CN101473024A - Detergent compositions - Google Patents

Abstract

Detergent compositions containing an alkaline bacterial enzyme exhibiting endo-beta-1,4-glucanase activity (E.C. 3.2.1.4) and specific detergent formulations comprising less than 10 wt% zeolite and phosphate builder are described. Preferred formulations comprise surfactants selected from alkyl benzene sulphonates in combination with alkyl ethoxylated sulfates or MES or non-ionic surfactants.

Description

Detergent composition

Invention field

This invention relates to the cleaning compositions that comprises derivatived cellulose.The invention still further relates to the detergent composition that comprises cellulase, described cellulase is such as showing interior-β-1, the bacterium alkalescence enzyme of 4-dextranase activity (E.C.3.2.1.4).The invention still further relates to the method for preparing and use this series products.

Background of invention

Cellulase is because their known defeatherings, softening and color care benefit effect and be used to up to now in the detergent composition for many years.Yet the use of most of cellulases is restricted always, and this is because cellulase may the tensile strength to fabric fibre have adverse influence via the hydrolysis crystalline cellulose.In recent years, developed amorphous cellulose has been had the cleaning potential that highly narrow spectrum cellulase utilizes cellulase, avoided disadvantageous tensile strength to reduce simultaneously.Especially developed alkaline endo-dextranase, more to be applicable in the alkalis situation.

For example, Novozymes in WO02/099091, disclose a kind of show by bacterial strain genus bacillus (DSM 12648) endogenous in-novel enzyme of 1,4 beta-glucanase activity (EC 3.2.1.4) uses to be used for washing composition and yarn fabric.Novozymes has also described detergent composition in WO04/053039, described detergent composition comprise anti-reppd endo-dextranase and with the combination of some cellulase, described cellulase is improved the stability of anion surfactant and/or other concrete enzyme.The EP 265 832 of Kao has described by separate novel alkaline cellulase K, CMCase I and the CMCase II that obtains from genus bacillus KSM-635 cultured products.Kao has also described alkali cellulose enzyme in EP 1 350 843, described cellulase can advantageously act in the alkaline environment, and is easy to mass production owing to having secretion performance highly or having the enhanced given activity.

Confirm that anion-modified derivatived cellulose such as carboxymethyl cellulose (CMC) is the anti-redeposition polymkeric substance in the detergent composition.The combination of Mierocrystalline cellulose and CMC for example has been disclosed among the GB-A-2095275.The inventor finds that specific alkaline bacteria cellulose and the cellulosic combination of particular modification can cause textile anti-staining significantly to improve.Not bound by theory, it is believed that through a plurality of cycles of washing, the modified-cellulose derivative is deposited on the cotton goods, and by alkaline bacteria cellulose effect, washed hole in the surface fiber of the fabric with sealing.This can obtain fabric face unlikely and particulate fouling formation mortise.Therefore, improve the appearance of fabrics of washing, and also improved cleaning effect.

Summary of the invention

The present invention relates to comprise the composition of modified-cellulose derivative and cellulase, described composition is characterised in that cellulase is to show interior-β-1, the bacterium of 4-dextranase activity (E.C.3.2.1.4) alkalescence enzyme, and modified-cellulose component and the proteinic weight ratio of active cellulase are 1:1 to 10000:1.Composition of the present invention does not comprise the acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems of 0.7% weight to 0.9% weight usually.Composition of the present invention does not comprise the Sodium peroxoborate monohydrate of 10% weight usually.Composition of the present invention comprises by weight usually less than 8% and/or by weight greater than 8.5% sodium sulfate (anhydrous).More particularly, composition of the present invention does not comprise the sodium sulfate of 8.0% weight to 8.3% weight.

The present invention also comprises the composition that comprises modified-cellulose derivative or their mixture and cellulase, described composition is characterised in that modified-cellulose derivative and the proteinic weight ratio of active cellulase are 1:1 to 10000:1, and wherein said composition does not comprise the acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems by the weight 0.7% to 0.9% of described total composition, and does not comprise the Sodium peroxoborate monohydrate by the weight 10% of described total composition.In Ding Yi " the enzyme test ", described enzyme produces the reduction end amount greater than 5mM hereinafter.

The enzyme test

The contriver finds that the short oligose product that forms during the polymkeric substance hydrolysis can promote the effectiveness of interior-β-(1,4)-dextranase/modified-cellulose derivative combination.The inventor finds, measure by using the reduction end according to the 32nd to 40 page of modification of 2002 the 63rd volumes of people such as J.Karlsson " Biopolymers " as described below, the most effective combination relates to uses modified-cellulose derivative and interior-β-(1 as described herein, 4)-dextranase, in described-β-(1,4)-dextranase effectively is hydrolyzed into little oligose with the CMC polymkeric substance.

In the 50mM of pH5.0 sodium-acetate, 10g/L CMC (weight-average molecular weight 250kDa, DS 0.7, by Aldrich, Stenheim, Germany supply) is hydrolyzed with 72 hours lasting hydrolysis times with excessive enzyme 2 β M.Then hydrolysate is cooled to+4 ℃, the scheme of in the 153rd to 157 page of " Enzyme Microb.Technol. " 1981 the 3rd volume, describing according to people such as M.Bailey subsequently, use glucose to make typical curve, use edlefsen's reagent to implement reduction end and measure.

In this test, interior-β required for the present invention-(1,4)-dextranase produces the reduction end amount greater than 5mM, and this is corresponding to～10% reduction end.Employing enzyme test, preferred enzyme produces greater than 10%, is preferably greater than 12%, or even greater than 15% reduction end amount.

Sequence list

Sequence identification number: 1 has shown the aminoacid sequence derived from the endo-dextranase of genus bacillus AA349.

Sequence identification number: 2 have shown the aminoacid sequence derived from the endo-dextranase of genus bacillus KSM-S237.

Detailed Description Of The Invention

Definition

As used herein, except as otherwise noted, term " cleaning compositions " comprises granule type or powder-type is multi-functional or " heavy duty type " washing composition, especially laundry detergent; Liquid, gel or paste type multifunctional detergent, especially so-called heavy-filth liquid type; Liquid high-count fabric washing composition; And the cleaning assistant agent, such as bleaching additive and " decontamination rod " or pre-treatment type.

As used herein, term " modified-cellulose derivative " comprises the polymkeric substance that comprises cellulosic backbone, and wherein said Mierocrystalline cellulose is replaced by at least one substituting group or modification group.The Mierocrystalline cellulose monomer is as follows.

R1, R2 and R3 have shown can be for the position that replaces in the Mierocrystalline cellulose monomer.In the natural cellulose polymkeric substance, these groups comprise hydrogen atom.According to the present invention, required modified-cellulose derivative comprises substituting group in one or more these positions of described polymkeric substance.Usually, the modification group is nonionic or anionic group, makes nonionic or anion-modified Mierocrystalline cellulose respectively.Alternatively, can pass through other β-1, polygalactomannan (as xanthan gum), chitosan or the chitosan salts of polysaccharide such as Portugal's polyxylose (as derived from tamarind seed gum) that 4-connects, glucomannan (as konjak glucomannan), polygalactomannan (as derived from guar gum or Viscogum BE), side chain branching provide the modified-cellulose derivative.Also can have starch, α-1,4-connects the derivative of polysaccharide.No matter be that β-1,4 still is α-1,4 natural polysaccharide, all can be by amine (primary amine, secondary amine, tertiary amine), acid amides, ester, ether, urethane, alcohol, carboxylic acid, tosylate, sulfonate radical, sulfate radical, nitrate radical, phosphate radical and their mixture modification.The example of suitable derivative is shown among the WO 06/117071 (Unilever), such as carboxymethyl Viscogum BE and Viscogum BE esilate.

The derivatived cellulose of preferred anionic modification is such as carboxymethyl cellulose.

Composition

Composition of the present invention can comprise the weight 0.00002% to 0.15%, 0.00005% to 0.12% by pure enzyme usually, or even 0.0002% to 0.02%, or even one or more endo-dextranases of 0.005% to 0.025%.The surplus of any aspect of above-mentioned cleaning compositions is made up of derivatived cellulose and one or more promoter materials.

Suitable endo-dextranase

The endo-dextranase of waiting to be incorporated in the detergent composition of the present invention is to show interior-β-1, one or more bacteriums alkalescence enzymes of 4-dextranase activity (E.C.3.2.1.4).

As used herein, term " alkaline endo-dextranase " should refer to have and be higher than 7 optimum pH and can keep the endo-dextranase of its optimum activity more than 70% under pH10.

Preferably, described endo-dextranase is by shaft-like Pseudomonas member endogenous bacterial peptide.

More preferably, in showing-β-1, the described alkaline enzyme of 4-dextranase activity (E.C.3.2.1.4) is a polypeptide, comprises (i) at least a the 17th family's carbohydrate integrated structure module (the 17th CBM of family) and/or (ii) at least a the 28th family's carbohydrate integrated structure module (the 28th CBM of family).Definition and classification for CBM for example see also: exercise question is in (593 to 600 pages of calendar year 2001s) at " Current Opinion in Structural Biology " for Y.Bourne and B.Henrissat: their article of " Glycoside hydrolases andglycosyltransferases:families and functional modules ".In addition, characteristic for the 17th and the 28th CBM of family, seeing also people such as A.B.Boraston exercise question in " Biochemical Journal " (2002, the 35th to 40 page of the 361st volume) is: their article of " Identification and glucan-binding properties of a newcarbohydrate-binding module family ".

In a more preferred embodiment, described enzyme comprises by following a kind of rod bacterium bacterial classification endogenous polypeptide (or its varient):

Genus bacillus	Described in following document:
		AA349(DSM 12648)	WO 2002/099091A (Novozymes), page 2, the 25th row WO 2004/053039A (Novozymes), page 3, the 19th row
KSM S237	EP 1350843A (Kao), page 3, the 18th row
		1139	EP 1350843A (Kao), page 3, the 22nd row
KSM 64	EP 1350843A (Kao), page 3, the 24th row
		KSM N131	EP 1350843A (Kao), page 3, the 25th row
KSM 635，FERM BP 1485	EP 265832A (Kao), the 7th page, the 45th row
		KSM 534，FERM BP 1508	EP 0271044 A (Kao), the 9th page, the 21st row
KSM 539，FERM BP 1509	EP 0271044 A (Kao), the 9th page, the 22nd row
		KSM 577，FERM BP 1510	EP 0271044 A (Kao), the 9th page, the 22nd row
KSM 521，FERM BP 1507	EP 0271044 A (Kao), the 9th page, the 19th row
		KSM 580，FERM BP 1511	EP 0271044 A (Kao), the 9th page, the 20th row
KSM 588，FERM BP 1513	EP 0271044 A (Kao), the 9th page, the 23rd row
		KSM 597，FERM BP 1514	EP 0271044 A (Kao), the 9th page, the 24th row
KSM 522，FERM BP 1512	EP 0271044 A (Kao), the 9th page, the 20th row
		KSM 3445，FERM BP 1506	EP 0271044 A (Kao), the 10th page, the 3rd row
KSM 425，FERM BP 1505	EP 0271044 A (Kao), the 10th page, the 3rd row

Be applicable to that the endo-dextranase in the present composition is:

1) shows interior-β-1, the enzyme of 4-dextranase activity (E.C.3.2.1.4).When the GAP that expands point penalty and provide in by the GCG program as GAP that the GAP that adopts 3.0 produces point penalty and 0.1 determined identity, described enzyme had and sequence identification number: 1 (corresponding to the sequence identification number among the WO02/099091: 2) 1 to 773 amino acids sequences at least 90%, preferred 94%, more preferably 97% and even the more preferably sequence of 99%, 100% identity; In perhaps it has-and β-1, the fragment of 4-dextranase activity.The described enzyme and the method that generates accordingly are general to be set forth in by Novozymes A/S in the patent application WO02/099091 that announced on December 12nd, 2002.See also the 20th page to 26 pages of detailed Description Of The Invention page 4 to 17 page and embodiment.A kind of this fermentoid can trade(brand)name Celluclean ^TMCommercially available from Novozymes A/S.

(San Diego, CA, the sequence analysis software bag that USA) provides by Accelrys are provided GCG.This has incorporated the program that is called GAP into, its adopt Needleman and Wunsch algorithm to find to mate number maximum and room to count two complete sequence of minimum right.

2) also suitable is alkaline endo-dextranase described in EP 1 350843A that is announced on October 8th, 2003 by Kao company.For the detailed description of enzyme and preparation thereof, see also detailed Description Of The Invention [0011] to [0039] and embodiment 1 to 4, [0067] is to [0077].Described alkaline endo-dextranase varient passes through in sequence identification number: in 2 (a) position 10, (b) position 16, (c) position 22, (d) position 33, (e) position 39, (f) position 76, (g) position 109, (h) position 242, (i) position 263, (j) position 308, (k) position 462, (l) position 466, (m) position 468, (n) position 552, (o) position 564, and/or (p) sequence identification number: position 608 and/or the position corresponding with it obtain with the amino-acid residue of another aminoacid replacement cellulase in 2, the aminoacid sequence of described cellulase with by sequence identification number: the aminoacid sequences of 2 representatives have at least 90%, preferred 95%, more preferably 98%, 100% identity.

The example that " has by sequence identification number: the alkali cellulose enzyme of the aminoacid sequence of 2 expressions " comprises that Egl-237[is derived from Bacillus strain KSM-S237 (FERM BP-7875), people such as Hakamada, " Biosci.Biotechnol.Biochem. ", 64,2281-2289,2000]." have show with by sequence identification number: the alkali cellulose enzyme of the aminoacid sequence of aminoacid sequence at least 90% homologys of 2 expressions " example comprise have show with by sequence identification number: preferred at least 95% homology of the aminoacid sequences of 2 expressions, the more preferably alkali cellulose enzyme of the aminoacid sequence of at least 98% homology.Specific examples comprises derived from the alkali cellulose enzyme of Bacillus strain 1139 (Egl-1139) (people such as Fukumori, " J.Gen.Microbiol. ", 132,2329-2335) (91.4% homology), alkali cellulose enzyme (people such as Sumitomo derived from Bacillus strain KSM-64 (Egl-64), " Biosci.Biotechnol.Biochem. ", 56,872-877,1992) (homology: 91.9%), with cellulase (Japanese patent application 2000-47237) (homology: 95.0%) derived from Bacillus strain KSM-N131 (Egl-N131b).

Described amino acid is preferably replaced by following material: glutamine, L-Ala, proline(Pro) or methionine(Met) (especially glutamine) are preferably placed at position (a), l-asparagine or arginine (especially l-asparagine) are preferably placed at position (b), proline(Pro) is preferably placed at position (c), Histidine is preferably placed at position (d), L-Ala, Threonine or tyrosine (especially L-Ala) are preferably placed at position (e), Histidine, methionine(Met), Xie Ansuan, Threonine or L-Ala (especially Histidine) are preferably placed at position (f), Isoleucine, leucine, Serine or Xie Ansuan (especially Isoleucine) are preferably placed at position (g), L-Ala, phenylalanine, Xie Ansuan, Serine, aspartic acid, L-glutamic acid, leucine, Isoleucine, tyrosine, Threonine, methionine(Met) or glycine (L-Ala especially, phenylalanine or Serine) be preferably placed at position (h), Isoleucine, leucine, proline(Pro) or Xie Ansuan (especially Isoleucine) are preferably placed at position (i), L-Ala, Serine, glycine or Xie Ansuan (especially L-Ala) are preferably placed at position (j), Threonine, leucine, phenylalanine or arginine (especially Threonine) are preferably placed at position (k), leucine, L-Ala or Serine (especially leucine) are preferably placed at position (l), L-Ala, aspartic acid, glycine or Methionin (especially L-Ala) are preferably placed at position (m), methionine(Met) is preferably placed at position (n), Xie Ansuan, Threonine or leucine (especially Xie Ansuan) are preferably placed at position (o), and Isoleucine or arginine (especially Isoleucine) are preferably placed at position (p).

By using for example algorithm in the Lipman-Pearson method and a plurality of similar areas in every kind of alkali cellulose enzyme amino acid sequence are provided maximum comparability must assign to compare aminoacid sequence and can determine " the correspondingly amino-acid residue of position " of known algorithm.Can determine the position of homologous amino acid residue in every kind of cellulase sequence by the aminoacid sequence of fiber arranged plain enzyme (Fig. 1 among the EP 1 350 843) in this way, and the insertion or the disappearance that do not exist in the considered amino acid sequence.Can infer, be present in three-dimensional identical position, and it produces similar effects aspect the concrete effect of the plain enzyme of target fibers with the source position.

Show and sequence identification number for having: for the another kind of alkali cellulose enzyme of the aminoacid sequence of 2 at least 90% homologys, corresponding to by sequence identification number: (a) position 10 in the alkali cellulose enzymes (Egl-237) of 2 expressions, (b) position 16, (c) position 22, (d) position 33, (e) position 39, (f) position 76, (g) position 109, (h) position 242, (i) position 263, (j) position 308, (k) position 462, (l) position 466, (m) position 468, (n) position 552, (o) position 564 and (p) position of position 608 and the specific examples of these position amino-acid residues will be shown in hereinafter:

	Egl-237	Egl-1139	Egl-64	Egl-N131b
					(a)	10Leu	10Leu	10Leu	10Leu
(b)	16Ile	16Ile	16Ile	Do not have corresponding with it
					(c)	22Ser	22Ser	22Ser	Do not have corresponding with it
(d)	33Asn	33Asn	33Asn	19Asn
					(e)	39Phe	39Phe	39Phe	25Phe
(f)	76Ile	76Ile	76Ile	62Ile
					(g)	109Met	109Met	109Met	95Met
(h)	242Gln	242Gln	242Gln	228Gln
					(i)	263Phe	263Phe	263Phe	249Phe
(j)	308Thr	308Thr	308Thr	294Thr
					(k)	462Asn	461Asn	461Asn	448Asn
(l)	466Lys	465Lys	465Lys	452Lys
					(m)	468Val	467Val	467Val	454Val
(n)	552Ile	550Ile	550Ile	538Ile
					(o)	564Ile	562Ile	562Ile	550Ile
(p)	608Ser	606Ser	606Ser	594Ser

3) also suitable is alkali cellulose enzyme K described in EP 265 832A that announced on May 4th, 1988 by Kao.For the detailed description of enzyme and preparation thereof, see also specification sheets page 4 the 35th and walk to embodiment 1 and 2 on the 12nd page of the 22nd row and the 19th page.Described alkali cellulose enzyme K has following physics and chemical property:

(1) activity: have the Cx enzymic activity and the weak C that act on carboxymethyl cellulose ₁Enzymic activity and weak β-glucose oxidase activity;

(2) to the specificity of matrix: act on carboxymethyl cellulose (CMC), crystalline cellulose, Avicell, cellobiose and p-nitrophenyl cellobiose (PNPC);

(3) have working pH and the best pH in 9 to 10 scopes in 4 to 12 scopes;

(4) when allowing under 40 ℃, to leave standstill respectively 10 minutes and 30 minutes the time, having 4.5 to 10.5 and 6.8 to 10 stable pH value respectively;

(5) can in 10 to 65 ℃ wide temperature range, work, and about 40 ℃ are recognized as optimum temps;

(6) influence of sequestrant: ethylenediamine tetraacetic acid (EDTA) (EDTA), ethylene glycol-two-(β--amino-ethyl ether) N, N, N N ', N " tetraacethyl (EGTA), N, N-two (carboxymethyl) glycine (nitrilotriacetic acid(NTA)) are (NTA), tripoly phosphate sodium STPP (STPP) and zeolite do not hinder described activity;

(7) influence of surface-active agents: the active inhibition that is subjected to surface-active agents hardly, surface-active agents such as linear alkylbenzene sulphonic acid (LAS), sodium alkyl sulfate (AS), polyxyethylated sodium sulfate (ES), alpha-olefin sodium sulfonate (AOS), α-sodium sulfonate aliphatic acid ester (α-SFE), alkyl sodium sulfonate (SAS), the secondary alkyl oxide of polyoxyethylene, soap (sodium salt) and dimethyl dialkyl ammonium chloride;

(8) proteolytic enzyme had strong resistance; With

(9) molecular weight (by gel chromatography): 180,000 ± 0,000 place has maximum peak.

Preferably, can obtain this fermentoid by from the cultured product of genus bacillus KSM-635, separating.

Cellulase K can be commercially available from Kao company: for example be called

Cellulase preparation Eg-X be all derived from E-H and the E-L mixture of genus bacillus KSM-635 bacterium.Cellulase E-H and E-L have been described in " Agric Biol Chem " (rolling up the 1275th to 1278 page in 1989 the 53rd) of people such as S.Ito's " Extremophiles " (1997, the 1st volume the 61st to 66 page) and S.Ito.

4) the alkaline bacterium endo-dextranase of being described in EP 271 004A that announced on June 15th, 1988 by Kao also is applicable to the object of the invention.For the detailed description of enzyme and preparation thereof, see also Instructions Page 9 the 15th and walk to the 23rd page of the 17th row and the 31st page the 1st and walk to the 33rd page of the 17th row.They are:

Derived from the alkali cellulose enzyme K-534 of KSM 534 (FERM BP 1508),

Derived from the alkali cellulose enzyme K-539 of KSM 539 (FERM BP 1509),

Derived from the alkali cellulose enzyme K-577 of KSM 577 (FERM BP 1510),

Derived from the alkali cellulose enzyme K-521 of KSM 521 (FERM BP 1507),

Derived from the alkali cellulose enzyme K-580 of KSM 580 (FERM BP 1511),

Derived from the alkali cellulose enzyme K-588 of KSM 588 (FERM BP 1513),

Derived from the alkali cellulose enzyme K-597 of KSM 597 (FERM BP 1514),

Derived from the alkali cellulose enzyme K-522 of KSM 522 (FERM BP 1512),

Derived from the alkali cellulose enzyme E-II of KSM 522 (FERM BP 1512),

Derived from the alkali cellulose enzyme E-III of KSM 522 (FERM BP 1512),

Derived from the alkali cellulose enzyme K-344 of KSM 344 (FERM BP 1506) and

Alkali cellulose enzyme K-425 derived from KSM 425 (FERM BP 1505).

5) last, the alkaline endo-dextranase of being described in the JP2005287441A that announced on October 20th, 2005 by Kao derived from rod bacterium bacterial classification KSM-N also is applicable to purpose of the present invention.For the detailed description of enzyme and preparation thereof, see also specification sheets page 4 the 39th and walk to the 10th page of the 14th row.The example of this type of alkaline endo-dextranase is:

Alkali cellulose enzyme Egl-546H derived from genus bacillus KSM-N546

Alkali cellulose enzyme Egl-115 derived from genus bacillus KSM-N115

Alkali cellulose enzyme Egl-145 derived from genus bacillus KSM-N145

Alkali cellulose enzyme Egl-659 derived from genus bacillus KSM-N659

Alkali cellulose enzyme Egl-640 derived from genus bacillus KSM-N440

The varient of the above-mentioned enzyme that obtains via various technology well known by persons skilled in the art such as orthogenesis is also included among the present invention.

The modified-cellulose derivative

Modified-cellulose derivative required among the present invention comprises the polymkeric substance that comprises cellulosic backbone.Described Mierocrystalline cellulose can be a negatively charged ion or nonionic modified, the preferred anionic modification.The Mierocrystalline cellulose monomer is as follows.

R1, R2 and R3 have shown can be for the position that replaces in the Mierocrystalline cellulose monomer.In the natural cellulose polymkeric substance, these groups comprise hydrogen atom.The modified-cellulose derivative that can be used for this paper comprises substituting group in one or more these positions.For example, negatively charged ion is replaced, one or more these positions can be replaced by anionic group in the described polymkeric substance, in the anionic group of for example following its acid or salt form (particular certain cancers (shown here) or potassium salt form) one.

-L-CO ₂Na

-L-SO ₃Na

-PO ₃Na

-SO ₃Na

Wherein:

L is C _1-6Alkyl, more preferably C _1-4Alkyl

Anion-modified derivatived cellulose also can comprise the nonionic substituting group, one or more can replacement among position R1, R2 and the R3 wherein by non-ionic group, for example,

-A

-L-OH

-L-CN

-C(＝O)A

-C(＝O)NH ₂

-C(＝O)NHA

-C(＝O)N(A)B

-C(＝O)OA

-(CH ₂CH ₂CH ₂O) _nZ

-(CH ₂CH ₂O) _nZ

-(CH ₂CH(CH ₃)O) _nZ

-(CH ₂O) _nZ

Wherein:

A and B are C _1-30Alkyl

L is C _1-6Alkyl

N=1 to 100

Z is H or C _1-6Alkyl

The limiting examples of suitable modified-cellulose derivative is the sodium salt or the sylvite of following material: carboxymethyl cellulose; carboxyethyl cellulose; sulfoethylcellulose; the sulfopropyl Mierocrystalline cellulose; cellulose sulfate; phosphorylated cellulose; carboxymethyl hydroxyethyl cellulose; carboxymethyl hydroxypropyl cellulose; the sulfoethyl Natvosol; the sulfoethyl hydroxypropylcellulose; the carboxymethyl methyl hydroxyethylcellulose; carboxy methyl cellulose; the sulfoethyl methyl hydroxyethylcellulose; the sulfoethyl methylcellulose gum; the carboxymethyl Type 3U; carboxymethylethylcellulose; the sulfoethyl Type 3U; the sulfoethyl ethyl cellulose; the carboxymethyl methylhydroxypropylcellulose; the sulfoethyl methylhydroxypropylcellulose; carboxymethyl dodecyl Mierocrystalline cellulose; carboxymethyl lauroyl Mierocrystalline cellulose; carboxymethyl cyanoethyl cellulose and sulfoethyl cyanoethyl cellulose.

Nonionic modified Mierocrystalline cellulose

Replace or except anion-modified cellulose polymer compound, also can provide the modified-cellulose derivative by nonionic modified derivatived cellulose.The example of nonionic modified cellulose polymer compound comprises methylcellulose gum, ethyl cellulose, propyl cellulose, Natvosol, hydroxypropylcellulose, methyl hydroxyethylcellulose, Type 3U, dodecyl Natvosol, ethyl hydroxypropyl cellulose, rhodia, methylhydroxypropylcellulose, methyl ethyl hydroxyethyl cellulose, butyl glycidyl base ether-Natvosol and lauryl glycidyl ether-Natvosol.

Specific examples comprises that Finnfix BDA (deriving from Noviant), Tylose CR1500 G2 (deriving from Clariant), Carbose number D65, D72, LT-30 and LT-20 (deriving from PennCarbose); The hydrophobically modified derivatived cellulose, for example described in the WO99/61479 (Noviant) those; Poly ethyldiol modified derivatived cellulose, for example described in the DE102004063766 those.

Especially preferred modified-cellulose derivative has at least 20 000 or at least 50 000 or even at least 100,000 or even the weight-average molecular weight of at least 150 000kDa.The weight-average molecular weight of modified-cellulose derivative generally is not more than 500,000, or is not more than 300,000, or is not more than 250 000kDa.Preferred substitution value (DS) be 0.3 to or 0.4 to or 0.45 at most for example 0.7 or even 0.8 or even 0.9.Especially preferably the modified methylated cellulose that has this molecular weight as described herein and/or substitution value and/or content is such as CMC.

Based on the gross weight of detergent composition, the content of modified-cellulose derivative in detergent composition of the present invention is generally at least 0.005% weight or 0.01% weight or 0.02% weight or at least 0.05% weight or even at least 0.1% weight.Usually, described content is not more than 5% by the weight of described detergent composition, or even be not more than 2% by the weight of described detergent composition, or even be not more than 1.5% by the weight of described detergent composition.In the especially preferred embodiment of the present invention, the proteinic weight ratio of modified-cellulose derivative and active cellulase is 1:1 to 10000:1, preferred 20:1 to 1000:1, most preferably 30:1 to 800:1.

For many years, derivatived cellulose is incorporated in the detergent composition such as methylcellulose gum.They are deposited on surface of cotton fabric to form electronegative stain-proofing layer, and it comes antifouling on fabric face by reducing dirt deposition.The inventor finds, has than the more low-molecular-weight derivatived cellulose of the used derivatived cellulose of tradition because they can be used as anti-redeposition auxiliary agent by dirt is suspended in the washing liq, therefore can provide more wonderful beneficial effect.By the reaction of concrete Mierocrystalline cellulose reagent precursor, can generate these derivatived celluloses on the spot.

Described modified-cellulose derivative can be used as the dried particles component and adds, and described grain fraction for example comprises by weight greater than 50%, or even greater than 60% or 70% or 80% to maximum 100% modified-cellulose derivative.Described modified-cellulose derivative can be used as by conventional detergent particles preparation method such as spraying drying, agglomeration or extrudes a processing particulate part that makes, and is incorporated in the detergent composition of the present invention.In the case, the content of the modified-cellulose derivative in this type of particle counts at least 0.1% or 0.5% or 1% by described processing particulate weight, and may be, and more may be less than 60% or 50%, 40%, 30% or even less than 20% or 10% less than 70%.For comprising low levels phosphoric acid salt and/or zeolite builders, for example comprise weight by total detergent composition less than 15%, or even less than 14% or 12% or 10% or 8% detergent composition down to 0% phosphoric acid salt and/or zeolite builders, to come incorporating modified derivatived cellulose be especially preferred as handling a particulate part.Because when detergent composition was added to the water, it can promote the uniform distribution of Mierocrystalline cellulose in whole washing liq by the solubleness that helps derivatived cellulose, is preferred therefore.Be present under the situation about handling in the detergent particles at the modified-cellulose derivative, described processing detergent particles can comprise any other conventional detergent ingredients or its component, all as mentioned below or any promoter materials described in any method described in the subtitle " preparation composition method " described in the JP 2,002 265999 (Kao) or hereinafter for example.Specifically, with described processing particulate weight is benchmark, this type of particle can comprise polymeric polycarboxylate's polymkeric substance of at least 1% or at least 5% or 10% to maximum 15% or 20% or 30% by weight, such as homopolymer or the multipolymer (for example deriving from the Sokalan polymkeric substance of BASF) based on vinylformic acid and/or toxilic acid.Described processing particle can comprise negatively charged ion, nonionic, positively charged ion, zwitterionic and/or amphoterics, or their mixture.With described processing particulate gross weight is benchmark, and described amount can be 1% to 70% by weight, or 2% to 60%, or 5% to 850%.For example, handle particle and can comprise nonionogenic tenside optional and negatively charged ion and/or cats product combination.Suitable tensio-active agent is described in this specification sheets " tensio-active agent " part.Specifically, suitable ionic surfactant pack is drawn together alkyl alkoxylated surfactants, for example has 3 to 20 or even the ethoxylated surfactant of higher (such as 20 to 50) degree of alkoxylation.

It is 1% to 30% by weight that the processing particle can comprise content, or 2% to 25%, or 5% to 20% water glass (especially 1 to 2 ratio).

According to the present invention, preferred compositions comprises polymeric polycarboxylate's polymkeric substance, and its content makes the weight ratio of polymeric polycarboxylate and modified-cellulose derivative be 2:1 at least, more preferably 2.5:1 at least, and most preferably 3:1 or even 4:1 or 5:1 at least.Exist therein in the above-mentioned processing particle of polymeric polycarboxylate, this ratio also is preferred.

The present composition and/or more particularly, the particulate bulk density that comprises the modified-cellulose derivative are generally at least 450g/L or 550g/L or 650g/L or 700g/L, 1500g/L at most at least at least.Can measure bulk density by simple funnel-cup device, described device comprises conical funnel, described funnel firmly is installed on the pedestal, and has clack valve bottom so that the funnel content can be transferred in the cylindrical cup of axially aligning that is placed in below the funnel fully at it.The high 130mm of described funnel, and its topmost and internal diameter bottom be respectively 130mm and 40mm.It is mounted, so that bottom than the high 140mm of pedestal upper surface.Described cup total height is 90mm, and interior height is 87mm, and internal diameter is 84mm.Its nominal volume is 500ml.For measuring, by falling, funnel is filled up powder with hand, clack valve is opened, and made powder get overfill to described cup.From frame, shift out the cup that fills up, and by with the instrument that straight flange arranged for example cutter cross its upper limb, from cup, remove too much powder.The cup that fills up of weighing then, and the powder weight that is obtained is on duty 2, be the bulk density of unit to obtain g/L.Carry out replicate measurement, and the mean value of getting three results is bulk density.

The inventor further provides the detergent composition that the dirt suspension characteristic can be provided.

According to another embodiment of the invention, thereby provide a kind of detergent composition that comprises oligose, described oligose has less than 20, the weight-average molecular weight of 000kDa, this type of oligose can by enzyme as defined above with have 30,000kDa to 500, the anion-modified cellulosic reaction of 000kDa molecular-weight average obtains.In another embodiment of described invention, a kind of aqueous cleaning liquid that comprises detergent composition is provided, the content of wherein said oligose is 0.5ppm to 1000ppm, or 0.8 to 1500ppm, or 1.0 to 1000ppm.

According to another embodiment of the invention, providing with oligose comes preparing washing agent composition to be used for the application of soil suspension, described oligose has less than 20, the weight-average molecular weight of 000kDa, this type of oligose can and have 30 by aforesaid enzyme, 000kDa to 500, the reaction of the negatively charged ion of 000kDa weight-average molecular weight or nonionic (preferred anionic) modified-cellulose derivative obtains.

According to another aspect of the present invention, a kind of detergent composition also is provided, described composition comprises aforesaid enzyme and at least 2% weight, or even at least 5% weight, 10% weight, 15% weight, 20% weight or higher phosphate builders salt to for example maximum 50% weight or 40% weight or 30% weight or 25% weight, at least 25% weight, or 30% weight or 40% weight or 45% weight or 50% weight or even 55% weight to the described phosphate builders of maximum 100% weight or 90% weight or 80% weight comprise the pyrophosphate salt washing assistant.

By in spray drying process, to comprise the sodium salt of tri-polyphosphate or the composition spray drying of other salt or its sour form, other chemical composition in controlled temperature and/or air-flow and/or the spraying drying slurries wherein, so that the reaction to pyrophosphate salt of desired tri-polyphosphate to be provided, generate this pyrophosphate salt washing assistant on the spot.Described method can be operated described in for example WO03/091378 or US4310431.

Auxiliary material

Though it is optional for the present invention, but hereinafter the non-limiting tabulation of illustrational promoter material be applicable to composition of the present invention, and can expect it is incorporated in certain embodiments of the present invention, for example helping or to improve the clean-up performance of handling substrate to be cleaned, or under the situation that contains spices, tinting material, dyestuff etc., regulate the aesthetic property of cleaning compositions.The physical form that the clear and definite character of these annexing ingredients and incorporation thereof will depend on composition with and the character of the clean operation used.Suitable promoter material includes but not limited to dispersion agent, the agent of clay soil removal/anti redeposition, whitening agent, suds suppressor, dyestuff, spices, structural elasticity agent, fabric softener, carrier, hydrotropic agent, processing aid, solvent and/or the pigment of tensio-active agent, washing assistant, sequestrant, dye transfer inhibitor, dispersion agent, additional enzyme and enzyme stabilizers, catalytic specie, bleach-activating agent, hydrogen peroxide, hydrogen peroxide cource, preformed peracid, polymkeric substance.Except the following discloses content, the suitable example of these other auxiliary agents and consumption also are present in United States Patent (USP) 5,576, and 282,6,306,812 B1 and 6,326, among 348 B1, described document is incorporated into way of reference.When having one or more auxiliary agents, these one or more auxiliary agents can exist as detailed below:

SYNTHETIC OPTICAL WHITNER-cleaning compositions of the present invention can comprise one or more SYNTHETIC OPTICAL WHITNER.The suitable SYNTHETIC OPTICAL WHITNER that is different from bleaching catalyst comprises other optical white, bleach-activating agent, hydrogen peroxide, hydrogen peroxide cource, preliminary shaping peracid and their mixture.Usually, when using SYNTHETIC OPTICAL WHITNER, composition of the present invention can comprise by weight of this theme cleaning compositions about 0.1% to about 50% or even about 0.1% to about 25% SYNTHETIC OPTICAL WHITNER.The example of suitable SYNTHETIC OPTICAL WHITNER comprises:

(1) other optical white, for example vitamin K3;

(2) preliminary shaping peracid: suitable preliminary shaping peracid includes but not limited to be selected from the compound by the following group of forming: percarboxylic acids and salt thereof, percarbonic acid and salt thereof, mistake imidic acid and salt, permonosulphuric acid and salt thereof are (for example

) and their mixture.Suitable percarboxylic acids comprises the hydrophobic and hydrophilic peracid with formula R-(C=O) O-O-M, and wherein R is an alkyl, optional branched-chain alkyl, and when peracid was hydrophobic, it had 6 to 14 carbon atoms or 8 to 12 carbon atoms; When peracid is hydrophilic, its have less than 6 carbon atoms or even less than 4 carbon atoms; And M is counter ion, for example sodium, potassium or hydrogen;

(3) hydrogen peroxide cource, for example inorganic over hydrogenation adduct salt comprises following an alkali metal salt: as peroxyboric acid sodium salt (being generally monohydrate or tetrahydrate), percarbonic acid sodium salt, persulfuric acid sodium salt, peroxophosphoric acid sodium salt, mistake metso and their mixture.In one aspect of the invention, inorganic over hydrogenation adduct salt is selected from the group of being made up of following: peroxyboric acid sodium salt, percarbonic acid sodium salt and their mixture.If be used, inorganic over hydrogenation adduct salt typically exists with 0.05% to 40% weight of total composition or the content of 1% to 30% weight, and typically as can coated crystalline solid being incorporated in this composition.Suitable coating compounds comprises: inorganic salt such as alkalimetal silicate, carbonate or borate or their mixture, or organism such as water-soluble or dispersible polymer, wax, oil or fatty soap; With

(4) has the bleach-activating agent of R-(C=O)-L, wherein R is an alkyl, optional branched-chain alkyl, when bleach-activating agent when being hydrophobic, it has 6 to 14 carbon atoms or 8 to 12 carbon atoms, and when bleach-activating agent when being hydrophilic, its have less than 6 carbon atoms or even less than 4 carbon atoms; And L is a leavings group.The example of suitable leavings group is the benzene sulfonate of phenylformic acid and derivative thereof-especially.Suitable bleach-activating agent comprises dodecane acyl-oxygen base benzene sulfonate, last of the ten Heavenly stems acyloxy benzene sulfonate, caprinoyl aminobenzoic acid and salt, 3 thereof; 5,5-trimethyl acetyl oxygen base benzene sulfonate, tetra acetyl ethylene diamine (TAED) and nonanoly acyloxy benzene sulfonate (NOBS).Suitable bleach-activating agent also is disclosed among the WO 98/17767.Although can adopt any suitable bleach-activating agent, in one aspect of the invention, the cleaning compositions of this theme can comprise NOBS, TAED or their mixture.

If present, peracid and/or bleach-activating agent usually with based on described composition about 0.1% to about 60% weight, about 0.5% to about 40% weight or even about 0.6% content to about 10% weight be present in the described composition.One or more hydrophobicity peracid or its precursor can be united use with one or more wetting ability peracid or its precursor.

Can select the amount of hydrogen peroxide cource and peracid or bleach-activating agent, make that the mol ratio of available oxygen (from peroxide source) and peracid is 1:1 to 35:1, perhaps even be 2:1 to 10:1.

Tensio-active agent-cleaning compositions can comprise tensio-active agent or surfactant system as described in the present invention, and wherein said tensio-active agent can be selected from nonionogenic tenside, anion surfactant, cats product, amphoterics, zwitterionics, semi-polar nonionic surfactants and their mixture.If present, tensio-active agent typically in by the weight of this theme composition about 0.1% to about 60%, about 1% to about 50% or even about 5% to about 40% content exist.

Washing assistant-cleaning compositions of the present invention can comprise one or more detergent builder or builder system.When using washing assistant, this theme composition will comprise weight by this theme composition usually at least about 1%, and about 5% to about 60% or even about 10% to about 40% washing assistant.

Washing assistant includes but not limited to: basic metal, the poly-phosphate of ammonium and alkanol ammonium, alkalimetal silicate, alkaline-earth metal and alkaline carbonate, silico-aluminate washing assistant and polycarboxylic acid salt compound, the ether hydroxy-polycarboxylate, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and the acid of carboxyl methoxy apple, the various an alkali metal salts of polynary acetate such as ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), ammonium salt and substituted ammonium salt, and polycarboxylate such as mellitic acid, succsinic acid, citric acid, oxygen di-succsinic acid, polynary toxilic acid, 1,3,5-three phenylformic acid, carboxymethyl oxysuccinic acid and their soluble salt.

The cleaning compositions of sequestrant-this paper can comprise sequestrant.Suitable sequestrant comprises copper, iron and/or manganese sequestrant and their mixture.When using sequestrant, this theme composition can comprise by weight of this theme composition about 0.005% to about 15% or even about 3.0% to about 10% sequestrant.

Dye transfer inhibitor-cleaning compositions of the present invention also can comprise one or more dye transfer inhibitors.Suitable polymeric dye transfer inhibitor includes but not limited to: the multipolymer of polyvinyl pyrrolidone polymers, polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole, Ju Yi Xi oxazolidinone and polyvinyl imidazol or their mixture.In the time of in being present in this theme composition, dye transfer inhibitor can by the weight of described composition about 0.0001% to about 10%, about 0.01% to about 5% or even about 0.1% to about 3% content exist.

White dyes-cleaning compositions of the present invention also preferably comprises can give the annexing ingredient of color articles to be cleaned, such as white dyes.Be applicable to that any white dyes in the laundry detergent composition can be used in the composition of the present invention.The most frequently used white dyes is to belong in the following classification those: diaminostilbene sulfonic acid, diaryl pyrazole quinoline derivant and xenyl toluylene radical derivative.The example of diaminostilbene sulfonic acid type white dyes comprises the sodium salt of following material:

4,4 '-two-(2-dihydroxy ethyl amino-4-phenylamino-s-triazine-6-base is amino) toluylene-2,2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate,

4,4 '-two-(2,4-hexichol amido-s-triazine-6-base is amino) toluylene-2.2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate,

4,4 '-two-(2-phenylamino-4 (N-methyl-N-2-hydroxyethylamino)-s-triazine-6-base is amino) toluylene-2,2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate,

4,4 '-two-(4-phenyl-2,1,3-triazole-2-yl) toluylene-2,2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate,

4,4 '-two-(2-phenylamino-4 (1-methyl-2-hydroxyethylamino)-s-triazine-6-base amino) toluylene-2,2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate and

2-(diphenylethyllene-4 ＂-naphtho--1., 2 ': 4,5)-1,2,3-triazoles-2 ＂-sulfonate.

Preferred white dyes be derive from Ciba-Geigy AG (Basel, Switzerland) DMS and

CBS. DMS is 4,4 '-two-(2-morpholinyl-4-phenylamino-s-triazine-6-base is amino) stilbene disulfonic acid disodium salts.

CBS is 2,2 '-two-(styryl phenyl base) disulfonic acid disodium salts.

The white dyes that also preferably has following structure:

R wherein ₁And R ₂Form unsubstituted or C altogether with the nitrogen-atoms that is connected them ₁-C ₄Morpholine, piperidines or pyrrolidine ring that alkyl replaces, and preferred morpholine ring (can trade(brand)name Parawhite KX commercially available, by Paramount Minerals and Chemicals (Mumbai India) provides).

Other is applicable to that fluorescent agent of the present invention comprises 1-3-diaryl pyrazole quinoline and 7-alkylamino tonka bean camphor.

Suitable fluorescent brightener levels comprises from about 0.01% weight, 0.05% weight, about 0.1% weight or even lower aq to 0.5% weight of about 0.2% weight or even the high level of 0.75% weight.

During fabric hueing agent-in being formulated into detergent composition, dyestuff or pigment can be deposited on the fabric when described fabric contacts with the washing liq that comprises described cleaning composition, thereby by absorbing the color that visible light changes described fabric.White dyes is issued to the small part visible light.In contrast, to change surface color be because their absorb at least a portion visible spectrum to fabric hueing agent.Suitable fabric hueing agent comprises dyestuff and dyestuff-clay binding substances, and can comprise pigment.The dyestuff that is suitable for comprises small molecules dyestuff and polymeric dye.Suitable small molecules dyestuff comprises the small molecules dyestuff that is selected from by the following group of forming: the dyestuff that belongs to following color index (C.I.) classification: sun blue, directly red, direct purple, acid blue, Xylene Red, acid violet, alkali blue, alkalescence is purple and alkalescence is red, or their mixture, for example those described in the common unsettled european patent application of submitting in WO2005/03274, WO 2005/03275, WO 2005/03276 and on July 7th, 2,006 6116780.5.

Dispersion agent-composition of the present invention also can comprise dispersion agent.Suitable water soluble organic substance comprises homopolymerization or co-polymeric acids or their salt, and wherein polycarboxylic acid comprises at least two and is separated by and is no more than the carboxyl of two carbon atoms.

Enzyme-except bacterium alkalescence endo-dextranase, described cleaning compositions also can comprise one or more other enzymes that clean-up performance and/or fabric care benefit effect can be provided.The example of suitable enzyme includes but not limited to, hemicellulase, peroxidase, proteolytic enzyme, other cellulase, zytase, lipase, Phospholipid hydrolase, esterase, at, polygalacturonase, mannase, pectin lyase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, ligninase, Starch debranching enzyme, tannase, pentosanase, Mai Laning enzyme, beta-glucanase, arabinase, Unidasa, chondroitinase, laccase and amylase, or their mixture.In preferred embodiments, composition of the present invention also comprises lipase, with further improvement cleaning and whitening performance.Typical combination is the enzyme combination that for example can comprise with amylase bonded proteolytic enzyme and lipase.In the time of in being present in cleaning compositions, above-mentioned additional enzymes can be by described composition weight meter about 0.00001% to about 2%, about 0.0001% to about 1% or even about 0.001% exist to the content of about 0.5% zymoprotein.

Enzyme stabilizers-can stablize the enzyme that is used for washing composition by various technology.The enzyme that the present invention uses can be stablized by calcium that exists in the final composition and/or magnesium ion water-soluble sources, and final product offers enzyme with this ion.Comprising under the aqueous composition situation of proteolytic enzyme, for example boron compound is stable with further improvement can to add reversible protease inhibitors.

Catalytic metal complexes-applicant's cleaning compositions can comprise catalytic metal complexes.The metallic bleaching catalyst of one class is such catalyst system, this system comprises and has the active transition-metal cation of definite bleach catalyst, as copper positively charged ion, iron positively charged ion, titanium positively charged ion, ruthenium positively charged ion, tungsten positively charged ion, molybdenum positively charged ion or manganese positively charged ion; Comprise and have very low or do not have the active assistant metal positively charged ion of bleach catalyst, as zinc cation or aluminium cations; And comprise sequestrant, especially ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and their water-soluble salt that definite stability constant is arranged for catalytic and auxiliary metallic cation.Above-mentioned catalyzer is disclosed in U.S.4, in 430,243.

If desired, the present composition can carry out catalysis by manganic compound.These compounds and consumption are well known in the art, and comprise and for example be disclosed in U.S.5, the manganese-based catalyst in 576,282.

It is known can be used for cobalt bleaching catalyst of the present invention, and is described in for example U.S.5, in 597,936, U.S.5,595,967.Above-mentioned cobalt catalyst is easy to by the preparation of known method, U.S.5 for example, the method that is proposed in 597,936 and U.S.5,595,967.

The composition of this paper also can comprise the transition metal complex of part aptly, and described part is bicyclic piperidine (WO 05/042532 A1) and/or encircle rigid ligand (being abbreviated as " MRL ") mostly for example.As practical matter, and it is unrestricted, the composition of adjustable abridged edition literary composition and method, make approximately at least one 1/100000000th active MRL material is provided in the aqueous cleaning medium, and in washing liq, will typically be provided as about 0.005ppm to about 25ppm, about 0.05ppm is to about 10ppm, or even about 0.1ppm MRL of about 5ppm extremely.

Suitable transition metal comprises for example manganese, iron and chromium in the transition metal bleach catalyzer of the present invention.Suitable MRL comprises 5,12-diethyl-1,5,8,12-four azabicyclos [6.6.2] n-Hexadecane.

Be easy to prepare suitable transition metal M RL by known steps,, proposed in 225,464 for example at WO00/32601 and U.S.6.

Solvent-suitable solvent comprises water and other solvent such as lipophilic fluid.The example of suitable lipophilic fluid comprises siloxanes, other silicone, hydrocarbon, glycol ether, glycerol derivative such as glyceryl ether, perfluoroamine, perfluorination and hydrogen fluorine ether solvents, the floride-free organic solvent of low volatility, diol solvent, other environment amenable solvent and their mixture.

Softening system-composition of the present invention can comprise tenderizer such as clay and optionally have flocculation agent and an enzyme; Optional being used for by washing softening.

The preparation method for compositions

Composition of the present invention can be formulated into any suitable form and any method preparation of adopting the prescription teacher to select, and its limiting examples is described in applicant's embodiment and United States Patent (USP) 4,990,280, United States Patent (USP) 20030087791A1; United States Patent (USP) 20030087790A1; United States Patent (USP) 20050003983A1; United States Patent (USP) 20040048764A1; United States Patent (USP) 4,762,636; United States Patent (USP) 6,291,412; United States Patent (USP) 20050227891A1; EP1070115A2; United States Patent (USP) 5,879,584; United States Patent (USP) 5,691,297; United States Patent (USP) 5,574,005; United States Patent (USP) 5,569,645; United States Patent (USP) 5,565,422; United States Patent (USP) 5,516,448; United States Patent (USP) 5,489,392; United States Patent (USP) 5,486, in 303, these patents are all incorporated this paper into way of reference.

Using method

The present invention includes the method that is used for laundering of textile fabrics.Said method comprising the steps of: fabric that will be to be washed contacts with described cleaning washing soln, and described washing soln comprises at least one embodiment of applicant's cleaning compositions, cleaning additive or their mixture.Fabric can comprise any most of any fabric that can wash under the normal consumer working conditions.Described solution preferably has about 8 to about 10.5 pH.Described composition can solution in about 500ppm to about 15, the concentration of 000ppm is used.Water temperature typically is about 5 ℃ to about 90 ℃.The ratio of water and fabric is generally about 1:1 to about 30:1.

Embodiment

Except as otherwise noted, raw material can be available from Aldrich, and P.O.Box 2060, Milwaukee, and WI 53201, USA.

(a) Embodiment 1 to 6

The granular laundry cleaning composition is designed for the washing machine of hand washing or top-loaded.

Embodiment 7 to 12

The granular laundry cleaning composition is designed for preceding loaded type automatic washing machine device.

20 ℃ under 90 ℃, the concentration of aqueous solution with 7000 to 10000ppm, and the ratio of the water of 5:1 and fabric use any above-mentioned composition to come laundering of textile fabrics.Typical pH is about 10.

Above the proteinic ratio of CMC and organized enzyme is shown in the following table in the preparation:

Embodiment	1	2	3	4	5	6	7	8	9	10	11	12
													CMC％	1	0.3	0.3	0.1	1.1	0.9	0.15	1.4	0.2	1.4	1	0.5
Celluclean 5T ％ (15.6mg/g)	0.1	0.2	0.1	0.2	0.3	0.1	0.2	0.15	0.2	0.3	0.15	0.15
													Active cellulase %	0.00156	0.00312	0.00156	0.00312	0.00468	0.00156	0.00312	0.00234	0.00312	0.00468	0.00234	0.00234
CMC and cellulase ratio	641	96	192	32	235	577	48	598	64	299	427	214

Be used for raw material and the explanation of composition embodiment 1 to 12

Linear alkyl benzene sulfonate, its average fatty carbon chain length is C ₁₁-C ₁₂, by Stepan, Northfield, Illinois, USA supply

C _12-14Dimethyl hydroxyethyl ammonium chloride, by Clariant GmbH, Sulzbach, Germany supply

AE3S is C _12-15Alkyl ethoxy (3) sulfuric ester, by Stepan, Northfield, Illinois, USA supply

AE7 is C _12-15Alcohol ethoxylate, its average degree of ethoxylation is 7, by Huntsman, Salt Lake City, Utah, USA supply

Tripoly phosphate sodium STPP, by Rhodia, Paris, France supply

Zeolite A, by Industrial Zeolite (UK) Ltd, Grays, Essex, UK supply

1.6R silicate, by Koma, Nestemica, Czech Republic supply

Yellow soda ash, by Solvay, Houston, Texas, USA supply

Molecular weight is 4500 polyacrylic ester, by BASF, and Ludwigshafen, Germany supply

Carboxymethyl cellulose is that (Arnhem Netherlands) supplies by the Noviant branch of CPKelco BDA

By Novozymes (Bagsvaerd, Denmark) supply

Proteolytic enzyme described in the patent application US 6312936B1 (embodiment 7 to 12) is by Genencor International (Palo Alto, California, USA) supply

White dyes 1 is

AMS, white dyes 2 is CBS-X.Sulfonated Phthalocyanine Zinc is by Ciba Specialty Chemicals (Basel, Switzerland) supply

Diethylene triaminepentaacetic acid(DTPA), by Dow Chemical, Midland, Michigan, USA supply

SPC-D, by Solvay, Houston, Texas, USA supply

Sodium peroxoborate, by Degussa, Hanau, Germany supply

NOBS is an acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems, by Eastman, and Batesville, Arkansas, USA supply

TAED is a tetra acetyl ethylene diamine, trade(brand)name

By Clariant GmbH, Sulzbach, Germany supply

Stain remover is

PF, by Rhodia, Paris, France supply

The molecular weight of vinylformic acid/maleic acid is 70,000, and the ratio of propylene acid group and maleate is 70:30, by BASF, and Ludwigshafen, Germany supply

1-N, the sodium salt of N '-disuccinic acid, (S, S) isomer (EDDS) is by Octel, Ellesmere Port, UK supply

1-Hydroxy Ethylidene-1,1-Diphosphonic Acid salt (HEDP), by Dow Chemical, Midland, Michigan, USA supply

The suds suppressor agglomerate, by Dow Corning, Midland, Michigan, USA supply

Sequence table

<110>The Procter & Gamble Company

＜120〉detergent composition

<130>CM3098FM

<150>EP06115574.3

<151>2006-06-16

<160>2

<170>PatentIn version 3.3

<210>1

<211>773

<212>PRT

＜213〉genus bacillus species (Bacillus sp.)

<400>1

<210>2

<211>824

<212>PRT

＜213〉genus bacillus species (Bacillus sp.) KSM-S237

<400>2

Claims (20)

1. A composition comprising a modified cellulose derivative or a mixture thereof and a cellulase, wherein the weight ratio of the modified cellulose derivative to the active cellulase protein is 1:1 to 10000 : 1, and wherein said composition does not contain 0.7% to 0.9% by weight of said total composition of sodium nonanoyloxybenzene sulfonate, and does not contain 10% by weight of said total composition of Sodium perborate monohydrate, wherein the enzyme is a bacterial alkaline enzyme exhibiting endo-beta-1,4-glucanase activity (E.C. 3.2.1.4). 2. A composition comprising a modified cellulose derivative or a mixture thereof and cellulase, characterized in that the weight ratio of the modified cellulose derivative to the active cellulase protein is 1:1 to 10000 : 1, and wherein said composition does not contain 0.7% to 0.9% by weight of said total composition of sodium nonanoyloxybenzene sulfonate, and does not contain 10% by weight of said total composition of Sodium perborate monohydrate, which enzyme produces a reducing end amount of greater than 5 mM in an "enzyme test" as defined herein. 3. A composition as claimed in claim 1 or claim 2, wherein the enzyme is a bacterial polypeptide endogenous to a member of the genus Bacillus. 4. The composition of any one of claims 1 to 3, wherein the enzyme is a polypeptide comprising (i) at least one carbohydrate-binding structural module of the 17th family and/or (ii) at least A family 28 carbohydrate-binding structural module. 5. The composition of any one of claims 1 to 4, wherein the enzyme comprises a polypeptide endogenous to one of the following bacillus species selected from the group consisting of : AA349(DSM 12648), KSM S237, 1139, KSM 64, KSM N131, KSM635(FERM BP 1485), KSM 534(FERM BP 1508), KSM 53(FERM BP1509), KSM 577(FERM BP 1510), KSM 521 (FERM BP 1507), KSM580(FERM BP 1511), KSM 588(FERM BP 1513), KSM 597(FERM BP 1514), KSM 522(FERM BP 1512), KSM 3445(FERM BP 1506), KSM 425(FERM BP 1505 ), and their mixtures. 6. The composition of any one of claims 1 to 5, wherein the enzyme is selected from the group consisting of: (i) an endoglucanase having the amino acid sequence from position 1 to position 773 in SEQ ID NO: 1; (ii) an endoglucanase having a sequence identification number when identity is determined by GAP provided in the GCG program using a GAP generation penalty of 3.0 and a GAP extension penalty of 0.1 : a sequence of at least 90%, preferably 94%, more preferably 97%, and even more preferably 99%, 100% identical to the amino acid sequence from position 1 to position 773 in 1; or a fragment thereof having an endo-β-1,4- Glucanase activity; (iii) mixtures thereof. 7. The composition of any one of claims 1 to 6, wherein the enzyme is an alkaline endoglucanase variant, which is identified by the sequence identification number: 2 (a) position 10, (b) position 16, (c) position 22, (d) position 33, (e) position 39, (f) position 76, (g) position 109, (h) position 242, (i) position 263, (j) position 308, (k) position 462, (l) position 466, (m) position 468, (n) position 552, (o) position 564, and/or (p) sequence identification No.: 2, position 608 and/or positions corresponding thereto are obtained by substituting another amino acid for an amino acid residue of a cellulase whose amino acid sequence has at least 90 %, preferably 95%, more preferably 98%, 100% identity. 8. The composition of claim 6, wherein the enzyme is characterized by at least one of the following substituents: (a) at position 10: glutamine, alanine, proline or methionine, preferably glutamine; (b) at position 16: asparagine or arginine, preferably asparagine; (c) at position 22: proline; (d) at position 33: histidine; (e) at position 39: alanine, threonine or tyrosine, preferably alanine; (f) at position 76: histidine, methionine, valine, threonine or alanine, preferably histidine; (g) at position 109: isoleucine, leucine, serine or valine, preferably isoleucine; (h) At position 242: alanine, phenylalanine, valine, serine, aspartic acid, glutamic acid, leucine, isoleucine, tyrosine, threonine, formazine Thionine or glycine, preferably alanine, phenylalanine or serine; (i) at position 263: isoleucine, leucine, proline or valine, preferably isoleucine; (j) at position 308: alanine, serine, glycine or valine, preferably alanine; (k) at position 462: threonine, leucine, phenylalanine or arginine, preferably threonine; (1) at position 466: leucine, alanine or serine, preferably leucine; (m) at position 468: alanine, aspartic acid, glycine or lysine, preferably alanine; (n) at position 552: methionine; (o) at position 564: valine, threonine or leucine, preferably valine; and/or (p) At position 608: isoleucine or arginine, preferably isoleucine. 9. The composition of claim 7 or claim 8, wherein the enzyme is selected from the group consisting of the following endoglucanase variants: Egl-237, Egl-1139, Egl-64, Egl-N131b and their mixture. 10. The composition of any one of claims 1 to 4, wherein the enzyme is alkaline cellulase K, which has the following physical and chemical properties: (1) Activity: It has Cx enzyme activity acting on carboxymethylcellulose, weak C1 enzyme activity and weak β-glucose oxidase activity; (2) Specificity to the matrix: acting on carboxymethylcellulose (CMC), crystalline cellulose, Avicell, cellobiose and p-nitrophenyl cellobiose (PNPC); (3) have a working pH in the range of 4 to 12 and an optimum pH in the range of 9 to 10; (4) have stable pH values of 4.5 to 10.5 and 6.8 to 10, respectively, when allowed to stand at 40°C for 10 minutes and 30 minutes, respectively; (5) It can work in a wide temperature range from 10°C to 65°C, and about 40°C is recognized as the optimum temperature; (6) The influence of chelating agents: ethylenediaminetetraacetic acid (EDTA), ethylene glycol-bis-(β-aminoethyl ether) N, N, N', N"-tetraacetic acid (EGTA), N, N - bis(carboxymethyl)glycine (nitrilotriacetic acid) (NTA), sodium tripolyphosphate (STPP) and zeolites do not interfere with the activity; (7) Influence of surface active reagents: the activity is hardly inhibited by surface active reagents, such as linear alkylbenzene sulfonate sodium (LAS), alkyl sodium sulfate (AS), polyoxyethylene alkyl sodium sulfate (ES), α-olefin sulfonate sodium (AOS), α-sodium sulfonate fatty acid ester (α-SFE), sodium alkyl sulfonate (SAS), polyoxyethylene secondary alkyl ether, fatty acid salt ( sodium salt) and dimethyldialkylammonium chloride; (8) are strongly resistant to proteases; and (9) Molecular weight (measured by gel chromatography): has a maximum peak at 180,000±10,000. 11. The composition of any one of the preceding claims, wherein the bacterial alkaline enzyme exhibiting endo-beta-1,4-glucanase activity is present in an amount of 0.00005% by weight of pure enzyme to 0.15%, preferably 0.0002% to 0.02%, or more preferably 0.0005% to 0.01%. 12. The composition according to any one of the preceding claims, wherein the weight ratio of the modified cellulose derivative to the active cellulase protein is from 20:1 to 1000:1, preferably from 30:1 to 800 :1. 13. A composition according to any preceding claim, wherein the modified cellulose derivative has a molecular weight of 20,000 to 500,000, preferably 100,000 to 300,000 kDa. 14. A composition according to any one of the preceding claims, wherein the modified cellulose derivative is present in the composition in an amount of from 0.02% to 5%, preferably from 0.05% to 2%, by weight, or More preferably 0.1% to 1.5%. 15. Composition according to any one of the preceding claims, wherein the modified cellulose derivative is selected from the group consisting of anionically and non-ionically modified cellulose, preferably anionically modified. 16. A composition according to any preceding claim, wherein the modified cellulose derivative has an average degree of substitution of 0.3 to 0.9, preferably 0.4 to 0.8. 17. A detergent composition comprising oligosaccharides having a weight average molecular weight of less than 20,000 kDa, which can be combined with an enzyme as defined in any one of claims 1 to 10 obtained by the reaction of anionically modified cellulose with a weight average molecular weight of 30,000 to 500,000 kDa. 18. An aqueous wash liquor comprising the detergent composition according to claim 17, wherein the oligosaccharides are present in an amount of 0.5 ppm to 1000 ppm, preferably 0.1 ppm to 500 ppm. 19. A method of cleaning and/or treating a surface or fabric, said method comprising the steps of: optionally washing and/or rinsing said surface or fabric so that said surface or fabric is compatible with any one of the preceding claims The composition is contacted and then optionally washed and/or rinsed of the surface or fabric. 20. Use of oligosaccharides having a weight average molecular weight of less than 20,000 kDa which can be modified by an enzyme as defined in any one of claims 1 to 10 with an anion having a weight average molecular weight of 30,000 to 500,000 kDa Obtained by the reaction of cellulose, the oligosaccharides are useful in the preparation of detergent compositions for suspending soils.