATGGCTTACAGGAAACCTCCAAACCATCCACCGTAT TTACAGATGATAACGGTGGTCACCCTGAACCGCCAACTGCTACTACCTTGTA TGACTTTGAAGGAAGCACACAAGGGTGGCATGGAAGCAACGTGACCGGTG GCCCTTGGTCCGTAACAGAATGGGGTGCTTCAGGTAACTACTCTTTAAAAGC CGATGTAAATTTAACCTCAAATTCTTCACATGAACTGTATAGTGAACAAAGTC GTAATCTACACGGATACTCTCAGCTCAACGCAACCGTTCGCCATGCCAATTG GGGAAATCCCGGTAATGGCATGAATGCAAGACTTTACGTGAAAACGGGCTC TGATTATACATGGCATAGCGGTCCTTTTACACGTATCAATAGCTCCAACTCA GGAACAACGTTATCTTTTGATTTAAACAACATCGAAAATAGTCATCATGTTAG GGAAATAGGCGTGCAATTTTCAGCGGCAGATAATAGCAGTGGTCAAACTGC TCTATACGTTGATAACGTTACTTTAAGATAG SEQ ID NO: 2 SEQUENCE CHARACTERISTICS: Length: 493 amino acids TYPE: amino acid Topology: straight chain MOLECULE TYPE: protein SEQUENCE DESCRIPTION: SEQ ID NO: 2 MKKKLSQIYHLIICTLIISVGIMGITTSPSAASTGFYVDGNTLYDANGQPFVMRGIN HGHAWYKDTASTAIPAIAEQGANTIRIVLSDGGQWEKDDIDTIREVIELAEQNKM VAWEVHDATGRDSRSDLNRAVDYWIEMKDALIGKEDTVIINIANEWYGSWDGS AWADGYIDVIPKLRDAGLTHTLMVDAAGWGQYPQSIHDYGQDVFNADPLKNTM FSIHMYEYAGGDANTVRSNIDRVIDQDLALVIGEFGHRHTDGDVDEDTILSYSEE TGTGWLAWSWKGNSTEWDYLDLSEDWAGQHLTDWGNRIVHGADGLQETSKP STVFTDDNGGHPEPPTATTLYDFEGSTQGWHGSNVTGGPWSVTEWGASGNY SLKADVNLTSNSSHELYSEQSRNLHGYSQLNATVRHANWGNPGNGMNARLYV KTGSDYTWHSGPFTRINSSNSGTTLSFDLNNIENSHHVREIGVQFSAADNSSGQ TALYVDNVTLR SEQ ID NO: 3 SEQUENCE CHARACTERISTICS: Length: 1407 base pairs TYPE: nucleic acid Chain Type: Single Topology: straight chain MOLECULE TYPE: genomic DNA SEQUENCE DESCRIPTION: SEQ ID NO: 3 ATGAAAAAAAAGTTATCACAGATTTATCATTTAATTATTTGCACACTTATAATA AGTGTGGGAATAATGGGGATTACAACGTCCCCATCAGCAGCAAGTACAGGC TTTTATGTTGATGGCAATACGTTATATGACGCAAATGGGCAGCCATTTGTCAT GAGAGGTATTAACCATGGACATGCTTGGTATAAAGACACCGCTTCAACAGCT ATTCCTGCCATTGCAGAGCAAGGCGCCAACACGATTCGTATTGTTTTATCAG ATGGCGGTCAATGGGAAAAAGACGACATTGACACCATTCGTGAAGTCATTG AGCTTGCGGAGCAAAATAAAATGGTGGCTGTCGTTGAAGTTCATGATGCCA CGGGTCGCGATTCGCGCAGTGATTTAAATCGAGCCGTTGATTATTGGATAG AAATGAAAGATGCGCTTATCGGTAAAGAAGATACGGTTATTATTAACATTGCA AACGAGTGGTATGGGAGTTGGGATGGCTCAGCTTGGGCCGATGGCTATATT GATGTCATTCCGAAGCTTCGCGATGCCGGCTTAACACACACCTTAATGGTTG ATGCAGCAGGATGGGGGCAATATCCGCAATCTATTCATGATTACGGACAAG ATGTGTTTAATGCAGATCCGTTAAAAAATACGATGTTCTCCATCCATATGTAT GAGTATGCTGGTGGTGATGCTAACACTGTTAGATCAAATATTGATAGAGTCA TAGATCAAGACCTTGCTCTCGTAATAGGTGAATTCGGTCATAGACATACTGA TGGTGATGTTGATGAAGATACAATCCTTAGTTATTCTGAAGAAACTGGCACA GGGTGGCTCGCTTGGTCTTGGAAAGGCAACAGTACCGAATGGGACTATTTA GACCTTTCAGAAGACTGGGCTGGTCAACATTTAACTGATTGGGGGAATAGAA TTGTCCACGGGGCCGATGGCTTACAGGAAACCTCCAAACCATCCACCGTAT TTACAGATGATAACGGTGGTCACCCTGAACCGCCAACTGCTACTACCTTGTA TGACTTTGAAGGAAGCACACAAGGGTGGCATGGAAGCAACGTGACCGGTG GCCCTTGGTCCGTAACAGAATGGGGTGCTTCAGGTAACTACTCTTTAAAAGC CGATGTAAATTTAACCTCAAATTCTTCACATGAACTGTATAGTGAACAAAGTC GTAATCTACACGGATACTCTCAGCTCAACGCAACCGTTCGCCATGCCAATTG GGGAAATCCCGGTAATGGCATGAATGCAAGACTTTACGTGAAAACGGGCTC TGATTATACATGGCATAGCGGTCCTTTTACACGTATCAATAGCTCCAACTCA GGAACAACGTTATCTTTTGATTTAAACAACATCGAAAATATCATCATGTTAGG GAAATAG SEQ ID NO: 4 SEQUENCE CHARACTERISTICS: Length: 468 amino acids TYPE: amino acid Topology: straight chain MOLECULE TYPE: protein SEQUENCE DESCRIPTION: SEQ ID NO: 4 MKKKLSQIYHLIICTLIISVGIMGITTSPSAASTGFYVDGNTLYDANGQPFVMRGIN HGHAWYKDTASTAIPAIAEQGANTIRIVLSDGGQWEKDDIDTIREVIELAEQNKM VAWEVHDATGRDSRSDLNRAVDYWIEMKDALIGKEDTVIINIANEWYGSWDGS AWADGYIDVIPKLRDAGLTHTLMVDAAGWGQYPQSIHDYGQDVFNADPLKNTM FSIHMYEYAGGDANTVRSNIDRVIDQDLALVIGEFGHRHTDGDVDEDTILSYSEE TGTGWLAWSWKGNSTEWDYLDLSEDWAGQHLTDWGNRIVHGADGLQETSKP STVFTDDNGGHPEPPTATTLYDFEGSTQGWHGSNVTGGPWSVTEWGASGNY SLKADVNLTSNSSHELYSEQSRNLHGYSQLNATVRHANWGNPGNGMNARLYV KTGSDYTWHSGPFTRINSSNSGTTLSFDLNNIENIIMLGK SEQ ID NO: 5 SEQUENCE CHARACTERISTICS: Length: 1029 base pairs TYPE: nucleic acid Chain Type: Single Topology: straight chain MOLECULE TYPE: genomic DNA SEQUENCE DESCRIPTION: SEQ ID NO: 5 5'AAT TGG CGC ATA CTG TGT CGC CTG TGA ATC CTA ATG CCC AGC AGA CAA CAA AAA CAG TGA TGA ACT GGC TTG CGC ACC TGC CGA ACC GAA CGG AAA ACA GAG TCC TTT CCG GAG CGT TCG GAG GTT ACA GCC ATG ACA CAT TTT CTA TGG CTG AGG CTG ATA GAA TCC GAA GCG CCA CCG GGC AAT CGC CTG CTA TTT ATG GCT GCG ATT ATG CCA GAG GAT GGC TTG AAA CAG CAA ATA TTG AAG ATT CAA TAG ATG TAA GCT GCA ACG GCG ATT TAA TGT CGT ATT GGA AAA ATG GCG GAA TTC CGC AAA TCA GTT TGC ACC TGG CGA ACC CTG CTT TTC AGT CAG GGC ATT TTA AAA CAC CGA TTA CAA ATG ATC AGT ATA AAA ACA TAT TAG ATT CAG CAA CAG CGG AAG GGA AGC GGC TAA ATG CCA TGC TCA GCA AAA TTG CTG ACG GAC TTC AAG AGT TGG AGA ACC AAG GTG TGC CTG TTC TGT TCA GGC CGC TGC ATG AAA TGA ACG GCG AAT GGT TTT GGT GGG GAC TCA CAT CAT ATA ACC AAA AGG ATA ATG AAA GAA TCT CTC TAT ATA AAC AGC TCT ACA AGA AAA TCT ATC ATT ATA TGA CCG ACA CAA GAG GAC TTG ATC ATT TGA TTT GGG TTT ACT CTC CCG ACG CCA ACC GAG ATT TTA AAA CTG ATT TTT ACC CGG GCG CGT CTT ACG TGG ATA TTG TCG GAT TAG ATG CGT ATT TTC AAG ATG CCT ACT CGA TCA ATG GAT ACG ATC AGC TAA CAG CGC TTA ATA AAC CAT TTG CTT TTA CAG AAG TCG GCC CGC AAA CAG CAA ACG GCA GCT TCG ATT ACA GCC TGT TCA TCA ATG CAA TAA AAC AAA AAT ATC CTA AAA CCA TTT ACT TTC TGG CAT GGA ATG ATG AAT GGA GCG CAG CAG TAA ACA AGG GTG CTT CAG CTT TAT ATC ATG ACA GCT GGA CAC TCA ACA AGG GAG AAA TAT GGA ATG GTG ATT CTT TAA CGC CAA TCG TTG AGT GAA TCC GGG ATC 3 ' SEQ ID NO: 6 SEQUENCE CHARACTERISTICS: Length: 363 amino acids TYPE: amino acid Topology: straight chain MOLECULE TYPE: protein SEQUENCE DESCRIPTION: SEQ ID NO: 6 ydhT 1 LFKKHTISLLIIFLLASAVLAKPIEAHTVSPVNPNAQQTTKTVMNVVLAHL 50 ydhT 51 PNRTENRVLSGAFGGYSHDTFSMAEADRIRSATGQSPAIYGCDYARGWLE 100 ydhT 101 TANIEDSIDVSCNGDLMSYWKNGGIPQISLHLANPAFQSGHFKTPITNDQ 150 ydhT 151 YKNILDSATAEGKRLNAMLSKIADGLQELENQGVPVLFRPLHEMNGEWFW 200 ydhT 201 WGLTSYNQKDNERISLYKQLYKKIYHYMTDTRGLDHLIWVYSPDANRDFK 250 ydhT 251 TDFYPGASYVDIVGLDAYFQDAYSINGYDQLTALNKPFAFTEVGPQTANG 300 ydhT 301 SFDYSLFINAIKQKYPKTIYFLAWNDEWSAAVNKGASALYHDSWTLNKGE 350 ydhT 351 IWNGDSLTPIVE *. 363 ...

Claims

1. laundry detergent composition, it contains mannase and cotton goods polymine soil release polymer.

2. according to the laundry detergent composition of claim 1, wherein said mannase to be being 0.0001%-2% by the pure enzyme amount of general composition weight meter, preferred 0.0005%-0.5%, and more preferably the content of 0.001%-0.1% exists.

3. according to the laundry detergent composition of claim 1-2, wherein cotton goods polymine soil release polymer is with 0.0001%-20%, preferred 0.001%-15%, and more preferably the content of 0.01%-10% exists.

4. according to the laundry detergent composition of claim 1-3, wherein cotton goods polymine soil release polymer is the polyamine formula V with modification _(n+1)W _mY _nThe material of the following general formula of Z: Or has a polyamine formula V of modification _(n-k+1)W _mY _nY ' _kThe polyamine backbone of Z corresponding to following formula:

I) the V unit is the terminal units with following formula: Or Or

Ii) the W unit is the skeleton unit with following formula:

Or

Or

Iii) the Y unit is the chain unit with following formula:

Or

Or With

Iv) the Z unit is the terminal units with following formula:

Or

Or

The R unit that wherein connects skeleton is selected from C ₂-C ₁₂Alkylidene group, C ₄-C ₁₂Alkenylene, C ₃-C ₁₂Hydroxy alkylidene, C ₄-C ₁₂Alkyl sub-dihydroxy, C ₈-C ₁₂The dialkyl group arylidene ,-(R ¹O) _xR ¹,-(R ¹O) _xR ⁵(OR ¹) _x-,-(CH ₂CH (OR ²) CH ₂O) _z-(R ¹O) _yR ¹(OCH ₂CH (OR ²) CH ₂) _w-,-C (O) (R ⁴) _rC (O)-,-CH ₂CH (OR ²) CH ₂-and their mixture; R wherein ¹Be C ₂-C ₆Alkylidene group and their mixture; R ₂Be hydrogen ,-(R ¹O) _xB and their mixture; R ³Be C ₁-C ₁₈Alkyl, C ₇-C ₁₂Arylalkyl, C ₇-C ₁₂Aryl, C that alkyl replaces ₆-C ₁₂Aryl and their mixture; R ⁴Be C ₁-C ₁₂Alkylidene group, C ₄-C ₁₂Alkenylene, C ₈-C ₁₂Aryl alkylene, C ₆-C ₁₀Arylidene and their mixture; R ⁵Be C ₁-C ₁₂Alkylidene group, C ₃-C ₁₂Hydroxy alkylidene, C ₄-C ₁₂Alkyl sub-dihydroxy, C ₈-C ₁₂The dialkyl group arylidene ,-C (O)-,-C (O) NHR ⁶NHC (O)-,-R ¹(OR ¹)-,-C (O) (R ⁴) _rC (O)-,-CH ₂CH (OH) CH ₂-,-CH ₂CH (OH) CH ₂O (R ¹O) _yR ¹-OCH ₂CH (OH) CH ₂-and their mixture; R ⁶Be C ₂-C ₁₂Alkylidene group or C ₆-C ₁₂Arylidene; The E unit is selected from hydrogen, C ₁-C ₂₂Alkyl, C ₃-C ₂₂Thiazolinyl, C ₇-C ₂₂Arylalkyl, C ₂-C ₂₂Hydroxyalkyl ,-(CH ₂) _pCO ₂M-,-(CH ₂) _qSO ₃M ,-CH (CH ₂CO ₂M) CO ₂M ,-(CH ₂) _pPO ₃M ,-(R ¹O) _xB ,-C (O) R ³With their mixture; Its prerequisite is when any E unit of nitrogen is hydrogen, and described nitrogen neither the N-oxide compound; B is hydrogen, C ₁-C ₆Alkyl ,-(CH ₂) _qSO ₃M ,-(CH ₂) _pCO ₂M ,-(CH ₂) _q(CHSO ₃M) CH ₂SO ₃M ,-(CH ₂) _q(CHSO ₂M)-CH ₂SO ₃M ,-(CH ₂) _pPO ₃M ,-PO ₃M and their mixture; M is hydrogen or the water-soluble cationic that presents in an amount at least sufficient to satisfy charge balance; X is a water soluble anion;

K and k ' are 1-15; M is 4-400; N is 0-200; P is 1-6, and q is 0-6; R is 0 or 1; W is 0 or 1; X is 1-100; Y is 0-100; Z is 0 or 1.

5. according to the laundry detergent composition of above-mentioned arbitrary claim, wherein cotton goods polymine soil release polymer is selected from polymine 1800E7 and its amine oxide derivative, polymine 1200E7 and its oxidation and/or quaternary ammonium derivative, polymine 600E20, and/or their mixture.

6. according to the laundry detergent composition of above-mentioned arbitrary claim, it also contains tensio-active agent, preferred nonionic surfactants.

7. according to the laundry detergent composition of claim 6, wherein nonionogenic tenside is to have the C8-C20 chain length, and preferred C12-C16 and ethoxylation degree are 2-9, the alkyl ethoxylated nonionogenic tenside of preferred 3-7.

8. according to the laundry detergent composition of claim 6, wherein nonionogenic tenside is that alkyl chain length is C8-C20, the alkyl methyl glucamide of preferred C12-C18.

9. according to the laundry detergent composition of above-mentioned arbitrary claim, it also contains washing assistant, is preferably selected from the washing assistant of zeolite, tripoly phosphate sodium STPP, layered silicate and/or their mixture.

10. according to the laundry detergent composition of above-mentioned arbitrary claim, it also contains conventional soil release polymer, the end capped polyester of preferred anionic, diethoxy polytrimethylene-terephthalate and/or their mixture.

11. method with the laundry detergent composition laundering of textile fabrics of above-mentioned arbitrary claim.