CN1374999A

CN1374999A - Detergent compositions comprising a retrograded starch degrading enzyme

Info

Publication number: CN1374999A
Application number: CN00812301A
Authority: CN
Inventors: J·斯梅茨; A·布施
Original assignee: Procter and Gamble Ltd
Current assignee: Procter and Gamble Ltd; Procter and Gamble Co
Priority date: 1999-07-01
Filing date: 2000-06-30
Publication date: 2002-10-16
Also published as: EP1065261A3; CA2377723A1; EP1065261A2; JP2003511482A; AU6061600A; WO2001002530A1; BR0012144A; MXPA02000271A; EP1196531A1

Abstract

The present invention relates to laundry detergent compositions comprising a retrograded starch degrading enzyme characterised by a Retrograded Starch Index (ReSI) below 4%, preferably below 3%. Such compositions provide excellent removal of starch-containing stains and soils, and therefore excellent whiteness maintenance and dingy cleaning.

Description

The detergent composition that comprises retrograded starch degrading enzyme

Invention field

The present invention relates to comprise the detergent composition of retrogradation (retrograded) starch degrading enzyme.

Background of invention

The performance of Betengent product is determined by multiple factor, comprises the ability of removing dirt.Therefore, detergent components such as tensio-active agent, SYNTHETIC OPTICAL WHITNER and enzyme are incorporated in the washing composition.A kind of specific examples like this is to use proteolytic enzyme, lipase, amylase and/or cellulase.

Proteolytic enzyme is normally used enzyme in cleaning application.The known protein enzyme has other proteinic abilities of hydrolysis.Utilized this ability by in laundry detergent composition, mixing proteolytic enzyme natural generation or genetic engineering modified.The known lipolytic enzyme that mixes in detergent composition improves cleaning performance, for example strengthens from fabric to remove dirt and the spot that contains triglyceride level.The activity of cellulase is a kind of activity of cellulase attack cellulosic fibre or substrate and depends on cellulase and the specific function of corresponding hemicellulase that described cellulase can be the plain enzyme of inner cellulose enzyme or outer fiber.Cellulosic structure is by depolymerization or resolve into less also easier thus dissolving and dispersive part.Particularly this activity to fabric provides cleaning, recovery, softness and the common feel character of improving to woven fabric structure.Having recognized that amylase provides in detergent composition from tableware or crust removes starch food products residue or starch film or provides the starch soil that generally runs into laundry and wash up application and the cleaning performance of other dirts.

In fact, starchy material such as amylose starch and amylopectin have constituted one of major ingredient of the dirt/spot that runs in laundry, wash up or hard surface cleaning operation.In addition, industrial textile is used starchy material in their textile finishing operation.Thus, since a long time ago, amylase has been impregnated in the Betengent product, is used to remove amyloid spot.Yet, find the starch that this normally used washing composition amylase can not the hydrolysis retrogradation surprisingly.

As what in J.A.Radiey " Starch and its Derivatives " the 4th edition Chapman and Hall Ltd 194-201 page or leaf, studied; To be that explanation starch is mutually spontaneous change or through a term of aging gel in retrogradation.This is the increase that is caused and cause degree of crystallinity by starch molecule inherently in conjunction with the trend of another molecule.Low concentration solution becomes muddiness all the more owing to starch molecule associates than macroparticle gradually.Spontaneous deposited phenomenon generation and sedimentary starch show and are returned to the insoluble virgin state of its cold water.Higher concentration gel takes place through cooling, through aging, because starch molecule associates further, it firmly becomes harder.This is to cause owing to the strong hydrogen bonding between the hydroxyl on the adjacent starch molecule forms trend.

In starch industry was used, the variation that takes place in the retrogradation process was quite important.In the structural changes of the aging and for example canned soup of amyloid other foods, pea, meat product etc., this is considered to important factor at bread.Starch and retrogradation starch are also found in textiles, papermaking and adhesives industry.In fact, in textiles processing, fabric starch gluing.According to photoresist coating process, forming retrogradation starch on the fabric and in degumming technology afterwards, can not be removed.In addition, most of stain of finding on fabric contains starch, and for example in laundry basket, it will return to this associating starch reticulated structure through aging.Therefore, afterwards, on the fabric that is cleaned, find to contain the material of this retrogradation starch.In addition, find that surprisingly the starch of this retrogradation has further been held back the stolen goods dirt, in the time of on being presented on fabric face, there is dirty outward appearance on the surface that causes being cleaned.

The starch of this retrogradation shows the ability of the anti-amylorrhexis of enhanced, only slightly micro dissolution and redispersion difficulty under common temperature, and if particularly the starch of retrogradation dry situation at first, this has confirmed that further the gel soundness increases gradually.In fact, having found that retrogradation starch forms highly stable structure and only fusion under unusual high-temperature, is 150 ℃ for amylose starch for example, is 60 ℃ or is 120 ℃ for the amylose starch lipid of complexity for amylopectin.The degree and the time of retrogradation are depended on starch type: it can change in 10%-90% starch containment.It is very little of not effect to have found that common washing composition amylase has retrogradation starch.

From as can be seen above-mentioned, need preparation can solve the Betengent product of removing the dirt/spot problem that contains this retrogradation starch.Therefore, satisfy above-mentioned purpose by preparing a kind of detergent composition that can efficiently act on the enzyme of retrogradation starch that contains.This kind of enzyme is characterised in that retrogradation starch index (ReSI) is lower than 4%, preferably is lower than 3%.Preferably, detergent composition of the present invention will comprise the combination of several retrograded starch degrading enzymes.

Preferably, detergent composition of the present invention further comprises detergent components such as proteolytic enzyme, lipase and/or conventional amylase, starch-debranching enzyme or Starch debranching enzyme Type II, nonionogenic tenside, SYNTHETIC OPTICAL WHITNER and/or the anti redeposition agent that is selected from another kind of detergent enzyme.

EP368341 has described detergent composition, and at least a starch-debranching enzyme that it comprises tensio-active agent and is selected from Starch debranching enzyme, isopullulanase and isoamylase is preferably used α-Dian Fenmei, improved starch based spot washing composition.GB2228945 discloses a kind of wash up machine composition, and it comprises the α-1 that can rupture, the enzyme of 6-glucoside bond.WO98/26078 relates to the H mutant alpha-amylases of improved stability.EP450627 has described a kind of new detergent composition that the starch based dirt is had the alkaline Starch debranching enzyme of fabulous soil release characteristics that contains.WO94/19468 relates to a kind of dna fragmentation that contains as the gene of the alkaline Starch debranching enzyme of detergent components.US5665585 relates to amino acid and the dna sequence dna of the unique glucoamylase P with high debranching activity, Trichoderma host cell with this sequence conversion, the expression of this reorganization glucoamylase P and this recombinase and use its host transformed, the particularly industrial application in zymamsis.US3640877 has described production of detergents, it contains as the system of the glucose of hydrogen peroxide precursor and glucose oxidase or starch, amyloglucosidase and glucose oxidase and is stabilized in the oxyamine that uses the hydrogen peroxide that forms in the washing composition process.WO95/29996 discloses a kind of new glucose oxidase, its production method and its application in bleaching and detergent composition with and as the application of dough reinforcer.Described enzyme has many application, preferred combination to be selected from the another kind of enzyme of amyloglucosidase, lactoperoxidase, α-Dian Fenmei or Fructus Hordei Germinatus sugar exoamylases aspect the human body nursing and in the baking industry.

Yet, in laundry detergent composition, use the enzyme that can efficiently act on retrogradation starch, be used to remove the spot-dirt that contains retrogradation starch, also never be realized in the past.

Summary of the invention

The present invention relates to laundry detergent composition, it comprises retrograded starch degrading enzyme, is characterised in that retrogradation starch index (ReSI) is lower than 4%, preferably is lower than 3%.Therefore this composition can be removed amyloid spot and dirt admirably, can keep fabulous whiteness and take out stains.

Detailed Description Of The Invention

The necessary component of detergent composition of the present invention is the enzyme (hereinafter referred to as " retrograded starch degrading enzyme ") that α-polysaccharide is had active and efficient degradation retrogradation starch material.This kind of enzyme is characterised in that retrogradation starch index (ReSI) is lower than 4%, preferably is lower than 3%.

In fact, found to satisfy the retrogradation starch that the enzyme of these standards can efficient degradation exists on fabric, therefore excellent Fouling Cleaning power is provided.The fabric that has shown repeated washing, especially white fabrics have been gathered low-density ash, yellow.Without being limited by theory, believe that this retrogradation starch that retains has attracted dirt and caused fabric that canescent dark outward appearance is arranged.Believe this retrogradation starch layer of the selected endonuclease capable hydrolysis of the present invention, therefore excellent Fouling Cleaning power is provided.In view of above-mentioned, the objective of the invention is specifically to solve the cleaning performance problem of this dirt.Therefore, the present invention specifically relates to select to have the enzyme that high Fouling Cleaning is renderd a service, and it is specifically selected by following scheme, wherein uses carbon black to imitate the dirt outward appearance.

Measure the enzymic hydrolysis of retrograded starch degrading enzyme of the present invention by color index.Retrogradation starch index (ReSI) is defined as follows:

With retrogradation starch and carbon black on the fabric load.Retrogradation starch deposited on the fabric and with carbon black be embedded in the starch structure color indicator that it exists as retrogradation starch.Before handling and afterwards, use spectrometry, be determined at the retrogradation starch that retains on the tested fabrics by the mensuration color with enzyme.The colour intensity % that remains in the carbon black on the fabric that is measured with by the experiment enzymic hydrolysis be not directly proportional from the retrogradation starch that fabric is removed.The colour intensity % of carbon black is lower, illustrates and has removed carbon black well, and it has reacted has removed retrogradation starch preferably.Therefore, colour intensity % is low is the indication of high-performance enzyme.

Press following mensuration retrogradation starch index (ReSI):

1. knitted cotton is cut into sheet (8 * 20cm)

2. in the 500ml softening water, put into 50g W-Gum (Amylum).

3. on magnetic stirring plate, stir this solution (Ikamag, position 4)

4. in beaker, add the 10g carbon black (gac of buying by Fluka gradually

05100)。

5. heat this starch-carbon black solution: maximum heating, 4 stir in the position.

6. when temperature is between 60-70 ℃, form gel.Heated this gel about 5 minutes

Clock.

7. remove beaker from hot-plate.

8. cover this knitted cotton with starch-carbon black gel, use little wallpaper roller little by little will coagulate

Glue is coated with to be spread, and surface-coatedly covers black gel until this.

With each knitted cotton sample packaging in aluminium foil and be stored in the refrigerator, through 3 days.

10. after 3 days, open the packing and the arrangement of fabric and dry.

11. the above-mentioned tested fabrics that obtains is put into bottle formula detergency test instrument (each bottle formula

The detergency test instrument has 4 fabrics) 40 ℃ under the 400ml sodium acetate buffer

In and by the experiment enzyme best pH under, through 1 hour, and Rotary drying was knitted

Thing.Measure fabric with Spectraflash Datacolor International

Colour intensity.The incidental technical data sheet of enzyme sample that-usefulness is purchased finds by the best pH of experiment enzyme and/or can be obtained by the curve of the relative pH of active %.For example, the data slice indication pH of the amyloglucosidase AMG300L that is sold by Novo Nordisk is 4.3.-this is tested under excessive experiment enzyme exists and carries out.When the concentration of further increase experiment enzyme can not cause corresponding ReSI exponential further to reduce, just reached this excessive concentrations.For example, this concentration is corresponding to the 4ml amyloglucosidase AMG3000L that is sold by Novo Nordisk A/S (the active and 145mg/ml protein content of 300GA/ml).

12. before handling and afterwards, measure the colour intensity of fabric with enzyme.Have equipment

The scheme of Spectraflash 500 Datacolor International:

^*SPECULAR：Exclude； ^*APERTURE：Ultrasmall； ^*UV?FILTER

The cut-off cock strainer of 400nm).

13. colour intensity % calculates the K/S curvilinear integral that is based on visible spectrum range, wherein

K/S is that the ratio of Kubelka-Munk constant K and S is (by Datacolor

The Datamaster software program that International obtains).By handling with enzyme

Before and the ratio of the area below the K/S curve of fabric afterwards to obtain color strong

Degree.Colour intensity is lower than 4%, and preferred 3% is the indication of very white and Fouling Cleaning performance.The amyloglucosidase of selling with trade(brand)name AMG by NovoNordisk A/S-in bottle formula detergency test instrument, tested sample AMG300L under 4ml content with active 300AG/ml, obtaining colour intensity % is 3.8% (standard deviation 0.15).

By the weight of total detergent composition, this retrograded starch degrading enzyme general content in detergent composition of the present invention is 0.0002%-10%, preferred 0.001%-2%, the more preferably pure enzyme of 0.001%-1%.

For concrete application, preferred retrograded starch degrading enzyme is alkaline retrograded starch degrading enzyme, and the enzymic activity that promptly has is at pH7-12, at least 10% of its maximum activity under preferred 10.5, preferably at least 25%, more preferably at least 40% enzyme.Preferred retrograded starch degrading enzyme is at pH7-12, the preferred enzyme that has its maximum activity for 10.5 times.

For the object of the invention, having ReSI is lower than 4% retrograded starch degrading enzyme and can be selected from following type enzyme (IUPAC classification): amyloglucosidase EC3.2.1.3, α-Dian Fenmei EC3.2.1.1, βDian Fenmei EC3.2.1.2, isoamylase EC3.2.1.68, Starch debranching enzyme type i EC3.2.1.41, isopullulanase EC3.2.1.57, new Starch debranching enzyme EC3.2.1.135, the Starch debranching enzyme Type II, dextrin dextranase EC2.4.1.24, Maltose 4-glucosyltransferase EC2.4.1.19 and (product) maltogenic alpha-amylase enzyme EC3.2.1.133.Preferably, detergent composition of the present invention comprises the combination of several retrograded starch degrading enzymes.

Amyloglucosidase, EC3.2.1.3 are dextran 1, and the 4-alpha-glucosidase is also referred to as " glucoamylase; gamma amylase, lysosmal, acid maltase or outer-1; 4-alpha-glucosidase ", and its systematic name is 1,4-α-D-dextran glucose lytic enzyme.Amyloglucosidase Polysaccharides such as α in the starch-1,4 and α-1,6 key dissociate glucose unit from the non-reduced end of polysaccharide.These two kinds of activity are different.By hydrolyzing alpha-1,4 and α-1,6 glucoside bond, amyloglucosidase is from the non-reduced end of glucose polymer such as the starch β-D-glucose unit that dissociates.The ability of their hydrolyzing alphas-1,6 glucoside bond is different from starch-debranching enzyme greatly.

α-Dian Fenmei, EC3.2.1.1 is to make 1 in the polysaccharide of the D-glucose unit that contains three or more α-1,45 bonding, in 4-α-D-glucoside bond 1 of hydrolysis, 4-α-D-dextran glucan hydrolase.

Beta-amylase, EC3.2.1.2 is 1,4-α-D-dextran maltose lytic enzyme, it makes 1 in the polysaccharide, and the outer hydrolysis of 4-α-D-glucoside bond is removed in succession maltose unit from the non-reducing end of this chain.

This group starch-debranching enzyme generally includes Starch debranching enzyme Class1, isopullulanase and isoamylase.

Starch debranching enzyme Class1 enzyme is classified as EC3.2.1.41 by the IUPAC classification and systematic name is a Schardinger dextrin 6-glucan hydrolase.In amylopectin enzymic hydrolysis pullulan (amylopectin), amylopectin and the glycogen 1,6-α-D-glucoside bond and the α of amylopectin and glycogen-and the beta-amylase limit dextrin in 1,6-α-D-glucoside bond and anti-ly partly decompose a chain oligosaccharides of generation by them.Because this character, Starch debranching enzyme is called as " debranching factor ".In fact, Starch debranching enzyme is the α-1 of amylopectin of only rupturing, 6-glucoside bond and the final enzyme that produces trisaccharide maltose.

Isopullulanase is classified as EC3.2.1.57 by the IUPAC classification and systematic name is an amylopectin 4-glucan hydrolase.This isopullulanase is hydrolyzed into different panose (6-α-malt-base glucose) with amylopectin.

Isoamylase has makes glycogen take off the ability of propping up.They are classified into EC3.2.1.68 by the IUPAC classification and systematic name is a glycogen 6-glucan hydrolase.In this isoamylase hydrolysis glycogen, amylopectin and their the β-limit dextrin 1,6-α-D-glucoside Zhi Jian.This isoamylase is inequality in Starch debranching enzyme, and they do not have the ability of attack amylopectin, has limited effect and them that glycogen is had effect fully to α-limit dextrin.

New Starch debranching enzyme is defined as that amylopectin is degraded into the enzyme of panose and they are classified as EC3.2.1.135 by the IUPAC classification.New Starch debranching enzyme is an amylopectin 4-D-glucan hydrolase, have that division finds in starch and carbohydrate type spot or dirt usually 1,4-and 1, the ability of 6-glucoside bond.For example, this kind of enzyme is hydrolyzed into panose (6-alpha-D-glucose base maltose) with amylopectin.Particularly, but the reaction that new Starch debranching enzyme catalysis is four types, comprise hydrolyzing alpha-(1 → 4)-glucoside bond, hydrolyzing alpha-(1 → 6)-glucoside bond forms α-(1 → 4)-glucoside bond and forms α-(1 → 6)-glucoside bond by transglycosylation by transglycosylation.On the contrary, a kind of or two kinds of reactions of catalysis in these reactions of other known enzyme catalysis, second kind of catalyzed reaction is weak.In addition, this reaction of four types is by same mechanism catalysis.

Starch debranching enzyme Type II enzyme is defined as starch Starch debranching enzyme (amylopullulanase) and except (the α-1 of the side chain in Polysaccharides and the dextrin, the 6-key) outside, hydrolyzing alpha brokenly also, the 1-4 key, this is opposite with Starch debranching enzyme Class1 enzyme, Starch debranching enzyme Class1 enzyme is the α in the hydrolysis side chain polysaccharide only, and 1, the 6-key.

Suitable in addition enzyme in the amylase type is a dextrin dextranase.Dextrin dextranase (EC2.4.1.2) is the enzyme that produces dextran and be derived from the low molecular weight oligomeric sugar of starch.

Cyclomaltodextrin glucanotransferase (CGTASE), EC2.4.1.19 is by forming 1,4-α-D-glucoside bond and cyclisation part 1, the enzyme of 4-α-D-dextran chain and to have systematic name be 1,4-α-D-Dextran 4-α-D-(1,4-α-D-dextran) transferring enzyme (cyclisation).

(product) maltogenic alpha-amylase enzyme

What also be fit to is (product) maltogenic alpha-amylase enzyme with IUPAC classification EC3.2.1.133,1 in its Polysaccharides, and 4-alpha-D-glucose glycosidic bond is so that remove in succession α-maltose unit from the non-reduced end of this chain.(product) maltogenic alpha-amylase enzyme that is fit to is the amylase by genus bacillus clone described in EP120693, commercial be to buy by trade(brand)name Novamyl from NovoNordisk A/S; The variant of the Fructus Hordei Germinatus sugar α-Dian Fenmei of in WO99/43793, describing and (product) maltogenic alpha-amylase enzyme variant (physicochemical property of variation, for example schizotype of the thermostability of the best pH of Bian Huaing, improvement, enhanced specific activity, variation or enhanced reduction starch retrogradation or bread aged ability) that has the hybrid enzyme of active CGT-enzyme variants of (products) maltogenic alpha-amylase enzyme and structure and in WO99/47394, describe based on the character improvement of (products) maltogenic alpha-amylase enzyme Novamyl of three-dimensional structure with CGT-enzymic activity.

The certain enzyme that satisfies ReSI standard of the present invention is the amyloglucosidase of for example being sold with trade(brand)name AMG by Novo Nordisk A/S.

Another embodiment of the present invention, detergent composition of the present invention also can comprise one or more starch binding domainss (Starch-binding domian).This starch binding domains can add in the detergent composition of the present invention, there to be or to can be used as the part of chimeric retrograded starch degrading hybrid enzyme like this.In fact, retrograded starch degrading enzyme of the present invention preferably has or is added into starch binding domains (SBD).General enzyme such as amylase, cellulase and zytase have the modular structure that is made of catalyst structure domain and at least a on-catalytic structural domain, and its function generally is described to the function of polysaccharide binding domains (PBD), starch binding domains (SBD), cellulose binding domain (CBD) and xylan binding domains.The effect of these binding domainss is substrates of selective binding enzyme, and especially, the major function of SBD is in conjunction with starch.Find that surprisingly the retrograded starch degrading enzyme that comprises the detergent composition of the present invention of one or more SBD and/or wherein comprise this SBD will provide more effective removal amyloid dirt/spot.Find that also this kind of enzyme can more effective one-tenth the manner preparation.Without being limited by theory, believe that this retrograded starch degrading enzyme more effectively acts on their substrates in washing soln especially, so improved the deposition on amyloid stain, improved and/or new performance.In addition, believe SBD decohesion the starch surface, cause higher hydrolysis rate.

Being used for SBD that the present invention is fit to is included in and is derived from black aspergillus (Aspergillusniger, glucoamylase Sigma) and be derived from SBDs in the beta-galactosidase enzymes of Aspergillus awamori (A.awamori).The recovery of SBDs and fusion can realize described in following document: Ford, C. etc., J.Cell.Biochem. (Suppl.) 14D:30 (1990) and Chen, L. etc., Abst.Annu.Meet.Am.Soc.Microbiol.90:269 (1990).Detergent components

Detergent composition of the present invention must contain at least a additional detergent components.The exact nature of these additional ingredients and its incorporation will depend on the physical form of composition and the classification of its cleaning operation that is used for.

Detergent composition of the present invention preferably comprises another kind of conventional amylase, conventional starch-debranching enzyme, conventional Starch debranching enzyme Type II, proteolytic enzyme or lipase; Nonionogenic tenside, SYNTHETIC OPTICAL WHITNER and/or anti redeposition agent.

The present invention relates to laundry detergent composition, it comprises retrograded starch degrading enzyme, is characterised in that retrogradation starch index (ReSI) is lower than 4%, preferably is lower than 3%.This composition can be removed amyloid spot and dirt admirably, therefore can keep fabulous whiteness and Fouling Cleaning.

In preferred embodiments, the present invention relates to comprise the laundry and/or the Fabrid care composition (embodiment 1-16) of retrograded starch degrading enzyme.When having found that the selected enzyme of the present invention is in being included in the application of wash up or hard surface cleaning, also confirm to remove amyloid stain excellently.Therefore, in second embodiment, the present invention relates to wash up or household cleaning composition (embodiment 17-23).

The present composition for example can be formulated as hand washing and machine dishwashing compositions, hand washing or machine laundry detergent composition, it comprises laundry additive composition and is applicable to fabric softener composition that soaks and/or add when the composition of the dirty fabric of pre-treatment, rinsing and the composition that is used for common family's hard surface cleaning operation.When being mixed with the composition that is used for the manual dishwashing method, the present composition preferably contains tensio-active agent and preferably contains other detergent components, is selected from metal ion, solvent, hydrotropic agent and the auxiliary enzymes of organic polyhydroxyl compound, suds booster, II group.

When being mixed with the composition that is suitable in the washing machine washing method, the present composition preferably contains tensio-active agent and these two kinds of components of washing-aid compound and additional one or more detergent components, and this detergent components is preferably selected from organic polyhydroxyl compound, SYNTHETIC OPTICAL WHITNER, auxiliary enzymes, suds suppressor, dispersion agent, lime soap dispersing agent, soil-suspending agent and anti redeposition agent and corrosion inhibitor.Laundry composition also can contain softening agent, and it is as additional detergent components.This composition that contains amyloglucosidase provides removal, maintenance whiteness and cleaning dirt to starch-containing spot when being mixed with laundry detergent composition.

The present composition also can be used as the detergent additives product.This additive product is the performance that is used for replenishing or promoting conventional detergent composition.

According to detergent composition of the present invention can be liquid, cream, gel, bar, sheet, spray, foams, powder or particle form.Particulate composition can also be " closely knit " form, and liquid composition can also be " concentrating " form.If necessary, laundry detergent composition of the present invention is 400-1200g/l 20 ℃ of density of measuring down, preferred 500-950g/l composition." closely knit " form of the present composition is reacted by the amount of mineral filler salt best by density with regard to forming.Mineral filler salt is the conventional component of powder detergent composition.In conventional detergent composition, filling salt is to exist in a large number, to be generally the 17-35% of total composition weight.In closely knit composition, the content of filling salt is no more than 15% of total composition, preferably is no more than 10%, is most preferably not exceeding 5% of composition weight.Mineral filler salt, for example the meaning is to be selected from basic metal and alkaline earth metal sulphate and muriate in the present composition.Preferred filling salt is a sodium sulfate.According to liquid detergent composition of the present invention can also be " conc forms ", and in this case, liquid detergent composition according to the present invention will contain the water of lower amount than conventional liq washing composition.The water-content of general concentrated liquid detergent by detergent composition weight, preferably is less than 40%, more preferably less than 30%, most preferably is less than 20%.

Be used for the detergent components that the present invention is fit to and be selected from following component.Surfactant system

Detergent composition of the present invention generally comprises surfactant system, and wherein tensio-active agent can be selected from non-ionic type and/or anionic and/or cationic and/or both sexes and/or amphoteric ion type and/or semi-polarity tensio-active agent.

Preferably, detergent composition of the present invention comprises nonionogenic tenside, is preferably based on the nonionogenic tenside of the condenses of polyoxyethylene and alcohol.In fact, find that surprisingly detergent composition of the present invention also comprises nonionogenic tenside, has improved from fabric, tableware and other crusts and has removed starch.Therefore without being limited by theory, believe that nonionogenic tenside is adsorbed onto on the starch particle surface, destroyed starch structure and influenced and suppressed the retrogradation process of starch.This interference to structure has increased the proximity of enzyme to its substrate.In addition, nonionogenic tenside also can be used in preprocessing process, therefore can reduce the retrogradation process of starch.Therefore, amyloid stain is easier by enzymic hydrolysis with by the collaborative starch soil that destroys of the nonionogenic tenside of retrograded starch degrading enzyme and existence.

The general content of tensio-active agent is 0.1% to 60% weight, and preferred incorporation is 1% to 35% of detergent composition weight of the present invention, most preferably 1%-30%.

The preferred tensio-active agent of being prepared be with composition in the enzyme component that exists compatible.In liquid or gelatinous composition, most preferably the tensio-active agent of being prepared makes its promotion or do not reduce the stability of any enzyme in these compositions at least.

Nonionogenic tenside: the condensation product of the polyoxyethylene of alkylphenol, polyoxypropylene and polyoxy butylene is suitable as the nonionic surface active agent in the surfactant system of the present invention, preferably polyoxyethylene condenses.These compounds comprise having and contain about 6 to about 14 carbon atoms, and preferred about 8 is the alkylphenol of alkyl of straight or branched configuration and the condensation product of oxyalkylene to about 14 carbon atoms.In preferred embodiments, the amount of the oxygen ethene that exists in every mole of alkylphenol equals about 2 to about 25 moles, more preferably from about 3 to about 15 moles.Commercial such ionic surfactant pack of buying is drawn together Igepal ^TMCO-630 is sold by GAF Corporation; And Triton ^TMX-45, X-114, X-100 and X-102, they all are by Rohm﹠amp; Haas company sells.These tensio-active agents are commonly referred to alkyl phenolic alkoxy thing (for example alkylphenol ethoxylate).

Primary and secondary Fatty Alcohol(C12-C14 and C12-C18) and about 1 condensation product to about 25 moles of ethylene oxide are suitable as the nonionogenic tenside in the nonionic surfactant system of the present invention.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) both can be straight chain also can be side chain, can be primary alconol or secondary alcohol, and generally contain and have an appointment 8 to about 22 carbon atoms.Preferably by every mol of alcohol, pure and about 2 condensation products to about 10 moles of ethylene oxide, wherein Chun alkyl contains and has an appointment 8 to about 20 carbon atoms, and more preferably from about 10 to about 18 carbon atoms.Every relatively mol of alcohol exists about 2 to about 7 mole oxygen ethene, most preferably 2 to 5 mole oxygen ethene in described condensation product.Commercial such ionic surfactant pack of buying is drawn together Tergitol ^TM15-S-9 (C ₁₁-C ₁₅The condensation product of straight chain alcohol and 9 moles of ethylene oxide), Tergitol ^TM24-L-6 NMW (C ₁₂-C ₁₄The condensation product of primary alconol and 6 moles of ethylene oxide, and have narrow molecular weight distribution), sell by Union Carbide Corporation for two kinds; The Neodol that also has Shell Chemical Company to sell ^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 Procter﹠amp; The Kyro that Gamble Company sells ^TMEOB (C ₁₃-C ₁₅The condensation product of alcohol and 9 moles of ethylene oxide); With the Genapol LA O3O or the LA O5O (C that sell by Hoechst ₁₂-C ₁₄The condensation product of alcohol and 3 or 5 moles of ethylene oxide).The preferred HLB scope of these products is 8-11, most preferably 8-10.

What also be suitable as nonionogenic tenside in the surfactant system of the present invention is the U.S. Pat 4 that is presented to Llenado on January 21st, 1986,565, disclosed alkyl polysaccharide in 647, it has about 6 to about 30 carbon atoms, preferred about 10 to hydrophobic grouping of about 16 carbon atoms and polysaccharide many glycosides hydrophilic radical for example, this hydrophilic radical contains has an appointment 1.3 to about 10, and preferred about 1.3 to about 3, and most preferably from about 1.3 to about 2.7 sugar units.Can use any reducing sugar that contains 5 or 6 carbon atoms, for example available glucose, semi-lactosi and galactosyl partly replace glycosyl part (hydrophobic group randomly is connected on the positions such as 2-, 3-, 4-, thereby obtains glucose or the semi-lactosi opposite with glucoside or galactoside).Key can be for example between a position of 2-, 3-, 4-and/or 6-position and another sugar unit of previous sugar unit between sugar.

Preferred alkyl polyglycoside has following formula:

R ²O (C _nH _2nO) _t(glycosyl) _xR wherein ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and its mixture, wherein alkyl contains and has an appointment 10 to about 18 carbon atoms, and preferred about 12 to about 14 carbon atoms; N is 2 or 3, preferred 2; T is 0 to about 10, preferred 0; X is about 1.3 to about 10, and preferred about 1.3 to about 3, most preferably from about 1.3 to about 2.7.Glycosyl is preferably by the glucose deutero-.For preparing these compounds, at first make alcohol or alkyl polyethoxye alcohol, form glucoside (being connected) with glucose or the reaction of grape glycogen then at 1.1 of another glycosyl units 2-, 3-, 4-and/or the 6-position with previous glycosyl units preferably mainly can be connected between 2 then.

Oxyethane also is suitable as the additional nonionic surfactant system of the present invention with the condensation product of the hydrophobic group that forms by propylene oxide and propylene glycol condensation.The hydrophobic part of these compounds preferably has molecular weight about 1500 to about 1800, and performance water outlet insoluble.The addition polyoxyethylene partly tends to increase the water-soluble of bulk molecule on this hydrophobic part, and the fluid characteristics of product is maintained to about 50% this point place that polyoxyethylated content is the condensation product gross weight, and this is equivalent to and the about 40 moles of ethylene oxide condensations of as many as.The example of this type compound comprises some commercial Plurafac that buy ^TMLF404 and Pluronic ^TMTensio-active agent, it is sold by BASF.

Other nonionogenic tensides that are fit to product that to be oxyethane carry out condensation with the product that is obtained by propylene oxide and reacting ethylenediamine.The hydrophobic part of these products is made of the reaction product of quadrol and excessive propylene oxide, and generally has about 2500 to about 3000 molecular weight.This hydrophobic part and ethylene oxide condensation be to a certain degree, and promptly condensation product contains and has an appointment 40% to about 80% weight polyoxyethylene, and has about 5000 to about 11000 molecular weight.The example of this type nonionogenic tenside comprises some commercial Tetronic that buy ^TMCompound is sold by BASF.

Preferred is polyoxyethylene condenses, primary and secondary Fatty Alcohol(C12-C14 and C12-C18) and about 1 condensation product to about 25 moles of ethylene oxide, alkyl polysaccharide and its mixture of alkylphenol as the nonionogenic tenside in the surfactant system of the present invention.The C that most preferably has 3 to 15 oxyethyl groups ₈-C ₁₄Alkylphenol ethoxylate and C with 2 to 10 oxyethyl groups ₈-C ₁₈Alcohol ethoxylate (preferred C ₁₀On average) and its mixture.

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

R wherein ¹Be H, or R ¹Be C _1-4Alkyl, 2 hydroxyethyls, 2-hydroxypropyl or its mixture, R ²Be C _5-31Alkyl, Z are the polyhydroxy alkyls with the straight-chain alkyl chain that directly is connected with at least 3 hydroxyls, or its oxyalkylated derivative.Preferred R ¹Be methyl, R ²It is straight chain C _11-15Alkyl or C _16-18Alkyl or alkenyl be Oleum Cocois alkyl or its mixture for example, and Z is that for example glucose, fructose, maltose, lactose obtain by the reducing sugar in reductive amination process.

Anion surfactant: the anion surfactant that is fit to use is linear alkylbenzene sulfonate, alkyl sulfonate surfactants, comprise according to " U.S. oiling scholar learns magazine " (" The Journal of the American Oil Chemists Society "), 52 (1975), the method for 323-329 page or leaf gaseous state SO ₃The sulfonated straight chain C ₈-C ₂₀Carboxylic acid (being lipid acid) ester.The raw material that is fit to comprises that natural lipoid material is as by butter, palm wet goods deutero-material.

The preferred alkyl sulfonate surfactants that is used in particular for laundry applications comprises the alkyl sulfonate surfactants with following structural formula:

R wherein ³Be C ₈-C ₂₀Alkyl, preferred alkyl, or its mixture, R ⁴Be C ₁-C ₆Alkyl, preferred alkyl, or its mixture, M is a positively charged ion, itself and alkyl ester sulfonate radical form water-soluble salt.The salt-forming cation that is fit to 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, R ⁴Be methyl, ethyl or sec.-propyl.Particularly preferably be wherein R of methyl ester sulfonate ³Be C ₁₀-C ₁₆Alkyl.

Other anion surfactants that are fit to comprise alkyl sulfate surfactant, and it is formula ROSO ₃The water-soluble salt of M or acid, wherein R C preferably ₁₀-C ₂₄Alkyl, preferred alkyl or have C ₁₀-C ₂₀The hydroxyalkyl of moieties, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl, M is H or positively charged ion, alkali metal cation (for example sodium, potassium, lithium) for example, or ammonium or replace ammonium (for example tetramethyl-ammonium and lupetidine positively charged ion of methyl, dimethyl and trimethyl ammonium positively charged ion and quaternary ammonium cation for example, and by alkylamine for example ethamine, diethylamine, triethylamine and its mixture deutero-quaternary ammonium cation etc.).General for lower wash temperature (for example being lower than about 50 ℃), preferred C ₁₂-C ₁₆Alkyl chain, and to higher wash temperature (for example being higher than about 50 ℃), preferred C ₁₆-C ₁₈Alkyl chain.

Other anion surfactants that can be used for washing purpose also can be included in the detergent composition of the present invention.These can comprise salt (ammonium salt that comprises for example sodium, potassium, ammonium and replacement is for example single, two and triethanolamine salt), the C of soap ₈-C ₂₂Uncle or secondary paraffin sulfonate, C ₈-C ₂₄The sulfonated poly carboxylic acid that alkene sulfonate, the pyrolysis product by the sulfonation alkaline earth metal citrate make, for example at british patent specification No.1, described in 082,179; C ₈-C ₂₄Alkyl polyglycol ether sulfate (containing as many as 10 mole oxygen ethene); Alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol sulfonate, alkylphenol oxygen Vinyl Ether vitriol, paraffin sulfonate, alkylphosphonic, isethionate be acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinic acid monoesters (particularly saturated and undersaturated C for example ₁₂-C ₁₈Monoesters) and sulfosuccinic acid diesters (particularly saturated and undersaturated C ₆-C ₁₂Diester), the vitriol of acyl sarcosinate, alkyl polysaccharide for example the primary alkyl sulphates of alkylpolyglucoside vitriol (compound of the non-sulfuric acidization of nonionic described below), side chain and alkyl polyethoxye carboxylate salt for example those have formula RO (CH ₂CH ₂O) _kCH ₂COO ^-M ⁺Salt, wherein R is C ₈-C ₂₂Alkyl, k are 1 to 10 integer, and M is the positively charged ion that forms soluble salt.Resinous acid and hydrogenated resin acid also are suitable for, for example rosin, staybelite, and be present in tallol or by tallol deutero-resinous acid and hydrogenated resin acid.

Other examples are described in " tensio-active agent and washing composition " (Surface ActiveAgents and Detergents) (I and II volume, by Schwartz, Perry and Berch write) book.Various such tensio-active agents also are disclosed in U.S. Pat the 3,929,678, the 23rd hurdle 58 of authorizing people such as Laughlin on December 30th, 1975 prevailingly and walk in 29 hurdles, 23 row (this paper quotes for referencial use).

When containing them, laundry detergent composition of the present invention typically contains has an appointment 1% to about 40%, and preferred about 3% to this anion surfactant of about 20% weight.

Highly preferred anion surfactant comprises alkyl alkoxylated sulfate surfactant, and it is formula RO (A) _mSO ₃The water-soluble salt of M or acid, wherein R is unsubstituted C ₁₀-C ₂₄Alkyl or have 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 the m value is greater than 0, generally between about 0.5 to about 6, more preferably between about 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.Alkyl ethoxylated sulfate and alkyl propoxylated sulphates are that the present invention expects.The specific examples of the ammonium cation that replaces comprises methyl, dimethyl, trimethyl ammonium positively charged ion and quaternary ammonium cation for example tetramethyl-ammonium and lupetidine positively charged ion, and those are by alkylamine for example ethamine, diethylamine, triethylamine and its mixture deutero-positively charged ion etc.The tensio-active agent that exemplifies has 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), suitable sodium and the potassium of being selected from of M wherein.

Detergent composition of the present invention also can contain positively charged ion, both sexes, zwitter-ion and semi-polarity tensio-active agent, and non-this paper nonionic and/or the anion surfactant stated.

Cats product: the cats product that is suitable in the detergent composition of the present invention is those tensio-active agents with a long chain hydrocarbon groups.The example of this cationic surfactant comprises for example alkyl trimethyl ammonium halide of ammonium salt tensio-active agent, and those tensio-active agents with following formula:

[R ²(OR ³) _Y] [R ⁴(OR ³) _Y] ₂R ⁵N ⁺X ^-R wherein ²Be in its alkyl chain, to contain 8 alkyl or the alkyl benzyls of having an appointment, each R to about 18 carbon atoms ³Be selected from-CH ₂CH ₂-,-CH ₂CH (CH ₃)-,-CH ₂CH (CH ₂OH)-,-CH ₂CH ₂CH ₂-and its 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 molecular weight less than about 1000 any hexose or hexose polymeric groups, and hydrogen (when y is not 0); R ⁵Be same R ⁴Identical group, or alkyl chain, wherein R ²Add R ⁵No more than about 18 of the total number of carbon atoms; Each y is 0 to about 10, and y value summation is 0 to about 15; X is any compatible negatively charged ion.

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

Formula I wherein R1 is the long alkyl (C6-C10) of short chain, or the alkyl amido alkyl of formula (II):

Formula IIy is 2-4, preferred 3.R wherein ₂Be H or C1-C3 alkyl, wherein x is 0-4, preferred 0-2, most preferably 0, R wherein ₃, R ₄And R ₅Being identical or different, can be the alkyl (C1-C3) of short chain, or the alkoxylated alkyl of formula III, wherein X ^-Be counter ion, preferred halogen ion, for example chlorine or methylsulfate,

Formula III R ₆Be C ₁-C ₄, z is 1 or 2.

Preferred quaternary ammonium surfactant be formula I defined those: R wherein ₁Be C ₈, C ₁₀Or its mixture, x=0, R ₃, R ₄=CH ₃, R ₅=CH ₂CH ₂OH.

The highly preferred cationic surfactant that is applicable to the present composition is the soluble quaternary ammonium compound, and it has following formula:

R ₁R ₂R ₃R ₄N ⁺X ^-(i) R wherein ₁Be C ₈-C ₁₆Alkyl, each R ₂, R ₃And R ₄Be C independently ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, benzyl and-(C ₂H ₄O) _xH, wherein the x value is 2 to 5, X is a negatively charged ion.R ₂, R ₃, R ₄In be benzyl can not be more than one.

R ₁Preferred alkyl chain length is C ₁₂-C ₁₅, particularly, alkyl is the mixture by coconut or palm-kernel fat deutero-chain length, or synthesizes by alkene or carbonyl (OXO) synthol and to obtain.R ₂, R ₃And R ₄Preferred group is methyl and hydroxyethyl, and negatively charged ion X can be selected from halogenide, methylsulfate, acetate moiety and phosphate anion.

Being used for the example with suitable quarternary ammonium salt compound of formula (i) of the present invention is: Oleum Cocois trimethyl ammonium chloride or brometo de amonio; Oleum Cocois methyl dihydroxy ethyl ammonium chloride or brometo de amonio; The decyl triethyl ammonium chloride; Decyl dimethyl hydroxyethyl ammonium chloride or brometo de amonio; C ₁₂-C ₁₅Dimethyl hydroxyethyl ammonium chloride or brometo de amonio; Oleum Cocois dimethyl hydroxyethyl ammonium chloride or brometo de amonio; Myristyl trimethylammonium methylsulfuric acid ammonium; Lauryl dimethyl benzyl ammonium chloride or brometo de amonio; Lauryl dimethyl (oxygen ethene) ₄Ammonium chloride or brometo de amonio; Cholinesterase (compound of formula (i), wherein R ₁Be Alkyl, and R ₂, R ₃, R ₄Be methyl); Dialkylimidazolium quinoline [compound of formula (i)].

Other useful cats products of the present invention also are described in the U.S. Pat 4,228,044 and European patent application EP 000,224 of the Cambre that authorized on October 14th, 1980.

The soft component of typical cationic fabric comprises the soft actives of water-insoluble quaternary ammonium fabric or their corresponding amine precursors, and the most normally used is chlorination or methylsulfuric acid double long-chain alkyl ammonium.

Wherein the preferred cation softening agent comprises following: 1) chlorination ditallow Dimethyl Ammonium (DTDMAC); 2) chlorination dihydro tallow Dimethyl Ammonium; 3) methylsulfuric acid dihydro tallow Dimethyl Ammonium; 4) Varisoft TA 100; 5) chlorination two oil base Dimethyl Ammonium; 6) chlorination two palmityl hydroxyethyl ammonium methyls; 7) chlorination stearyl benzyl dimethyl ammonium; 8) chlorination tallow trimethyl ammonium; 9) chlorination hydrogenation tallow trimethyl ammonium; 10) chlorination C _12-14Alkyl hydroxyethyl dimethyl ammonium; 11) chlorination C _12-18Alkyl dihydroxy ethyl ammonium methyl; 12) chlorination two (stearoyl-oxy ethyl) Dimethyl Ammonium (DSOEDMAC); 13) chlorination two (butter acyloxy ethyl) Dimethyl Ammonium; 14) methylsulfuric acid ditallow tetrahydroglyoxaline; 15) methylsulfuric acid 1-(2-butter amido ethyl)-2-tallow tetrahydroglyoxaline.

The chlorination that biodegradable quaternary ammonium compound has used as tradition and the surrogate of methylsulfuric acid double long-chain alkyl ammonium and exist.This quaternary ammonium compound contains by functional group carboxyl long-chain kiki alkenyl group at interval for example.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 following 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 ³R ²Be (CH ₂) _m-Q-T ⁴Or T ⁵Or R ³R 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 ⁴, T ⁵Be C independently ₁₁-C ₂₂Alkyl or alkenyl; N and m are the integers of 1-4; And X ^-It is the compatible negatively charged ion of softening agent.The anionic limiting examples compatible with softening agent comprises chlorion or methylsulfate.

Alkyl or alkenyl chain T ¹, T ², T ³, T ⁴, T ⁵Must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.This chain can be a straight or branched.Butter are convenience and cheap sources of chain alkyl and alkenyl material.T wherein ¹, T ², T ³, T ⁴, T ⁵The material of representing typical butter hybrid long chain is particularly 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 (butter acyloxy ethyl)-N, N-alkyl dimethyl ammonium chloride; 2) N, N-two (butter acyloxy ethyl) N-methyl, N-(2-hydroxyethyl) methylsulfuric acid ammonium; 3) N, N-two (2-butter acyloxy-2-oxygen base ethyl)-N, N-alkyl dimethyl ammonium chloride; 4) N, N-two (2-butter acyloxy-ethyl ketonic oxygen base ethyl)-N, N-alkyl dimethyl ammonium chloride; 5) N-(2-butter acyloxy-2-ethyl)-N-(2-butter acyloxy-2-oxygen base ethyl)-N, the N-alkyl dimethyl ammonium chloride; 6) N, N, N-three (butter acyloxy-ethyl)-N-ammonio methacrylate; 7) N-(2-butter acyloxy-2-oxygen base ethyl)-N-(butter acyl group-N, N-alkyl dimethyl ammonium chloride); With 8) 1,2-two butter acyloxy-3-trimethyl ammonium propane chloride; Mixture with any above-mentioned substance.

When comprising them, detergent composition of the present invention typically contains 0.2% to about 25%, and preferred about 1% to this cats product of about 8% weight.

Amphoterics: amphoterics also is applicable in the detergent composition of the present invention.These tensio-active agents can broadly be described to the aliphatic derivatives of the second month in a season or tertiary amine, the perhaps aliphatic derivatives of the heterocycle second month in a season or tertiary amine, and wherein aliphatic group can be a straight or branched.A kind of aliphatic substituting group contains at least about 8 carbon atoms, and typically about 8 to about 18 carbon atoms, and have at least an aliphatic substituting group to contain the water-soluble anionic group, for example carboxyl, sulfonate radical, sulfate radical.Referring to the U.S. Pat 3,929,678 of authorizing Laughlin etc. on December 30th, 1975, the capable relevant examples of amphoteric surfactants of the 19th hurdle 18-35.

When comprising them, detergent composition of the present invention typically contains 0.2% to about 15%, and preferred about 1% to this amphoterics of about 10% weight.

Zwitterionics: zwitterionics also is applicable in the cleaning combination.These tensio-active agents can broadly be described to the derivative of derivative, the heterocycle second month in a season or the tertiary amine of the second month in a season or tertiary amine, or the derivative of quaternary ammonium salt, quaternary phosphonium or uncle's sulfonium compound.Referring to the U.S. Pat 3,929,678 of authorizing Laughlin etc. on December 30th, 1975, the 19th hurdle 38 walks to the example of the relevant zwitterionicss of 22 hurdles, 48 row.

When comprising them, detergent composition of the present invention typically contains 0.2% to about 15%, and preferred about 1% to this zwitterionics of about 10% weight.

Semi-polar nonionic surfactants: semi-polar nonionic surfactants is a special class nonionogenic tenside, it comprises water-soluble amine oxides, and it comprises one about 10 to the moieties of about 18 carbon atoms and 2 and be selected from and contains 1 alkyl and the hydroxyalkyl part to about 3 carbon atoms of having an appointment; The water soluble oxidized phosphine, it comprises one about 10 to the moieties of about 18 carbon atoms and 2 and is selected from and contains 1 alkyl and the hydroxyalkyl part to about 3 carbon atoms of having an appointment; With water-soluble sulfoxide, it comprises one about 10 to the moieties of about 18 carbon atoms and one and is selected from and contains 1 alkyl and the hydroxyalkyl part to about 3 carbon atoms of having an appointment.

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

R wherein ³Be to contain have an appointment 8 alkyl, hydroxyalkyl or alkyl phenyl or their mixture to about 22 carbon atoms; R ⁴Be to contain 2 alkylidene group or hydroxyl alkylidene group or their mixtures of having an appointment to about 3 carbon atoms; X is 0 to about 3; Each R ⁵Be to contain to have an appointment 1 to the alkyl or the hydroxyalkyl of about 3 carbon atoms or contain 1 the polyoxyethylene group of having an appointment to about 3 oxyethylene groups group.R ⁵Group can be connected to each other, and for example is connected to form ring texture by oxygen or nitrogen-atoms.

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

When comprising them, cleaning combination of the present invention typically contains 0.2% to about 15%, and preferred about 1% to this semi-polar nonionic surfactants of about 10% weight.

Cosurfactant: detergent composition of the present invention also can comprise 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 1-5, preferred 3.R ₁Alkyl chain can be a straight or branched, and 12 of as many as at interval, preferably is less than 5 oxygen ethylene moieties.

According to following formula, preferred amine is positive alkylamine.Be used for the amine that the present invention is fit to and be selected from 1-hexylamine, 1-octylame, 1-decyl amine and lauryl amine.Other preferred primary amine comprise C8-C10 oxygen propylamine, octyloxy propyl group amine, 2-ethylhexyl oxygen propyl group amine, lauryl amido propyl group amine and amido propyl group amine.

Be used for the tertiary amine that the present invention is fit to and comprise 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, wherein X is-O-,-C (O) NH-or-NH-, R ₄Be C ₄-C ₁₂, n is 1-5, preferred 2-3, R ₅Be H or C ₁-C ₂Alkyl, x are 1-6.

R ₃And R ₄It can be straight or branched; R ₃Alkyl chain is 12 of as many as at interval, preferably are less than 5 oxygen ethylene moieties.

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 CH ₃, x=1-2.

The amidoamines of following formula further 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, C8-C10 oxygen propyl group amine, 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, C8-C10 amido propyl-dimethyl amine and C10 amido propyl-dimethyl amines.

Being used for the most preferred amine of the present composition is 1-hexylamine, 1-octylame, 1-decyl amine, 1-lauryl amine.Particularly suitable is oleyl amine, lauryl amido propyl group amine and the Oleum Cocois amido propyl group amine of dodecyl dimethyl amine and dihydroxy ethyl Oleum Cocois alkylamine and 7 moles of ethoxylations.

Conventional detergent enzyme

Detergent composition of the present invention also can comprise the enzyme that one or more provide cleaning performance, fabric nursing and/or disinfection except comprising retrograded starch degrading enzyme.Described enzyme comprises and is selected from those following enzymes: cellulase, hemicellulase, peroxidase, proteolytic enzyme, glucose-amylase, amylase, mannase, the wood Polyglucosidase, zytase, lipase, Phospholipid hydrolase, esterase, at, polygalacturonase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase, mannase, beta-glucanase, arabinofuranosidase/xylosidase, the hyaluronic enzyme, chondroitinase, laccase or their mixture.

In fact, detergent composition of the present invention preferably also comprises conventional amylase, conventional starch-debranching enzyme or conventional Starch debranching enzyme Type II, proteolytic enzyme and/or lipase.The conventional meaning of term is not drop on interior amylase, starch-debranching enzyme or the Starch debranching enzyme Type II of ReSI index of the present invention's definition.

In fact, found in detergent composition of the present invention that the combination of retrograded starch degrading enzyme and this conventional amylase, starch-debranching enzyme or Starch debranching enzyme Type II provides the collaborative removal effect to retrogradation starch.Therefore, the detergent composition that comprises this kind of enzyme combination has strengthened the removal of amyloid spot and dirt and has strengthened whiteness and kept and Fouling Cleaning power.In addition, the retrogradation starch layer of finding on fabric usually generally comprises amounts of protein and triglyceride compound.Especially, found that starch material is relevant with lipoid substance usually.Therefore, this detergent composition preferably comprises proteolytic enzyme and/or lipase, so that strengthen the removal to this complicated spot.

As mentioned above, detergent composition of the present invention preferably also comprises conventional amylase.For the object of the invention, suitable α-Dian Fenmei is described in hereinafter: the WO/94/02597 of the NovoNordisk A/S that on February 3rd, 1994 announced has described the cleaning combination that mixes mutant amylase.Also referring to the WO95/10603 of the Novo Nordisk A/S that announces April 20 nineteen ninety-five.Other known amylase that are used for cleaning combination comprise α-and beta-amylase.α-Dian Fenmei is that prior art is known, is included in US5003257; EP252666; WO91/00353; FR2676456; EP285123; EP525610; Those disclosed amylase in EP368341 and the british patent specification 1296839 (Novo).Other amylase that are fit to are stable enhanced amylase, its be described in the WO94/18314 that announced on August 18th, 1994 and the WO96/05295 of the Genencor that announces on February 22nd, 1996 in; From what Novo Nordisk A/S buied direct parent is added the amylase variants that modification obtains with disclosed among the WO95/10603 that announces in April, 95.What also be fit to is the amylase that is described among EP277216, WO95/26397 and the WO96/23873 (all being applied for by Novo Nordisk).The example of commercial α-Dian Fenmei product is the Purafect Ox Am that buys from Genencor ^And Termamyl ^, Ban ^, Fungamyl ^And Duramyl ^, they all can be buied from Novo NordiskA/S Denmark.WO95/26397 has described other amylase that are fit to: α-Dian Fenmei is characterized in that passing through Phadebas ^The alpha-amylase activity measuring, under the 8-10 scope, its specific activity is greater than Termamyl in 25 ℃ of-55 ℃ of temperature and pH value ^Specific activity at least 25%.Preferably be described in the variant of the above enzyme among the WO96/23873 (Novo Nordisk).Preferably, this variant is that proof has those that thermostability improves, more preferably wherein is equivalent at least one amino-acid residue of F180, R181, G182, T183, G184 or K185 lacks from the parent α-Dian Fenmei those.Particularly preferably be those variants of the thermostability with improvement, it comprises aminoacid deletion R181+G182 or T183+G184.Have improvement about activity level and thermostability and more other amylolytic enzymes of the horizontal combinatorial property of high reactivity be described among the WO95/35382.The amylase of Shi Heing is the H mutant alpha-amylases of describing among the WO98/26078 as Genencor that shows improved stability in addition.

The incorporation of amylolytic enzyme in detergent composition of the present invention by the weight of said composition, is 0.0001%-2%, preferred 0.00018%-0.06%, the more preferably pure enzyme of 0.00024%-0.048%.

The starch-debranching enzyme that can be used in the present composition can be obtained by each provenance.Yet generally it is derived from microorganism.The preferred kind of starch-debranching enzyme is Starch debranching enzyme Class1, isopullulanase and isoamylase.

These enzymes are commercially available, and the example comprises SPLENTASE ^(by AmanoPharmaceuticla Co., Ltd. produces) and PROMOZYME ^200L (being produced by NovoIndustri A/S) is as for Starch debranching enzyme; " Isoamylase " (reagent, by Seikagaku Kogyo Co., Ltd. produces) is as for isoamylase.This starch-debranching enzyme generally is to provide with particle form, and has about 10 ⁵-10 ⁸The units per liter enzyme is urged activity.

The starch-debranching enzyme generally content in detergent composition of the present invention is a 0.0001%-10% weight, preferred 0.001%-0.5% weight.

Microbial source comprises Aerobacter aerogenes (Aerobacter Aerogenes), Situ Kan Shi pseudomonas (Pseudomonas stutzeri), bacillus polymyxa (Bacilluspolymyxa), bacillus macerans (B.maceranas), Klebsiella pneumoniae (Klebsiella pneumonia) and streptomyces strain (Streptomyces sp.).The activity of this enzyme is demarcated at 200PUN/g (amylopectin unit of enzyme Novo).1UPN is defined under the standard conditions, the reduced carbohydrate that the hydrolysis amylopectin discharges, and reducing power equals per minute 1 μ-required enzyme amount of mole glucose.Also,, describe among 397 (1985) 188-193 as at Biochimica et BiophysicaActa preferably from the isolating Starch debranching enzyme of genus bacillus strain NO.202-1.It is about 8.55-9.0 that this Starch debranching enzyme has best pH, and useful especially in the stronger detergent composition of alkalescence thus.

Starch debranching enzyme at first is found in by what Bender and Wallenfels described in 1961 [Biochem.Z.334,79, (1961)] and is derived from the bacterial strain that belongs to Aerobacter aerogenes.Recently, the various microorganisms that can produce Starch debranching enzyme have been reported.These microorganisms are genus bacillus [J.Jpn.Soc.Starch Sci., 30,200, (1983)] for example; Bacillusacidopullulyticus[Agric.Biol.Chem., 52,2293, (1984)]; Bacstearothermophilus (Bacillus stearothermophilus) [Eur.J.Appl.Microbiol.Biotechnol., 17,24, (1983)] gentle suis (Streptococcusmitis) [Biochem, J., 108,33, (1968)]; Lactobacillus (Clostridiumsp.) [Denpun Kagaku, 28,72 (1981)]; Clostridium (Clostridiumsp.) [Appl., Environ.Microb., 53,7 (1987)]; The hot anaerobic bacillus(cillus anaerobicus) of hot sulfurization hydrogen (Clostridium thermohydrosulfuricum) [Appl.Environ.Microb., 49,5, (1985), J.Bacteriol., 164,3, (1985), Biochem.J., 246, (1987)], thermus aquaticus (Thermus aquaticus) [Enzyme Microb.Technol., 8, (1986)]; Hot bacterial classification (Thermus sp.) [J.Jpn.Soc.Starch Sci., 34,1, (1987)] and the heat of dwelling is produced the hot anaerobic bacillus(cillus anaerobicus) of sulphur (Clostridium thermosulfurogenes) [Appl.Microb.Biotechnol., 33,511, (1990)].In addition, two pieces of open source literatures have all been reported the method for preparing alkalescence or alkali-proof Starch debranching enzyme: the alkaline Starch debranching enzyme of having a liking for alkali bacterial strain and generation (Japanese patent application publication No. 277786/1978) that the bacillus of Horikoshi etc. (genus bacillus kind 202-1) is cultivated; With by the alkaline Starch debranching enzyme of in WO94/19468, describing (Japanese Unexamined Patent Publication No 87176/1991) that obtains by genus bacillus kind KSM-AP1876.

Relevant Starch debranching enzyme comprises that for example (B.acidopullulyticus that for example describes is such as the Promozyme that is buied by Novo Nordisk A/S by the genus bacillus kind in EP063909 ^TM) Starch debranching enzyme that obtains.The other Starch debranching enzyme of suitable detergent composition of the present invention is the alkaline Starch debranching enzyme that is described among the EP450627 of Kao company, and it has at the best pH of alkaline range and is stable to tensio-active agent.This alkaline Starch debranching enzyme comprises alkaline Starch debranching enzyme A and alkaline Starch debranching enzyme B, both's the object of the invention that suits.The another kind of alkaline Starch debranching enzyme of suitable washing composition is described among the WO94/19468 of Kao company.

That suitable is the Starch debranching enzyme that is described in following Japanese Patent/application: JP04073298 in addition, and it relates to the machine washing dish washing detergent compositions, and it comprises the alkaline Starch debranching enzyme of nonionogenic tenside, calcium sequestrant, lipase and high washing force; JP06264094, it has described a kind of laundry detergent composition, the alkali-proof Starch debranching enzyme that it comprises soap, tensio-active agent and has high washing force; All these documents all are Kao companies.

Particularly preferably be by the isolated Starch debranching enzyme Promozyme of genus bacillus kind Starch debranching enzyme (trade mark of Novo).

Isoamylase: isoamylase has the ability that makes glycogen take off side chain.This enzyme is detected in various microorganisms, comprises bacillus amyloliquefaciens (B.amyloliquefacines), Cytophaga kind (Cytophaga sp.), P.amyloderamosa and streptomyces strain numbering 28.The activity of this enzyme is to provide with MU (maltose unit).1MU is defined under the standard conditions, the reduced carbohydrate that the different amylose starch of hydrolysis discharges, and reducing power equals per minute 1 μ-required enzyme amount of mole maltose.

Isoamylase is classified into EC3.2.1.68 under the IUPAC classification and systematic name is a glycogen 6-glucan hydrolase.In this isoamylase hydrolysis glycogen, amylopectin and their the β-limit dextrin 1,6-α-D-glucoside Zhi Jian.This isoamylase is inequality in Starch debranching enzyme, and they do not have the ability of attack amylopectin, has limited effect and them that glycogen is had effect fully to α-limit dextrin.Relevant isoamylase comprises the isoamylase that is for example obtained by pseudomonas kind (for example the pseudomonas kind SMP1 or starch pseudomonas (Pseudomonasamyloderomosa) SB150 that is situated between), genus bacillus kind (for example bacillus amyloliquefaciens), Flavobacterium kind or phagocyte bacterial classification (Lysobacter).

Isoamylase can be from Sigma, and ICN and Hayashibara are purchased.

That also be fit to is Starch debranching enzyme, isopullulanase and the isoamylase that is described as starch-debranching enzyme in following Japanese Patent/application: JP07179900, JP06172796, JP06172792, JP04065494, JP02132193 and JP02132192, all these documents are Kao companies.

Starch debranching enzyme Type II enzyme is defined as the starch Starch debranching enzyme and except (the α-1 of the side chain in Polysaccharides and the dextrin, the 6-key) outside, hydrolyzing alpha brokenly also, the 1-4 key, this is opposite with Starch debranching enzyme Class1 enzyme, Starch debranching enzyme Class1 enzyme is the α in the hydrolysis side chain polysaccharide only, and 1, the 6-key.

The Starch debranching enzyme Type II can be derived from such as by for example in " A new BacterialWorld ", Extremophiles, 1997,1; The Wo Shi fireball bacterium of describing among the 2-13 (Pyrococcus woesei), fierce fireball bacterium (P.furiosus), Thermococcuslitoralis, speed is given birth to hot-bulb bacterium (Thermococcus celer), sticking sulphur reduction coccus (Desulfurococcus mucosus), bacteroides thetaiotaomicron (Bacteroidesthetiaotaomicron), glucose thermophile bacteria (Staphylotherrmus marinus), Pyrodictium abysii, isolated those of bacstearothermophilus (Bacillus stearothermophilus) are had a liking for special conditions, particularly have a liking for very hot and bacterium that have a liking for intensification.Other suitable Starch debranching enzymes that are used for the object of the invention be described in WO96/35794 show the active alkaline Starch debranching enzyme of alkali alpha amylase.That also suitable is the alkaline Starch debranching enzyme Y with alpha-amylase activity that is described among the EP418835, and it has best pH than the alkaline Starch debranching enzyme of routine and shows in the pH stability of the excellence of wide pH scope with to nearly all detergent components such as tensio-active agent, sequestrant and proteolytic enzyme in higher alkaline range have strong patience.

Also suitable is Starch debranching enzyme-diastatic combination enzyme (Agric.Biol.Chem., 51,9. (1987) that produced by subtilis TU; Japanese patent application publication No. 18717/1989).

The Starch debranching enzyme Type II generally content in detergent composition of the present invention is a 0.0001%-10% weight, preferred 0.001%-0.5% weight.

Suitable lipase comprises by the microorganism in the Rhodopseudomonas family, as those lipase of Situ Ci Shi aeruginosa atcc 19.154 generations, as is disclosed in the English Patent 1372034.The lipase that is fit to comprises that the antibody with lipase that is produced by microorganism Pseudomonas fluorescens (Pseudomonasfluorescent) IAM 1057 shows those lipase of positive immunological cross-reaction.This lipase can be by Amano Pharmacetical company limited, and Japan Nagoya has been bought, and commodity are called lipase P " Amano ", hereinafter are referred to as " Amano-P ".Other commercial lipase that are fit to comprise Amano-CES, the lipase that obtains by thickness look bacillus (Chromobacter viscosum), and for example by Toyo Jozo company, Tagata, the lipolyticum NRRLB 3673 of the thickness look bacillus variation that Japan obtains; By U.S.Biochemical company, thickness look bacillus lipase that the Disoynth company of U.S.A. and Holland obtains and the lipase that obtains by gladiolus pseudomonas (Pseudomonas gladioli).Particularly suitable lipase is such as M1 Lipase ^RAnd Lipomax ^R(Gist-Brocades) and Lipolase ^RWith Lipolase Ultra ^R(Novo) lipase has found that be very effective when they and the present composition are used in combination.What also be fit to is to be described in EP258068, WO92/05249 and WO95/22615 and to be described in lipolytic enzyme among WO94/03578, WO95/35381 and the WO96/00292 by Unilever by NovoNordisk.

Also the enzyme of Shi Heing is at [EC 3.1.1.50], and the lipase that it is considered to a kind of particular variety is called the lipase that does not need interface activation.In detergent composition, add at and be described in for example WO-A-88/09367 (Genencor); Among WO90/09446 (PlantGenetic System) and WO94/14963 and the WO94/14964 (Unilever).

Lipase and/or the at generally incorporation in this detergent composition are the pure enzyme of 0.0001%-2% of this detergent composition weight.

Suitable proteolytic enzyme is subtilisin, and it is that special bacterial strain by Bacillus subtillis (B.subtillis) and bacillus licheniformis (B.licheniformis) obtains (subtilisin BPN and BPN ').A kind of suitable proteolytic enzyme is to be obtained by bacillus strain, and it has maximum activity in the pH8-12 scope, and it is by the NovoIndustries A/S exploitation of Denmark and with ESPERASE ^Sell, hereinafter be called " Novo ".The preparation of this kind of enzyme and similar enzyme is described among the british patent specification GB1243784 of Novo company.Other proteolytic enzyme that are fit to comprise the ALCALASE from Novo ^, DURAZYM ^And SAVINASE ^With from the MAXATASE of Gist-Brocades ^, MAXACAL ^, PROPERASE ^And MAXAPEM ^(Maxacal of protein engineering).Also being suitable for of the present invention is to be described in proteolytic enzyme among patent application EP251446 and the WO91/06637, to be described in the proteolytic enzyme BLAP among the WO91/02792 ^With their variant that is described among the WO95/23221.Also referring to the high pH proteolytic enzyme that derives from bacillus NCIMB40338 among the WO93/18140A that is described in Novo.Contain proteolytic enzyme, the enzyme-containing detergent of one or more other enzymes and reversible protease inhibitors is described among the WO92/03529A of Novo.When needs, as at Procter ﹠amp; Describe among the WO95/07791 of Gamble, can obtain adsorbing the proteolytic enzyme of reduction and hydrolysis raising.The recombinant protein enzyme that is suitable for the trypsin-like of washing composition of the present invention is described among the WO94/25583 of Novo.Other proteolytic enzyme that are fit to are described among the EP516200 of Unilever.

Proteolytic ferment also comprises the bacterial serine proteolytic enzyme of modification, for example the European patent application serial of submitting on April 28th, 1987 is those that (particularly the 17th, 24 and 98 page) described in 87303761.8, it is called as " proteolytic enzyme B " at this paper, with in the European patent of disclosed Venegas on the 29th October in 1986, ask in 199404 those that describe, they are bacterial serine proteolytic ferments of modification, are called as at this paper " protease A ".What be fit to is the proteolytic enzyme that is called as " proteolytic enzyme C " at this paper, they are variants of the alkaline serine protease that obtained by bacillus, wherein Methionin replaces the arginine of 27 positions, Xie Ansuan, Serine that tyrosine replaces 104 positions replace the l-asparagine of 123 positions and the Threonine that L-Ala replaces 274 positions.Proteolytic enzyme C is described among the WO91/06637.Particularly the variant of the genetic modification of proteolytic enzyme C is also included among the present invention.

The preferred protease that is called as " proteolytic enzyme D " is to have the carbonylic hydrolase variant that does not have the aminoacid sequence found at occurring in nature, and it obtains from carbonylic hydrolase is precursor-derived, and this deriving is numbering according to the bacillus amyloliquefaciens subtilysin, in described carbonylic hydrolase, be equivalent to+76 position, also preferred combination be equivalent to be selected from+99 ,+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 residue position places of 274, with a plurality of amino-acid residues of the different said positions of aminoacid replacement, as described in WO95/10591 and the WO95/10592." proteolytic enzyme D " variant preferably has the aminoacid replacement of 76/103/104 position, more preferably replaces to occur in N76D/S103A/V1041.What also be fit to is the carbonylic hydrolase variant of the proteolytic enzyme described in WO95/10591, and its aminoacid sequence is to obtain by replacing in the pre-enzyme corresponding to a plurality of amino-acid residues of+210 positions and in conjunction with the replacement of following one or more residues :+33 ,+62, + 67 ,+76 ,+100, + 101, + 103 ,+104 ,+107, + 128, + 129 ,+130 ,+132, + 135, + 156 ,+158 ,+164, + 166, + 167 ,+170 ,+209, + 215, + 217 ,+218 and+222, Bian Hao position is corresponding to the subtilysin or the amino-acid residue that is equal in other carbonylic hydrolases or for example slow genus bacillus subtilysin of subtilysin (existing autre action pendante patent application WO98/55634) of the natural generation that is obtained by bacillus amyloliquefaciens here.

Preferred proteolytic enzyme is polysubstituted ease variants.These ease variants comprise with the amino-acid residue of another kind of natural generation and replace amino-acid residue corresponding to 103 positions of bacillus amyloliquefaciens subtilysin, simultaneously in conjunction with replacement with the amino-acid residue of upper/lower positions corresponding to the bacillus amyloliquefaciens subtilysin:

1,3,4,8,9,10,12,13,16,17,18,19,20,21,22,24,27,33,37,38,42,43,48,55,57,58,61,62,68,72,75,76,77,78,79,86,87,89,97,98,99,101,102,104,106,107,109,111,114,116,117,119,121,123,126,128,130,131,133,134,137,140,141,142,146,147,158,159,160,166,167,170,173,174,177,181,182,183,184,185,188,192,194,198,203,204,205,206,209,210,211,212,213,214,215,216,217,218,222,224,227,228,230,232,236,237,238,240,242,243,244,245,246,247,248,249,251,252,253,254,255,256,257,258,259,260,261,262,263,265,268,269,270,271,272,274 and 275; Wherein when described ease variants comprises replacement corresponding to the amino-acid residue of 103 and 76 positions, also exist non-corresponding to 27 of bacillus amyloliquefaciens subtilysin, 99,101,104,107,109,123,128,166,204,206,210,216,217,218,222,260, the replacement of the amino-acid residue at one or more amino acid residue positions place of 265 or 274 amino acid residue positions, and/or polysubstituted ease variants comprises that the amino-acid residue with another kind of natural generation replaces corresponding to 62 of bacillus amyloliquefaciens subtilysin, 212,230,232, the amino-acid residue at the one or more amino acid residue positions place in 252 and 257 is as Procter ﹠amp; Gamble company is at the PCT application number PCT/US98/22588 of application on October 23rd, 1998, described in PCT/US98/22482 and the PCT/US98/22486.Preferred polysubstituted ease variants is according to the numbering of bacillus amyloliquefaciens subtilysin, have and occur in 101/103/104/159/232/236/245/248/252, more preferably the aminoacid replacement at 101G/103A/104I/159D/232V/236H/245R/248D/252K place.

The present composition also can comprise other enzymes.

The cellulase that can be used among the present invention comprises bacterium and fungal cellulase.Preferred they have best pH scope 5-12 and specific activity is higher than 50CEVU/mg (Mierocrystalline cellulose viscosity unit).Suitable cellulase is disclosed in people's such as Barbesgoard U.S. Pat 4,435,307, among J61078384 and the WO96/02653, it discloses the fungal cellulase that is produced by Humicola insolens, Trichoderma, careless Rhizopus and Sporothrix respectively.EP739982 has described from the isolated cellulase of new bacillus specie.Suitable cellulase also is disclosed in GB-A-2075028; GB-A-2095275; Among DE-OS-2247832 and the WO95/26398.

The example of this cellulase is the cellulase that is produced by Humicola Humicolainsolens (thermoidea of grey humicola lanuginosa variation) bacterial strain, particularly Humicola strain DSM 1800.

Other cellulases that are fit to are to derive from Humicola insolens, it has the about 50KDa of molecular weight, iso-electric point is 5.5 and contains 415 amino acid, with by Humicola insolens, the DSM1800 deutero-show cellulase activity ~ endoglucanase of 43kD; Preferred endoglucanase component has disclosed aminoacid sequence in PCT application WO91/17243.Also the cellulase of Shi Heing is the EGIII cellulase that is obtained by Trichoderma longibrachiatum, and it is described among the WO94/21801 of disclosed Genencor on the 29th September in 1994.Particularly suitable cellulase is the cellulase with the effect of nursing color.The example of this cellulase is those cellulases of describing in the european patent application No.91202879.2 (Novo) that submitted on November 6th, 1991.Carezyme and Celluzyme (Novo Nordisk A/S) are particularly suitables.Also referring to WO91/17244 and WO91/21801.Other cellulases that are fit to nursing fabric and/or cleaning character are described among WO96/34092, WO96/17994 and the WO95/24471.

The described cellulase generally incorporation in this detergent composition is the pure enzyme of 0.0001%-2% of this detergent composition weight.

Peroxidase be with oxygen source for example percarbonate, perborate, persulphate, hydrogen peroxide etc. and be used in combination as the phenolic group matter that strengthens bleached molecules.They are used for " liquid lime chloride ", promptly are suppressed in the washing process on the dyestuff that comes off from substrate or pigment migration other substrates to the washing soln.Peroxidase is being known in the art, for example comprises, horseradish peroxidase, lignoenzyme and halo peroxidase are as chloro or bromoperoxidase.The detergent composition that contains peroxidase is disclosed in, for example among PCT International Application No. WO 89/099813, the WO89/09813 and among the european patent application No.91202882.6 that submitted on November 6th, 1991 and among the EP96870013.8 that submitted on February 20th, 1996.What also be fit to is laccase.

Synergistic agent generally accounts for the 0.1%-5% of total composition weight.The thiodiphenylamine that preferred synergistic agent is replacement is with phenoxazine, lysivane propionic acid (PPT), 10-ethyl thiodiphenylamine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP) and 10-Jia Ji phenoxazine (being described in WO94/12621) and the cloves ester (the alkyl cloves ester that C3-C5 replaces) and the phenol that replace.SPC-D or Sodium peroxoborate are preferred hydrogen peroxide cources.

The described peroxidase generally incorporation in this detergent composition is the pure enzyme of 0.0001%-2% of this detergent composition weight.

Above-mentioned enzyme can be from any suitable source, for example plant, animal, bacterium, fungi and yeast source.This source can also be have a liking for temperature or (extremophilic) that have a liking for special conditions (have a liking for cold, suitable cold, thermophilic, have a liking for pressure, that have a liking for alkali, have a liking for acid, have a liking for salt etc.).Can use the form of the purifying or the non-purifying of these enzymes.Current, the common practice is to improve wild-type enzyme by protein/gene engineering, so that make its performance in detergent composition of the present invention the most effective.For example, this variant can be designed such that the consistency of the component that generally includes in this enzyme and this composition improves.In addition, this variant can be made into and make best pH, bleaching or sequestrant stability, the catalytic activity etc. of this enzyme variants be suitable for specific cleaning application.

Particularly, with regard to bleach stability, should be primarily focused on, should be primarily focused on the surface charge on the amino acid of oxidation-sensitive and for compatible with tensio-active agent.The iso-electric point of this kind of enzyme can be improved by replacing amino acids with identical charges, for example increases iso-electric point and can help to improve consistency with anion surfactant.Salt bridge that also can be by for example producing other and strengthen calcium binding site strengthens enzyme with the stability that increases sequestrant stability.Must pay special attention to cellulase, because most of cellulase has independently binding domains (CBD).The character of this kind of enzyme can change by the modification to these structural domains.

This enzyme can be used as independently single component and adds and (contain a kind of ball, grain of enzyme, stable liquid etc..) or add (for example composite particles) as the mixture of two or more enzymes.

The detergent components that other that can add are fit to is the oxydasis scavenging agent, and it is described in the existing autre action pendante european patent application of submitting on January 31st, 1,992 92870018.6.The example of this kind of enzyme oxidation scavengers is four ethylidene polyamine of ethoxylation.

Various enzyme materials and their methods in the synthetic detergent composition of mixing also are disclosed in WO9307263A and the WO9307260A of Genencor International, in the people's such as McCarty that the WO8908694A of Novo and on January 5th, 1971 authorize the U.S. Pat 3553139.Some enzymes also be disclosed in the people's such as Place that authorized on July 18th, 1978 U.S. Pat 4101457 and the U.S. Pat 4507219 of the Hughes that authorized on March 26th, 1985 in.The enzyme material that is used for liquid detergent formula is disclosed in the people's such as Hora that authorized on April 14th, 1981 the U.S. Pat 4261868 with methods that they are incorporated into these prescriptions.The enzyme that is used for washing composition can make its stabilization with various technology.The enzyme stabilization technology discloses and illustrates the people's such as Gedge that authorize on August 17th, 1971 U.S. Pat 3600319, among the EP200586 of the EP199405 and the Venegas on October 29th, 1986.The enzyme stabilising system for example also is described in the U.S. Pat 3519570.The useful bacillus species AC13 that produces proteolytic enzyme, zytase and cellulase is described among the WO9401532A of Novo.SYNTHETIC OPTICAL WHITNER

The in addition preferred component of detergent composition of the present invention comprises SYNTHETIC OPTICAL WHITNER.In fact, found to make the easier dissolving of starch, so its easier removing by SYNTHETIC OPTICAL WHITNER Sumstar 190 material.In addition, SYNTHETIC OPTICAL WHITNER has been owing to reduced total color of processed fabric, and helps the Fouling Cleaning of fabric.Therefore, the present composition that also comprises SYNTHETIC OPTICAL WHITNER has improved the removal to amyloid spot and dirt, has improved whiteness and has kept and mainly improved soil cleaning power.

For the object of the invention, suitable SYNTHETIC OPTICAL WHITNER comprises hydrogen peroxide, PB1, PB4 and has the percarbonate of granularity 400-800 micron.These SYNTHETIC OPTICAL WHITNER components can comprise one or more oxygen bleaching agents and according to one or more bleach-activating agents of selected SYNTHETIC OPTICAL WHITNER.When having the oxygen bleaching compound, it generally exists with about 1%-25% content.

Being used for SYNTHETIC OPTICAL WHITNER component of the present invention can be any SYNTHETIC OPTICAL WHITNER that is applicable to cleaning combination, comprises oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER well known in the art.Be applicable to that SYNTHETIC OPTICAL WHITNER of the present invention can be activatory or inactive SYNTHETIC OPTICAL WHITNER.

The spendable oxygen bleaching agent of one class 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, 4-nonyl amino-4-oxo Perbutyric Acid magnesium and diperoxy dodecanedioic acid magnesium.These SYNTHETIC OPTICAL WHITNER are disclosed in U.S. Pat 4483781, and U.S. Patent application 740446 is in european patent application 0133354 and the U.S. Pat 4412934.Highly preferred SYNTHETIC OPTICAL WHITNER also comprises as 6-nonyl amino-6-oxo of describing in U.S. Pat 4634551 crosses oxy hexanoic acid.

Another kind of spendable SYNTHETIC OPTICAL WHITNER comprises halogen bleaching agent.The example of hypohalite SYNTHETIC OPTICAL WHITNER comprises for example TCCA (Trichloroisocyanuric acid), dichloroisocyanuric acid sodium and potassium and N-chloro and N-bromoalkane sulphonamide.The general add-on of this material is the 0.5-10% of finished weight, preferred 1-5% weight.

The hydrogen peroxide releasing agent can with bleach-activating agent for example tetra acetyl ethylene diamine (TAED), nonanoly acyloxy benzene sulfonate (NOBS; be described in US4; 412; in 934), 3; 5-trimethyl hexanol oxygen benzene sulfonate (ISONOBS; be described in EP120; in 591), the sulfocarbolate (NACA-OBS of penta-acetyl glucose (PAG) or N-nonanoyl-6-aminocaprolc acid; be described among the WO94/28106) combine use; these bleach-activating agents are crossed hydrolysis and are formed peracid; as active bleaching thing, thereby cause the bleaching effect that improves.Also the activator of Shi Heing is the citrate of acidylate, those disclosed and have the asymmetric acyclic imide bleach activators of following formula in autre action pendante european patent application No.91870207.7 for example, as be disclosed in Procter ﹠amp; In the autre action pendante u.s. patent application serial number 60/022786 of Gamble (submission on July 30th, 1996) and 60/028122 (submission on October 15th, 1996):

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

The SYNTHETIC OPTICAL WHITNER that is suitable for that is used for detergent composition of the present invention, comprise peroxy acid, be described in our autre action pendante application USSN 08/136 with the bleach system that comprises bleach-activating agent and peroxy bleaching compound, 626, PCT/US95/07823 is among WO95/27772, WO95/27773, WO95/27774 and the WO95/27775.

Hydrogen peroxide also can urge system (be enzyme and corresponding substrate) to provide by adding a kind of enzyme, and this enzyme system of urging can produce hydrogen peroxide in the beginning of washing and/or rinse cycle or process.This kind of enzyme system of urging is disclosed in the EP patent application 912022655.6 of application on October 9th, 1991.

The metallic catalyzer that is used for bleaching composition comprises the catalyzer that contains cobalt, and five amine cobaltous acetate (III) salt and manganiferous catalyzer for example are for example at EPA549271, EPA549272; EPA458397; US5246621; EPA458398; Those that describe among US5194416 and the US5114611.The bleaching composition that contains peralcohol, manganiferous bleaching catalyst and sequestrant is described in the patent application 94870206.3.Bleaching compounds can come catalysis with manganic compound.This compound is well known in the prior art, comprises for example being disclosed in US5, and 246,621, US5,244,594; US5194416; US5144606 and European patent application publication No. 549271A1,549272A1, the manganese basigamy compound among 544440A2 and the 544490A1.The preferred embodiment of these catalyzer comprises: Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(PF ₆) ₂, Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄(ClO ₄) ₂, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₃, Mn ^IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH ₃) ₃(PF ₆) and their mixture.Be used for more preferably transition metal bleach catalyzer of the present invention, it is the title complex of the crosslinked most ring ligand of transition metal and bridge, as Procter ﹠amp; Described in patent application WO98/39405, the WO98/39406 and WO98/39098 of Gamble.Formula [Mn (Bcyclam) Cl of most preferably following example explanation ₂] Mn title complex bleaching catalyst:

" Bcyclam " (5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] n-Hexadecane).This transition metal bleach catalyzer can be according to Procter ﹠amp; The patent application WO98/39335 of Gamble or according to J.Amer.Chem.Soc., (1990), 112,8604 preparations.

SYNTHETIC OPTICAL WHITNER except oxygen bleaching agent also is well known in the art, and can be with in the present invention.The non-oxygen bleaching agent that one class is good especially comprises photosensitization SYNTHETIC OPTICAL WHITNER such as sulfonated Phthalocyanine Zinc and/or aluminium.These materials can be deposited on the substrate in washing process.Under the condition that oxygen exists, when by rayed, for example clothes to be dried in the air outdoor under daylight when dry, the sulfonated Phthalocyanine Zinc is activated, and substrate is bleached as a result.Preferred Phthalocyanine Zinc and photoactivated bleaching method are described in the U.S. Pat 4033718.Detergent composition generally contains the 0.025% sulfonated Phthalocyanine Zinc to about 1.25% (weight) of having an appointment.Nursing color and the effect of nursing fabric

A kind of technology of nursing the color effect that provides also can be provided.The example of these technology is the metal catalysts that are used to keep color.This metal catalyst is described among the autre action pendante european patent application No.92870181.2.The other example of nursing color/nursing fabric technology is dye-fixing agent (laking agent), is used for amino-functional polymers crease-resistant and that improve polyolefine dispersion agent, the spices of water absorption and be used for color nursing processing and make spices have affinity that it is described among the autre action pendante patent application No.96870140.9 that submitted on November 7th, 1996.

Fabric softener also can mix in the detergent composition of the present invention.These softening agents can be inorganic or organic type.The example of inorganic softening agent is disclosed in GB-A-1400898 and USP5, the terre verte class in 019,292.The organic fabric softening agent comprises as being disclosed in the water-insoluble tertiary amine among GB-A 1 514276 and the EP-B 0 011 340 and being disclosed among EP-B-0 026 527 and the EP-B-0 026 528 mixture of the former tertiary amine and single C12-C14 quaternary ammonium salt, and as being disclosed in the two long-chain acid amides among the EP-B-0242 919.Other organic components that are fit to that are used for the fabric softener system comprise the high molecular weight peo material that is disclosed in EP-A-0299 575 and 0 313 146.

The content of terre verte is generally 2% to 20%, more preferably 5% to 15% weight, and this material is to mix component and join in all the other components of prescription as doing.The organic fabric softening agent for example incorporation of water-insoluble tertiary amine or two long-chain acid amides materials is 0.5% to 5% weight, 1% to 3% weight normally, and the add-on of high molecular weight peo material and water-soluble cationic material is 0.1% to 2%, normally 0.15% to 1.5% weight.Though mix that particle adds or they are sprayed onto as melt liquid may be more convenient on other solid constituents of composition as doing for these materials in some cases, usually their added in the spray-dired part of composition.Builder system

The present composition also can comprise builder system.The builder system of any routine all is applicable to the present invention, comprise aluminosilicate material, silicate, multi-carboxylate, alkyl or alkenyl succinic and lipid acid, such as material, metal ion chelation agent for example amino polyphosphonate, particularly ethylenediamine tetramethylene phosphonic acid and the diethylenetriamine pentamethylenophosphonic acid(DTPP) of ethylenediamine tetraacetic acid (EDTA), diethylenetriamine pentamethylene acetate.Phosphate builders also can be used for the present invention.

The washing assistant that is fit to can be a mineral ion exchange material, the aluminosilicate material of inorganic hydration normally, for example zeolite A, X, B, HS or the MAP of hydration of the synthetic zeolite of hydration more specifically.

The another kind of inorganic builders material that is fit to is a layered silicate, for example SKS-6 (Hoechst).SKS-6 is a kind of crystalline layered silicate (Na that is made of water glass ₂Si ₂O ₅).

The multi-carboxylate of containing a carboxyl who is fit to comprises lactic acid, oxyacetic acid and their ether derivant, as is disclosed in belgian patent Nos.831, in 368,821,369 and 821,370.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylidene dioxy) oxalic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid; and be described in German Patent 2; 446; 686 and 2,446,687 and U.S. Pat 3; 935; ether carboxylate in 257, and the sulfinyl carboxylate salt of describing in the belgian patent 840,623.The multi-carboxylate of containing three carboxyls comprises particularly water miscible Citrate trianion, aconitate and citraconate, and the succinate derivative for example is described in English Patent 1,379, carboxy methoxy-succinic acid salt in 241, be described in the newborn acyloxy succinate in the Netherlands patent applications 7205873, for example be described in English Patent No.1 with oxygen multi-carboxylate material, the 2-oxa--1 in 387,447,1,3-tricarballylic acid salt.

The multi-carboxylate of containing four carboxyls comprises English Patent No.1, disclosed oxygen di-succinate, 1,1,2 in 261,829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Containing the substituent multi-carboxylate of sulfo group comprises and is disclosed in English Patent Nos.1,398,421 and 1,398,422 and U.S. Pat 3,936,448 in the sulfo-succinic acid salt derivative, with English Patent No1, the sulfonated pyrolysis Citrate trianion of describing in 082,179 is disclosed in English Patent No.1 and contain the substituent multi-carboxylate of phosphine, in 439,000.

Alicyclic ring and heterocyclic multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2, the 5-tetrahydrofuran (THF)-along dicarboxylate, 2,2,5,5-tetrahydrofuran (THF) tetracarboxylic acid hydrochlorate, 1,2,3,4,5,6-hexane hexacarboxylic acid salt and polyvalent alcohol be the carboxymethyl derivant of sorbyl alcohol, N.F,USP MANNITOL and Xylitol for example.Aromatic multi-carboxy acid's salt comprises English Patent No.1, disclosed melitic acid, 1,2,4 in 425,343, the derivative of 5-pyromellitic acid and phthalic acid.

More than in these compounds, preferred multi-carboxylate is the hydroxycarboxylate of containing three carboxyls of as many as in each molecule, Citrate trianion more specifically.

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

Other washing assistant materials that can be configured for the part of the builder system in the particulate composition comprise for example for example organic phosphonate, amino polyalkylene phosphonate and aminopolycanboxylic acid's salt of alkaline carbonate, supercarbonate, silicate and organic materials of inorganic materials.

Other water-soluble organic salts that are fit to are the acid of homopolymerization or copolymerization or their salt, and wherein poly carboxylic acid comprises at least two carboxyls that are separated from each other by no more than two carbon atoms.Such polymkeric substance is disclosed in GB-A-1, in 596,756.The example of this class salt is the polyacrylate with MW2000-5000, and the multipolymer of they and maleic anhydride, and this multipolymer has molecular weight 20,000 to 70,000, particularly about 40,000.

The general content of detergent builder compound salt is 5% to 80% of composition weight, and is preferred 10% to 70%, the most normally 30% to 60%.Sequestrant

Cleaning composition of the present invention can also randomly contain one or more iron and/or manganese sequestrant.This class sequestrant can be selected from aminocarboxylate, amino phosphonates do, and aromatic chelating agent of multifunctional replacement and composition thereof, all sequestrants are as definition hereinafter.Do not accept the restriction of opinion, it is believed that the advantage of these materials is that partly they have the ability free from worldly cares of removing de-iron and manganese by forming the soluble chelating thing from washing soln.

Aminocarboxylate as optional sequestrant 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 an alkali metal salt, ammonium salt and substituted ammonium salt and their mixture.

When allowing to have low at least total phosphorous in detergent composition of the present invention, amino phosphonates do also is suitable as the sequestrant of the present composition, comprising: ethylenediamine tetraacetic (methylene phosphonic acid salt) is DEQUEST.These amino phosphonates do preferably do not contain alkyl or the alkenyl that surpasses about 6 carbon atoms.

In the present composition, can also use the aromatic chelating agent of multifunctional replacement.Referring to people's U.S. Pat 3812044 such as Connor of authorizing on May 21st, 1974.The compound of preferred this class acid form be the dihydroxyl disulfobenzene as 1,2-dihydroxyl-3,5-disulfobenzene.

The preferred in the present invention biodegradable cheating agent of using is ethylenediamine disuccinate (" EDDS "), especially its [S, the S] isomer as describing in the U.S. Pat 4704233 of authorizing Hartman and Perkins on November 3rd, 1987.

The present composition also can contain water miscible methylglycine oxalic acid (MGDA) salt (or sour form) as sequestrant, or as the auxiliary washing assistant that uses with for example insoluble washing assistant such as zeolite, layered silicate etc.

If the use sequestrant, then its consumption is generally about 0.1%-about 15% of detergent composition weight of the present invention.If the use sequestrant, more preferably its consumption is about 0.1%-about 3.0% of said composition weight.Suds suppressor

Another kind of optional component is a suds suppressor, example polysiloxane and silicon dioxide-poly-mixture of siloxanes.Polysiloxane general proxy thing has alkylating polysiloxane material, and dioxide generally is to use with the form of fine powder, and example has aerosil and xerogel and various types of water drain silica.These materials can the particulate form mix, and wherein suds suppressor is impregnated in the impervious carrier of water-soluble or water-dispersible, non-surface active substantially washing composition and can advantageously discharges.In addition, suds suppressor solubilized or be distributed in the liquid vehicle or by sprinkling is applied on one or more other components.

Preferred polysiloxane Foam Control is disclosed in people's such as Bartollota the United States Patent (USP) 3,933,672.Other useful especially suds suppressors are self-emulsifying polysiloxane suds suppressors, and it is described among the disclosed German patent application DTOS 2,646,126 on April 28th, 1977.This examples for compounds is DC-544, commercial can buying by Dow corning, and it is a kind of siloxane-glycol copolymer.Especially preferred Foam Control is the suds suppressor system that comprises the mixture of silicone oil and 2-alkyl alkanol.The 2-alkyl alkanol that is fit to is a 2-butyl octanol, and it can be buied by trade(brand)name Isofol 12 R commercial.

This suds suppressor system is described among the autre action pendante european patent application No.92870174.7 of 10 applications November in 1992.

Particularly preferred polysiloxane Foam Control is described among the autre action pendante european patent application No.92201649.8.Said composition can comprise and the imporosity silicon-dioxide of pyrolysis (fumed) Aerosil for example ^RPolysiloxane/the silica mixture that is used in combination.

The general usage quantity of above-mentioned suds suppressor is 0.001% to 2% of a composition weight, preferred 0.01% to 1%.Other components

Can use other components that are used for detergent composition, for example soil-suspending agent, dirt release agent, white dyes, abrasive material, sterilant, tarnish inhibitor, tinting material and/or that seal or the non-spices of sealing.

Particularly suitable encapsulating material is water miscible capsule, and it is by for example being described in GB1, and the polysaccharide in 464,616 and the matrix of polyol constitute.Other water-soluble encapsulating materials that are fit to comprise for example US3, the starch acid-ester deutero-dextrin of describing in 455,838 by the non-gelling of the dicarboxylic acid that replaces.These acid-ester dextrin is preferably by for example waxy corn, wax Chinese sorghum, western paddy rice, wood work starch and the potato preparation of this starch.The suitable example of said encapsulating material comprises the N-Lok that is produced by National Starch.This N-Lok encapsulating material is made of the W-Gum and the glucose of modification.This starch be by add group that simple function replaces for example the octenyl succinic glycosides be modified.

Preferred white dyes is an anionic, the example has 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 '-disodium sulfonate, 4,4 '-two (2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-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-hydroxyethylamino)-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-thio phenyl vinyl) biphenyl.Highly preferred whitening agent is a disclosed particular brightener in EP753567.

Other suitable polymeric materials are polyoxyethylene glycol, and particularly those molecular weight are 1000-10000, more particularly 2000-8000, most preferably from about 4000 polyoxyethylene glycol.The consumption of these materials is 0.20% to 5%, more preferably 0.25% to 2.5% weight.The multi-carboxylate of these polymkeric substance and aforesaid homopolymerization or copolymerization under the condition that transition metal impurity exists for the deposition of the maintenance that improves whiteness, fabric dust with aspect the cleaning performance of great soil group, protein-based and oxidable dirt, all be valuable.

Preferably, detergent composition of the present invention also comprises anti redeposition agent (also being called soil-suspending agent) and is used to improve Fouling Cleaning power.Bound by theory is not believed that this anti redeposition agent has captured the retrogradation starch in the washing soln and suppressed it to deposit on the fabric face again.So the combination of itself and retrograded starch degrading enzyme of the present invention has reached collaborative cleaning dirt.

Anti redeposition agent that the present invention is suitable for and soil-suspending agent comprise derivatived cellulose for example methylcellulose gum, carboxymethyl cellulose, Natvosol and homopolymerization or the poly carboxylic acid of copolymerization or their salt.Such polymkeric substance comprises above-mentioned polyacrylate and multipolymer, the maleic anhydride of maleic anhydride and acrylic acid multipolymer and maleic anhydride and ethene, methylvinylether or methylacrylic acid at least 20% (mole) that account for co-polymer as washing assistant.The common consumption of these materials is 0.5% to 10% of a composition weight, more preferably 0.75% to 8%, most preferably 1% to 6%.For the object of the invention, preferred anti redeposition agent is a carboxymethyl cellulose.

The dirt release agent that is used for the present composition is the multipolymer or the terpolymer that form with various arrangement modes of terephthalic acid and ethylene glycol and/or propylene glycol unit normally.The example of this multipolymer be disclosed in common transfer United States Patent (USP) 4116885 and 4711730 and European publication application 0 272 033 in.According to EP-A-0272033, a kind of particularly preferred polymkeric substance has formula:

(CH ₃(PEG) ₄₃) _0.75(POH) _0.25[T-PO) _2.8(T-PEG) _0.4] T (PO-H) _0.25((PEG) ₄₃CH ₃) _0.75Wherein PEG is-(OC ₂H ₄) O-, PO is (OC ₃H ₆O) and T be (pcOC ₆H ₄CO).

The polyester of modification very usefully also, as dimethyl terephthalate (DMT), sulfoisophthalic acid dimethyl ester, ethylene glycol and 1, the random copolymers of 2-propylene glycol, its end group mainly are made up of the monoesters of ethylene glycol and/or propylene glycol sulfosalicylic acid ester and next.Purpose is to obtain a kind of two ends all by the ester terminated polymkeric substance of sulfosalicylic acid." mainly " meaning in this article is that most of here said multipolymers are all ester terminated by sulfosalicylic acid.But some multipolymers are not fully by end-blocking, so their end group can be by ethylene glycol and/or 1, and the monoesters of 2-propylene glycol is formed, and it is that this class material " less important " is formed.

The polyester that this paper selects contains the 46% weight dimethyl terephthalate (DMT) of having an appointment, about 16% weight 1, and the 2-propylene glycol, about 10% weight ethylene glycol, about 13% weight sulfosalicylic acid dimethyl ester and about 15% weight sulfoisophthalic acid, its molecular weight is about 3000.This polyester and its preparation method are described in detail among the EPA311342.

Free chlorine in tap water known in the art can make the enzyme rapid deactivation that comprises in the detergent composition.Therefore, in prescription, use and account for chlorine scavenger that total composition weight is higher than 0.1% (weight) for example perborate, ammonium sulfate, S-WAT or polyethylene imine basedly will provide the detergent enzyme stability of improvement in the whole process of washing.The composition that comprises chlorine scavenger is described in the european patent application 92870018.6 of application on January 31st, 1992

The alkoxylate polycarboxylate for example by the polyacrylate preparation those, is applicable to that also the present invention is to provide extra degrease performance.This class material is described in WO91/08281 and PCT90/01815, page or leaf such as page 4 and back, and this paper quotes for referencial use.From chemically, these materials comprise that every 7-8 vinylformic acid root 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.This side chain is connected with polyacrylate " skeleton " by ester bond, obtains the polymkeric substance of " pectination " structure type, and its molecular weight can change, but generally in about 2000-50000 scope.This alkoxylate polycarboxylate can account for about 0.05%-10% of present composition weight.Dispersion agent

Detergent composition of the present invention also can contain dispersion agent: suitable water-soluble organic salt, and they are acid or its salt of homopolymerization or copolymerization, wherein poly carboxylic acid comprises at least two carboxyls that are separated from each other by no more than 2 carbon atoms.Such polymkeric substance is disclosed 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 polymkeric substance has molecular weight 1000-100000.

Especially the multipolymer of acrylate and methylacrylate, the 480N of molecular weight 4000 for example, by the weight of composition, it can 0.5%-20% weight add in the detergent composition of the present invention.

The present composition can contain calcium soap peptizing agent compound, and it preferably has the ability (LSDP) of disperseing calcium soap, is no more than 8 as the ability LSDP of the dispersion calcium soap of definition hereinafter, preferably is no more than 7, is most preferably not exceeding 6.The content of calcium soap peptizing agent compound is pressed composition weight meter, is preferably 0%-20%.

The numeric measure of calcium soap peptizing agent effect is provided by the ability (LSDP) of lime soap dispersing agent, the ability of described lime soap dispersing agent is to use H.C.Borghetty and C.A.Bergman, J.Am. learn association (Oil.Chem.Soc.) the 27th volume, the lime soap dispersing agent measuring of describing in the article of 88-90 page or leaf (1950) at oiling.This calcium soap dispersion experiment method is extensive use of by the professional in present technique field, and reference example is as, following survey article; W.N.Linfield, tensio-active agent science and technology series (Surfactant Science Series), the 7th volume, page 3; W.N.Linfield, surfactant detergent (Tenside Surf.Det.), the 27th volume, 159-163 page or leaf (1990); And M.K.Nagarajan, W.F.Masler, makeup and toilet articles (Cosmetic and Toiletries), the 104th volume, 71-73 page or leaf (1989).LSDP disperses the dispersion agent that the calcium soap settling needs and the weight % ratio of sodium oleate, and said calcium soap settling is by at the 333ppm of 30ml CaCO ₃(Ca: Mg=3: 2) the 0.025g sodium oleate in the equivalent hardness water forms.

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

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

Be applicable to that polymeric calcium soap sol of the present invention is described in M.K.Nagarajan, in the article of W.F.Masler, see makeup and toilet articles (Cosmetic andToiletries), the 104th volume, 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; Also can be used as this soap sol component with the combination of nonanoyl oxygen benzene sulfonate and hydrophilic/hydrophobic SYNTHETIC OPTICAL WHITNER preparation.The dye transfer restraining effect

Detergent composition of the present invention can comprise that also being used for being suppressed at the dyestuff that comprises dissolved that the laundering of textile fabrics operating process of being with yarn dyed fabric is run into and suspension is transferred to compound on the another kind of fabric from a kind of fabric.The polymeric dye transfer inhibitor

Detergent composition of the present invention also comprises 0.001% to 10%, and is preferred 0.01% to 2%, more preferably 0.05% to 1% weight polymeric dye transfer inhibitor.Usually described polymeric dye transfer inhibitor is mixed in the detergent composition is to be transferred on the fabric of washing simultaneously from the band yarn dyed fabric in order to suppress dyestuff.Washed the fugitive dye that gets off before other article of having an opportunity to contact the washing from the band yarn dyed fabric, these polymkeric substance have the ability with its chelating or absorption.

Particularly 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 can also strengthen the performance of enzyme of the present invention.A) polyamine N-oxide pllymers

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

Wherein P is polymerisable unit, the R-N-O group can connect thereon or wherein the R-N-O group constitute the part of this polymerizable unit or the two mixed form.

A is

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

R is aliphatic series, aliphatic, the aromatics of ethoxylation, heterocycle or alicyclic group or their any combination, the wherein part that the nitrogen-atoms of N-O group can connect thereon or wherein the nitrogen-atoms of N-O group is these groups.

The N-O group can be represented by following general structural formula: R wherein ₁, R ₂And R ₃Be aliphatic group, aromatics, heterocycle or alicyclic group or their mixture, x or/and y or/and z is 0 or 1, the part that the nitrogen-atoms of N-O group can connect thereon or wherein the nitrogen-atoms of N-O group forms these groups wherein.

The N-O group is that the part of polymerizable unit (P) maybe can be connected on the polymeric main chain or the two mixed form.

The polyamine N-oxide that is fit to that the N-O group constitutes the part of polymerizable unit comprises that R wherein is selected from the polyamine N-oxide of aliphatic series, aromatics, alicyclic ring or heterocyclic group.

The said polyamine N-oxide of one class comprises the wherein polyamine N-oxide of the part of the nitrogen-atoms formation R group of N-O group.Preferred polyamine N-oxide compound is that wherein R is that heterocyclic group for example sting and their those polyamine N-oxide of derivative by pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, a word used for translation.

Another kind of said polyamine N-oxide comprises that the nitrogen-atoms of N-O group wherein is connected the polyamine N-oxide on the R group.

Other polyamine N-oxide that are fit to are that wherein the N-O group is connected polyamine N-oxide on the polymerizable unit.

A preferred class is the polyamine N-oxide with general formula (I) in these polyamine N-oxide, and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen-atoms of N-O functional group is the part of said R group.

The example of these classes is that wherein R is for example polyamine oxide compound of pyridine, pyrroles, imidazoles and their derivative of heterogeneous ring compound.

Another kind of preferred polyamine N-oxide compound is the polyamine oxide compound with general formula (I), and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen-atoms of N-O functional group is connected on the said R group.

The example of these types is that wherein the R group is for example polyamine oxide compound of phenyl of aromatic group.

Can use any main polymer chain, as long as the amine oxide polymers that forms is water miscible and has the character that suppresses dye transfer.The example of the polymer main chain that is fit to is polyvinyl, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylate and their mixture.

The ratio that amine n-oxide polymkeric substance of the present invention typically has amine and amine n-oxide is 10: 1 to 1: 1000000.Yet the quantity that is present in the amine oxide group in the polyamine oxide polymer can change by suitable copolymerization or suitable N-oxidisability.The ratio of preferred amines and amine n-oxide is 2: 3 to 1: 1000000, more preferably 1: 4 to 1: 1000000, and most preferably 1: 7 to 1: 1000000.In fact polymkeric substance of the present invention comprises random and segmented copolymer, and wherein a kind of type monomers is an amine n-oxide, and the other types monomer is amine n-oxide or is not.Amine oxide unit in the polyamine N-oxide has PK _a＜10, preferred PK _a＜7, more preferably PK _a＜6.

Can almost obtain any polymerization degree the polyamine oxide compound.The polymerization degree is not crucial, as long as this material has the ability of the water-soluble of requirement and suspension dyestuff.

Typically, its molecular-weight average is 500 to 1000,000; Preferred 1000 to 50000, more preferably 2000 to 30000, most preferably 3000 to 20000.B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole

Being used for N-vinyl imidazole N-vinyl pyrrolidone polymer of the present invention, to have molecular-weight average be 5000-1,000,000, and preferred 5,000-200,000.

The highly preferred polymkeric substance that is used for detergent composition of the present invention comprises the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, and wherein said polymkeric substance has molecular-weight average 5,000 to 50,000, more preferably 8,000 to 30,000, most preferably 10,000 to 20,000.

This molecular-weight average is by for example at Barth H.G. and Mays J.W. chemical analysis (Chemical Analysis) the 113rd volume, the light scattering method measuring of describing among " modernism of polymer characterization " (ModernMethods of Polymer Characterization).

Highly preferred N-vinyl imidazole N-vinylpyrrolidone copolymer has molecular-weight average 5,000 to 50,000, and more preferably 8,000 to 30,000, most preferably 10,000 to 20,000.

Be characterised in that the N-vinyl imidazole N-vinylpyrrolidone copolymer with said average molecular weight range provides the character of fabulous inhibition dye transfer, the cleaning performance to the detergent composition prepared does not have opposite influence simultaneously.

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

Detergent composition of the present invention also can use has molecular-weight average about 2,500 to about 400,000, and preferred about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000, most preferably from about 5,000 to about 15,000 polyvinylpyrrolidone (" PVP ").The polyvinylpyrrolidone that is fit to commercial can be from ISP company, New York, NY and Montreal, Canada is by name of product PVP K-15 (viscosity molecular weight is 10,000); PVP K-30 (molecular-weight average 40,000); PVP K-60 (molecular-weight average 160,000) and PVP K-90 (molecular-weight average 360,000) buy.Can comprise Sokalan HP 165 and Sokalan HP 12 by other polyvinylpyrrolidones that are fit to that BASF AG buys commercial; The known polyvinylpyrrolidone of the technician of detergent applications (referring to for example EP-A-262,897 and EP-A-256,696).D) Ju Yi Xi oxazolidone

Detergent composition of the present invention also can use Ju Yi Xi oxazolidone as the polymeric dye transfer inhibitor.Said Ju Yi Xi oxazolidone has molecular-weight average about 2,500 to about 400,000, and preferred about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.E) polyvinyl imidazole

Detergent composition of the present invention also can use polyvinyl imidazole as the polymeric dye transfer inhibitor.Said polyvinyl imidazole has molecular-weight average about 2,500 to about 400,000, and preferred about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.F) crosslinked polymkeric substance

Cross-linked polymer is that its skeleton interconnects to polymkeric substance to a certain degree; These keys can be chemistry or physical property, can have active group on the skeleton or on side chain.Cross-linked polymer has been described in polymkeric substance science and technology magazine, the 22nd volume, 1035-1039 page or leaf.

In one embodiment, cross-linked polymer is to prepare with such method, and promptly they form three-dimensional rigid structure, and it can be captured in dyestuff in the hole that is formed by three-dimensional structure.In another embodiment, cross-linked polymer captures dyestuff by swelling (swelling).This cross-linked polymer is described in the patent application 94870213.9 of pending trial.Washing methods

The present composition can be used for comprising immersion process in any washing or the purging method basically, and pretreatment process and having in the method for rinse step can add the independent composition that helps rinsing in described rinse step.

Method described herein comprises by usual method and the method that hereinafter exemplifies explanation fabric, tableware or any other hard table is contacted with washing soln.Conventional clothes washing method comprises with dissolving or has disperseed the detergent for washing clothes of significant quantity and/or the aqueous solution of Fabrid care composition to handle the fabric of being with dirt.Preferred machine wash up method comprises with dissolving or has disperseed the machine wash up of significant quantity or the aqueous solution of rinse composition to handle the fabric of being with dirt.The conventional significant quantity of machine dishwashing compositions is to rise dissolving or dispersion 8-60g product in the wash volumes at 3-10.According to the manual dishwashing method, the tableware of band dirt contacts with the dishwashing compositions of significant quantity, generally is 0.5-20g (processed per 25 tablewares).Preferred manual dishwashing method comprises and concentrated solution is administered to the tableware surface or tableware is immersed in the Macrodilution solution of detergent composition.Conventional crust method comprises with for example sponge, brush, cloth etc., with dissolving or having disperseed the hard surface cleaner of significant quantity and/or with the dirty hard article of undiluted this compositions-treated.Its also comprise be immersed in the concentrated solution or the Macrodilution solution of detergent composition in.The inventive method suits to finish in washing process.This purging method preferably carries out under 5 ℃ to 95 ℃, particularly carries out under 10 ℃ to 60 ℃.The pH of treatment soln is preferably 7 to 12.

Following examples are to be used to illustrate composition of the present invention, rather than are used for restriction or define scope of the present invention in addition.

In detergent composition, the content of enzyme is to represent that by the weight that pure enzyme accounts for total composition unless otherwise indicated, detergent components is to represent by the weight that accounts for total composition.The component symbol of wherein writing a Chinese character in simplified form has to give a definition: LAS: straight chain C _11-13Sodium alkyl benzene sulfonate TAS: tallow alkyl sodium sulfate C _XyAS: C _1X-C _1ySodium alkyl sulfate C _XySAS: C _1x-C _1ySecondary (2,3) sodium alkyl sulfate C _XyE _Z: the average z moles of ethylene oxide of condensation mainly be the C of straight chain _1X-C _1y

Primary alconol C _XYE _ZS: the C of the average z moles of ethylene oxide of condensation _1X-C _1ySodium alkyl sulfate C _xEO _y: average degree of ethoxylation is the C of y _yThe alcohol non-ionic type: the blended ethoxylated/propoxylated fatty alcohol, for example

Plurafac LF404 is that average degree of ethoxylation is 3.8 and average

The propoxylation degree is 4.5 pure 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 ₁₁SADS: formula 2-(R) .C4H7-1,4-(SO ^4-) ₂C14-22 alkyl two sulphur

Acid sodium, wherein R=C10-18MBAS: on average have among the C12-18 of 1.5 methyl or ethyl branching group

The alkyl sulfate surfactant MES of chain branching: the x-sulfo methyl ester APA of C18 lipid acid: C _8-10Amido propyl-dimethyl amine soap: obtain by 80/20 mixture of butter and coco-nut oil fatty acid

Straight-chain alkyl carboxylic acid's sodium STS: toluenesulfonic acid sodium salt TFAA: C ₁₆-C ₁₈Alkyl N-methyl glucose amide TPKFA: the full cut DEQA of C12-C14 lipid acid topping: chlorination two (butter acyloxy ethyl) Dimethyl Ammonium DEQA (2): two (soft tallow acyloxy ethyl) hydroxyethyl ammonium methyl methylsulfuric acid

Salt SDASA: 1: 2 stearyl dimethyl amine: triple pressed stearic acid DTMAMS: two butter Dimethyl Ammonium Methylsulfate silicate: amorphous sodium silicate (SiO ₂: Na ₂O=1.6-3.2: 1) metasilicate: Starso (SiO ₂: Na ₂O=1.0) zeolite A: formula Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂The hydrated aluminum silicate of O, elementary

Granularity is 0.1 to 10 micron (weight of representing by moisture-free basis) SKS-6: formula δ-Na ₂Si ₂O ₅The crystalline layered silicate Citrate trianion: citrate trisodium dihydrate citric acid: Citric Acid, usp, Anhydrous Powder carbonate: anhydrous sodium carbonate supercarbonate: sodium bicarbonate 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, molecular-weight average

About 70000-80000MA/AA1: 6: 4 acrylate/maleate random copolymerss, molecular-weight average

About 10000AA: the sodium polyacrylate polymer poly carboxylate salt of molecular-weight average 4500: comprise carboxylic acidifying monomer such as vinylformic acid, toxilic acid and methyl-prop

The multipolymer of the mixture of olefin(e) acid, its MW are 2000-80000,

Such as the Sokolan that is purchased by BASF, it is the propylene of MW4500

Acid copolymer clay: wilkinite or terre verte PB1: anhydrous sodium perborate monohydrate PB4: standard type NaBO ₃.4H ₂The sodium perborate tetrahydrate percarbonate of O: standard type is Na ₂CO ₃3H ₂O ₂Anhydrous SPC-D NaDCC: dichloroisocyanuric acid sodium TAED: tetraacetyl ethylene diamine NOBS: the nonanoyl oxygen benzene sulfonate NACA of sodium-salt form-: (6-nonanoyl amino caproyl) oxygen benzene sulfonate OBSLOBS: the lauroyl oxygen benzene sulfonate DOBA of sodium-salt form: dodecanoyl yl benzoic acid DTPA: diethylene triaminepentaacetic acid(DTPA) HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid DETPMP: the diethyl of selling with trade(brand)name Dequest 2060 by Monsanto

Base triamine five (methylene radical) phosphonate EDDS: the quadrol-N of sodium-salt form, N '-disuccinic acid, (S, S) isomery

Body MnTACN: manganese 1,4, the 7-trimethylammonium-, 1,4, the photoactivation of 7-7-triazacyclononane: with the sulfonation phthalocyanine phthalocyanine zinc or the aluminium SYNTHETIC OPTICAL WHITNER PAAC of the dextrin polymeric encapsulate of solubility: five aminophenylsulfonic acid cobalt (III) salt paraffin: the paraffin oil NaBz that sells with trade(brand)name Winog 70 by Wintershall: Sodium Benzoate proteolytic enzyme: by Novo Nordisk A/S with trade(brand)name Savinase,

The proteolytic ferment that Alcalase sells, replacement occurs in

" proteolytic enzyme D " variant of N76D/S103A/V104I, and describe

At PCT application number PCT/US98/22588, PCT/US98/22482

With the proteolytic enzyme among the PCT/US98/22486, its aminoacid replacement is sent out

Give birth at 101G/103A/104I/159D/232V/236H/245R

/ 248D/ 252K amylase: by Novo Nordisk A/S with trade(brand)name Termamyl ^With

Duramyl ^The amylolytic enzyme of selling and to have the heat of improvement steady

Those variants qualitatively, its aminoacid deletion is at R181 + G182

Or T183 + G184 , lipase described in WO95/35382: by Novo Nordisk A/S with trade(brand)name Lipolase,

Lipolase Ultra and by Gist Brocades with trade(brand)name

The lipolytic enzyme ReSI-AMG that Lipomax sells: by the starch Portugal of Novo Nordisk A/S with trade(brand)name AMG sale

Glycosylase amylopectin:, have the enzyme Type II alkalescence Starch debranching enzyme Y cellulase of alpha-amylase activity as in EP418835, describing; By Novo Nordisk A/S with trade(brand)name Carezyme,

The cellulase CMC that Celluzyme and/or Endolase sell: Xylo-Mucine PVP: polyvinyl polymkeric substance, molecular-weight average is 60000PVNO: polyvinylpyridine-N-oxide compound, molecular-weight average 50000PVPVI: vinyl imidazole and vinylpyrrolidone copolymers, average mark

The son amount is 20000 whitening agent 1: 4,4 '-two (2-sulfo group styryl) biphenyl disodium whitening agent 2: 4,4 '-two (4-phenylaminos-6-morpholino-1,3,5-triazines-2-

Base) stilbene-2:2 '-disulfonic acid disodium whitening agent is 3: 4,4 '-two (4,6-diphenylamino-1,3,5-triazines-2-yl) amino

Stilbene-2:2 '-disulfonic acid disodium polysiloxane: polydimethylsiloxane foam control agent and mixture, described foam control agent and described dispersion as the siloxanes-defoamer oxyalkylene copolymers of dispersion agent

The weight ratio of agent is 10: 1-100: 1 suds suppressor: 12% polysiloxane/silicon-dioxide, 18% stearyl alcohol, 70%

Particle shape formula starch thickener: high molecular weight crosslinked polyacrylate is such as by B.F.Goodrich

The CarbopolSRP1 that Chemical Company and Polygel provide: the end capped polyester SRP2 of anionic group: the dirt release agent polymkeric substance, it is selected from 1) according to May 16 nineteen ninety-five

The Gosselink that day authorizes, Pan, U.S. of Kellett and Hall

The non-cotton dirt release agent polymkeric substance of state's patent 5415807 and/or

2) according to the non-cotton dirt release agent of U. S. application number 60/051517

Polymkeric substance QEA: 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, n=20-30PEI wherein: polyethylene imine based, molecular-weight average is 600-1800, each

The average degree of ethoxylation of nitrogen is 7-20 oxygen ethene residue SCS: cumene sodium sulfonate HMWPEO: high molecular weight peo PEGx: polyoxyethylene glycol, molecular weight is xPEO: polyoxyethylene, molecular-weight average is 5000TEPAE: tetren ethoxylate BTA: benzotriazole pH: by under 20 ℃, and the embodiment 1 that 1% distilled water solution is measured

Preparation is according to following granular laundry detergent compositions of the present invention:

Spray-dired particle LAS 10.0 10.0 15.0 5.0 5.0TAS-1.0 of I II III IV V---MBAS---5.0 5.0C ₄₅AS--1.0-2.0C ₄₅AE ₃S --- 1.0-QAS - 1.0 1.0-DTPA, HEDP and / or EDDS 0.3 0.3 0.5 0.3-magnesium-citrate 0.5 0.5 0.1 --- 3.0 5.0 Carbonate 10.0 7.0 15.0 - Sulfate 5.0 5.0 - silicate ---- 2.0 5.0 zeolite A 16.0 18.0 20.0 20.0-SKS-6 --- 3.0 5.0MA/AA or AA 1.0 2.0 11.0 - PEG 4000-2.0-1.0-QEA 1.0 --- 1.0 growth whitening agents 1, 2, or 3 silicone oil 0.05 0.05 0.05-0.05 0.01 0.01 0.01 - carbonate agglomerates ---- 4.0SKS-6 6.0 --- 6.0LAS 4.0 5.0 - 5.0 dry add group of particles of maleic acid / carbonate / bicarbonate 8.0 10.0 10.0 4.0-(40:20:40) QEA --- 0.2 0.5NACA-OBS 3.0 - 4.5-NOBS 1.0 3.0 3.0 - TAED 2.5 - 1.5 2.5MBAS --- 8.0-LAS (sheet) 10.0 10.0 ---

I II III IV V sprays brightening agent 1 or the 2 or 3 0.2 0.2 0.3 0.1 0.2 photoactivated bleaching agent 0.02 0.02 0.02 0.1 0.05 enzyme (cellulases of spices 1.0 0.5 1.1 0.8 0.3 dried additive--20.0 4.0-citrate 15.0 3.0 6.0 10.0-percarbonate----6.0 perborate; Amylase, proteinase-10 .04 0.01 0.02 0.02 0.05 and/or lipase) ReSI-AMG 1.0 0.05 0.002 0.001 0.05 carbonate 0.0 10.0---spices (sealing)-0.5 0.5-0.3 foam inhibitor 1.0 0.6 0.3-0.10 soap 0.5 0.2 0.3 3.0 0.5 citric acids---6.0 6.0SKS-6---4.0-

Filler to 100%

Embodiment 2

The powder MES 2.0 0.5 1.0-SADS of I II III IV blowing---2.0LAS 6.0 5.0 11.0 6.0TAS 2.0--2.0 Wessalith CSs 24.0--20.0STPP-27.0 24.0-sulfate 4.0 6.0 13.0-MA/AA 1.0 4.0 6.0 2.0 silicate 1.0 7.0 3.0 3.0CMC 1.0 1.0 0.5 0.6

I, II, III, IV brightening agent 1, 0.2, 0.2, 0.2, 0.2 polysiloxane defoamers, 1.0, 1.0, 1.0, 0.3DTPMP, 0.4, 0.4, 0.2, 0.4 spray brightening agent 1 or 2 or 3, 0.02,-,-, 0.02C45E7,-,-,-, 5.0C45E2, 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,-,-,-, 1.0EDDS, 0.3,-,-,-sulfate, 2.0, 3.0, 5.0, 10.0 carbonate, 6.0, 13.0, 15.0, 14.0 citric acid, 2.5,-,-, 2.0QAS, 0.5,-,-, 0.5SKS-6, 10.0,-,-,-percarbonate, 4.0, 3.0,-, 1.9PB4,-,-,-NOBS, 0.5,-,-, 0.3TAED, 0.75, 4.5,-, 0.5 clay,-,-, 10.0,-protease, 0.03, 0.03, 0.03, 0.03 lipase, 0.008, 0.008, 0.008, 0.004ReSI-AMG, 0.001, 0.01, 0.01, 0.004 amylopectase II,-,-, 0.01,-amylase, 0.003,-, 0.003, 0.006 brightening agent 1, 0.05,-,-, 0.05 other/adminicle and spot decorations, to 100%, embodiment 3

I, II, III, IV, V, the powder LAS of VI blowing, 23.0, 8.0, 7.0, 9.0, 7.0, 7.0QAS,-,-,-,-, 1.0,-C45AS, 6.0, 6.0, 5.0, 8.0,-,-C45AE11S,-, 1.0, 1.0, 1.0,-,-MES, 2.0,-,-,-, 2.0, 4.0 Wessalith CS, 10.0, 18.0, 14.0, 12.0, 10.0, 10.0MA/AA,-, 0.5,-,-,-, 2.0MA/AA1, 7.0,-,-,-,-,-AA,-, 3.0, 3.0, 2.0, 3.0, 3.0 sulfate, 5.0, 6.3, 11.1, 11.0, 11.0, 18.1 silicate, 10.0, 1.0, 1.0, 1.0, 1.0, 1.0 carbonate, 15.0, 20.0, 10.0, 20.7, 8.0, 6.0PEG, 4000, 0.4, 1.5, 1.5, 1.0, 1.0, 1.0DTPA,-, 0.9, 0.5,-,-, 0.5 brightening agent 2, 0.3, 0.2, 0.3,-, 0.1, 0.3 spray C45E7,-, 2.0,-,-, 2.0, 2.0C25E9, 3.0,-,-,-,-,-C23E9,-,-, 1.5, 2.0,-, 2.0 spices, 0.3, 0.3, 0.3, 2.0, 0.3, 0.3 agglomerate C45AS,-, 5.0, 5.0, 2.0,-, 5.0LAS,-, 2.0, 2.0,-,-, 2.0 Wessalith CS,-, 7.5, 7.5, 8.0,-, 7.5 carbonate,-, 4.0, 4.0, 5.0,-, 4.0PEG, 4000,-, 0.5, 0.5,-,-, 0.5 other, (water sheep),-, 2.0, 2.0, 2.0,-, 2.0 dried additive QASI,-,-,-,-, 1.0,-citric acid,-,-,-,-, 2.0,-PB4,-,-,-,-, 5,-PB1,-,-, 4, 1.0,-,-percarbonate, 2.0,-,-, 1.0,-, 2.0 carbonate,-, 5.3, 1.8,-, 4.0, 4.0

I, II, III, IV, V, VINOBS, 0.5,-, 0.4, 0.3,-,-clay,-,-,-,-,-, 10.0TAED, 0.6, 0.4, 0.6, 0.3, 0.9,-methylcellulose, 0.2,-,-,-,-, 0.5DTPA, 0.7, 0.5, 1.0, 0.5, 0.5, 1.2 look grain,-,-,-, 0.2., 0.5,-SKS-6, 8.0,-,-,-,-,-STS,-,-, 2.0,-, 1.0,-cumene sulfonic acid,-, 1.0,-,-,-, 2.0 lipase, 0.004,-, 0.004,-, 0.004, 0.008 cellulase, 0.0005, 0.0005, 0.0005, 0.0007, 0.0005, 0.0005 amylase, 0.003,-, 0.001,-, 0.003,-amylopectase II,-, 0.01,-,-, 0.001,-ReSI-AMG, 0.01, 5.0, 0.05, 0.002, 0.001, 0.05 protease, 0.01, 0.015, 0.015, 0.009, 0.01, 0.01PVPVI,-,-,-,-, 0.5, 0.1PVP,-,-,-,-, 0.5,-PVNO,-,-, 0.5, 0.3,-,-QEA,-,-,-,-, 1.0,-SRP1, 0.2, 0.5, 0.3,-, 0.2,-polysiloxane defoamers, 0.2, 0.4, 0.2, 0.4, 0.1,-magnesium sulfate,-,-, 0.2,-, 0.2,-

Other/subsidiary to 100%

Embodiment 4

I II III IV basic granules STPP-22.0-15.0 zeolite A 30.0-24.0 5.0 vitriol 5.5 5.0 7.0 7.0MA/AA 3.0---

I, II, III, IVAA,-, 1.6, 2.0,-MA/AA, 1,-, 12.0,-, 6.0LAS, 14.0, 10.0, 9.0, 20.0C45AS, 8.0, 7.0, 9.0, 7.0C45AE11S,-, 1.0,-, 1.0MES, 0.5, 4.0, 6.0,-SADS, 2.5,-,-, 1.0 silicate,-, 1.0, 0.5, 10.0 soap,-, 2.0,-,-brightening agent 1, 0.2, 0.2, 0.2, 0.2 carbonate, 6.0, 9.0, 8.0, 10.0PEG, 4000,-, 1.0, 1.5,-DTPA,-, 0.4,-,-spray C25E9,-,-,-, 5.0C45E7, 1.0, 1.0,-,-C23E9,-, 1.0, 2.5,-spices, 0.2, 0.3, 0.3,-dried additive carbonate, 5.0, 10.0, 13.0, 8.0PVPVI/PVNO, 0.5,-, 0.3,-protease, 0.03, 0.03, 0.03, 0.015 lipase, 0.008,-,-, 0.008ReSI-AMG, 0.01, 3.0, 0.05, 0.005 amylopectase II,-,-, 0.02, 0.001 amylase, 0.002,-,-, 0.002 cellulase, 0.0002, 0.0005, 0.0005, 0.0003DTPA, 0.5, 0.3, 0.5, 1.0LOBS,-, 0.8,-, 0.3PB1, 5, 3.0, 10, 4.0DOBA, 1.0,-, 0.4,-TAED, 0.5, 0.3, 0.5, 0.6 sulfate, 4.0, 5.0,-, 5.0SRP, 1,-, 0.4,-,-foam inhibitor,-, 0.5,-,-

I II III IV spot decorations 09-27 1.2

Other/subsidiary to 100%

Embodiment 5

I II III IV IV V VIC ₁₃LAS 12.0 16.0 23.0 19.0 18.0 20.0 16.0C ₄₅AS 4.5---4.0C ₄₅AE (3) S--2.0-1.0 1.0 1.0C ₄₅AE (3.0) 2.0 2.0-1.3--0.6C ₉-C ₁₄Alkyl dimethyl - 1.0 0.5 2.0 tallow fatty hydroxyethyl quaternary ------ 1.0STPP 23.0 25.0 24.0 22.0 20.0 15.0 20.0 Carbonate 15.0 12.0 15.0 10.0 13.0 11.0 10.0AA 0.5 0.5 0.5 0.5---MA/AA--1.0 1.0 1.0 2.0 0.5 silicate 3.0 6.0 9.0 8.0 9.0 6.0 8.0 sulfate 25.0 18.0 20.0 18.0 20.0 22.0 13.0 sodium percarbonate 5.0 5.0 10.0 8.0 3.0 1.0 2.0PEG 4000 1.5 1.5 1.0 1.0 - 0.5 CMC 1.0 1.0 1.0-0.5 0.5 0.5 citric acid -------NOBS/DOBS 0.5 1.0 0.5 0.5 1.0 0.7 0.3TAED 1.5 1.0 2.5 3.0 0.3 0.2 0.5SRP 2 1.5 1.5 1.0 1.0 1.0 1.0 1.0 7.5 7.5 6.0 7.0 moisture 5.0 3.0 5.0Mg ---- 1.0 0.5 1.5DTPA; HEDP and / or EDDS ---- 0.8 0.6 1.0ReSI-AMG 0.01 0.01 .005 0.05 1.0 1.0 .001 enzyme (amylase, cellulase ---- 0.05 0.04 0.05 and / or protease)

I II III IV IV V VI other, for example spices, whitening agent, to 100% optical white, spot decorations

Embodiment 6

I II III IVC ₁₃LAS 13.3 13.7 10.4 8.0C ₄₅AS 3.9 4.0 4.5-C ₄₅AE (0.5) S 2.0 2.0--C ₄₅AE (6.5) 0.5 0.5 0.5 5.0C ₉-C ₁₄Alkyl dimethyl 1.0 - 0.5 0.5 --- Ethyl tallow fatty quaternary ammonium tallow alcohol ethoxylate (50) - 1.0 0.3STPP-41.0-20.0 Zeolite A 26.3-21.3 1.0 23.9 Carbonate 12.4 25.2 17.0AA 3.4 0.0 2.7-MA/AA--1.0 1.5 silicate 2.4 6.4 2.1 6.0 10.5 10.9 8.2 15.0 sulfate sodium perborate 1.0 1.0 1.0 2.0PEG 4000 1.7 0.4 1.0-CMC 1.0 - 0.3 citric acid - 3.0-NOBS/DOBS 0.2 0.5 0.5 0.1TAED 0.6 0.5 0.4 0.3SRP 2 1.5 1.5 1.0 1.0 7.5 3.1 6.1 7.3 moisture magnesium --- 1.0DTPA, HEDP and / or EDDS --- 0.5

I II III IV enzyme (amylase, cellulase ,-0.025-0.04 proteolytic enzyme and/or lipase) ReSI-AMG 0.02 0.05 0.005 0.008 other/subsidiary comprises spices, to 100% whitening agent, optical white

Embodiment 7

Preparation is according to the laundry detergent composition of following sheet of the present invention or granular preparation form:

I II III IV V VIC ₁₃LAS 20.0 16.0 8.5 5 20.0 6.0C ₄₅AS-4.0---C ₄₅AE (3) S 1.0 1.0----C ₄₅AE-5.0 5.5 4.0-C ₉-C ₁₄Alkyl dimethyl hydroxyethyl quaternary ammonium ---- 0.5 2.0 tallow fatty acid-1.0---- STPP / Zeolite 10.0 20.0 30.0 20.0 25.0 25.0 Carbonate 41.0 30.0 30.0 25.0 45.0 24.0AA----- -MA/AA 2.0 0.5 0.5 1.0 - silicate 6.0 8.0 5.0 6.0 8.0 5.0 2.0 3.0 --- 8.0 sulfate sodium perborate / 1.0-20.0 14.0 - percarbonate PEG 4000-0.5 --- 0.5CMC 0.5 0.5 0.5 0.5-0.5 citric ------NOBS/DOBS 0.7 ----- TAED / preformed peracids 0.7-4.5 5.0 - DTPA, HEDP and / or EDDS - 0.5 0.5-SRP 1.0-1.0 1.0 - clay 6.0 8.0 4.0 3.0 7.0 10.0

I II III IV V VIPEO 1.0 0.5 2.0 0.5 1.0 0.5 wetting agents 0.5--0.5--paraffin 0.5--0.5--Mierocrystalline cellulose 2.0--1.5-1.0 sodium acetate--1.0 0.5 4.0 1.0 moisture content 3.0 5.0 5.0 5.0 8.0 10.0 sal epsom 0.5 1.5----soap/suds suppressor 0.6 1.0 1.0 0.8 0.5-enzyme (amylase, cellulase, 0.04 0.04 0.01 0.02 0.02 0.03 proteolytic enzyme and/or lipase) ReSI-AMG 0.03 0.01 0.05 .003 0.1 .005 Starch debranching enzyme II--0.02--the .002 subsidiary, spices for example, PVP, Up to 100%PVPVI/PVNO, whitening agent, optical white, the spot decorations,

Embodiment 8

Preparation is according to following laundry detergent composition of the present invention:

I II III IV VC ₁₃LAS 12.0 16.0 23.0 19.0 18.0C ₄₅AS-4.5---C ₄₅AE (3) S--2.0-1.0C ₄₅AE 2.0 2.0-1.3-C ₉-C ₁₄Alkyl dimethyl----1.0 ethoxyl quaternary ammonium salt STPP/ zeolite 23.0 25.0 14.0 22,0 20.0 carbonate 25.0 22.0 35.0 20.0 28.0AA 0.5 0.5 0.5 0.5-MA/AA--1.0 1.0 1.0 silicate 3.0 6.0 9.0 8.0 9.0 sodium perborate/percarbonate 5.0 5.0 10.0-3.0PEG 4,000 1.5 1.5 1.0 1.0-

I II III IV VCMC 1.0 1.0 1.0-0.5NOBS/DOBS-1.0--1.0TAED/ ready-formed peracid 1.5 1.0 2.5-3.0DTPA, HEDP and/or EDDS 0.5 0.5 0.5-1.0SRP 1.5 1.5 1.0 1.0-clay 5.0 6.0 12.0 7.0 10.0 flocculation agent PEO 0.2 0.2 3.0 2.0 0.1 humectants----0.5 paraffin 0.5----Mierocrystalline cellulose 0.5 2.0--3.0 sodium acetate 2.0 1.0 3.0--moisture content 7.5 7.5 6.0 7.0 5.0 soaps/suds suppressor--0.5 0.5 0.8ReSI-AMG 0.02 0.02 .005 .005 0.01 enzyme (amylase, cellulase,----0.045 proteolytic enzyme and/or lipase) other/subsidiary, spices for example, to 100%PVP, PVPVI/PVNO, the spot decorations, whitening agent, optical white,

Embodiment 9

Preparation is according to following liquid laundry detergent compositions of the present invention:

I II III IV V VILAS---1.0 2.0-C25AS 16.0 13.0 14.0 5.0-6.5C25AE3S 5.0 1.0-10.0,19.0 3.0C25E7 2.0 3.5-2.5 2.0 5.0TFAA 5.0 4.5 4.5 6.5 4.0-APA 2.0 1.0-3.0-0.5QAS--2.0-1.5-TPKFA 4.5 8.0 15.0-5.0 5.0 citric acids 2.2 3.0-0.5 1.0 2.0

I II III IV V VI rapeseed fatty acid 2.0 - 3.0 6.0 1.5 Ethanol 3.2 2.0 2.5 5.7 8.5 6.5 7.0 2.2-0.51,2 glycol 5.5 Monoethanolamine 7.0 5.0 7.5-5.0 1.0 2.0TEPAE-1.2-0.5 0.5-PE12-1.5-1.0 0.8-DTPMP 1.3 0.5 0.8 0.5-0.2HEDP-0.5 0.2 1.0 - protease 0.02 0.03 0.02 0.02 0.02 0.01ReSI-AMG 0.01 0.02 0.005 0.01 0.005 0.002 pullulanase II - 0.2 0.05 - lipase 0.002 0.001 0.001-0.001 - amylase .0008 .0006 .0006 0.002 0.001 0.001 cellulase 0.002 0.002-0.002 0.001-SRP1 0.20 0.15 0.10-0.17 0.04PVNO --- 0.05 0.10-0.20 0.15 0.10 0.05-0.05 brightener 3 suds 0.25 0.20 calcium 0.10 0.15 0.15 0.30 0.02 0.02-0.01 0.01-borate 2.5 2.0 1.5 2.2 1.5 1.2 bentonite - 5.5 --- NaOH to pH 8.0 7.5 7.7 8.0 7.0 7.5

Water/subsidiary to 100%

Embodiment 10

Preparation is according to following non-aqueous liquid detergent compositions of the present invention:

I??????????II?????????IIILAS?????????????????????????????16.0???????16.0???????16

I II IIIC23E05S 21.5 21.5 19.0 18.5-16.0 butoxy propoxy propanol hexanediol, sodium citrate dihydrate 5.0 -18.5 6.8 6.8 3.8 [NACA-OBS] Na salt 6.0 6.0 6.0 methyl tetra-substituted polyethoxy glycosylation 1.3 1.3 1.3 methyl hexamethylene diamine EDDS 1.2 1.2 1.2MA/AA--3.0 sodium sulfate 10.0 10.0 10.0 0.05 0.02 0.02 protease pullulanase II - 0.05ReSI-AMG 1.0 0.01 0.02 amylase cellulase 0.01 0.01 0.01 0.0001 0.0001 0.0001PB1 12.0 12.0 12.0 0.75 0.75 silicone antifoam 1.7 1.7 1.7 1.1 TiO spices 0.5 0.5 0.5-5; 12-dimethyl-1; 5; The C16-18 fatty acid sodium soap 11 0.5 look grains 0.4 0.4 0.4 of 8,12 - 0 .03,0.03 four azabicyclo [6.6.2] hexadecane manganous chloride (II) brightening agent 2 0.2 0.2 0.2 hydrogenations other to 100%

Embodiment 11

Preparation is according to following sheet laundry detergent composition of the present invention:

I) by being prepared as follows composition 1 washing composition original washing powder: all particulates matter of basic composition 1 is mixed together in mixing drum, makes the homogeneous granules mixture.In this mixing process, spray.

Ii) prepare sheet then as follows: with the ring mould of 50g substrate material injection diameter 5.5cm, compacting obtains tensile strength (diameter rupture strength) and is the sheet of 10kPa.

Iii) then this sheet is immersed in the Nymcel-ZSB16 that 90 parts of sebacic acid and 10 parts of weight are sold by Metsa Seria that comprise under 140 ℃ ^TMBody lotion in.Regulate this sheet and be immersed in time in the heating bath, make and use this body lotion mixture of 4g.Then this sheet is placed cooling 24 hours under 25 ℃ room temperature.The tensile strength that increases this coating tablet reaches 30kPa.

Anionic agglomerate 1 (40% anion surface activity 21.5

Agent, 27% zeolite and 33% carbonate)

Anionic agglomerate 2 (40% anion surface activity 13.0

Agent, 28% zeolite and 32% carbonate)

Cationic agglomerate (20% cats product, 5.5

56% zeolite and 24% vitriol)

Layered silicate (95%SKS 6 and 5% silicate) 10.8

SPC-D 14.2

Bleach-activating agent agglomerate (81%TAED, 17% vinylformic acid/5.5

Maleic acid (sour form) and 2% water)

Carbonate 10.98

EDDS/ sulphate particle (58%EDDS, 23% vitriol and 0.5

19% water)

HEDP???????????????????????????????????0.8

SRP????????????????????????????????????0.3

Fluorescent agent 0.2

Photoactivated SYNTHETIC OPTICAL WHITNER (phthalein mountain valley with clumps of trees and bamboo sulfonic acid zinc 10% activity) 0.02

Soap powder 1.4

Suds suppressor (11.5% polysiloxane oil; 59% zeolite and 1.9

29.5% water)

Citric acid 7.1

ReSI-AMG???????????????????????????????0.05

Proteinase-10 .03

Lipase 0.006

Cellulase 0.0005

Amylase 0.02

(25%Lutensit 4.0 for the adhesive composition that sprays

K-HD9675% weight PEG) embodiment 12

I, II, III, IV, V, VI first-phase percarbonate, 45.0, 45.0, 45.0, 45.0, 45.0, 45.0TAED, 9.7, 9.7, 9.7, 9.7, 9.7, 9.7 citric acid, 10.0, 15.0, 20.0, 15.0, 15.0, 15.0STPP,-,-,-,-,-, 6.0MA/AA, 6.0, 6.0, 1.0, 5.0,-,-silicate,-,-,-,-, 6.0,-bicarbonate, 15.0, 15.0, 10.0, 15.0, 15.0, 15.0 carbonate, 5.0,-,-,-,-,-brightening agent 1 or 2, 0.1, 0.1, 0.1, 0.1, 0.1, 0.1 spices, 0.2, 0.2, 0.2, 0.2, 0.2, 0.2C12-16 aliphatic acid,-,-,-, 1.0,-,-protease, 0.03, 0.03, 0.03, 0.03, 0.03, 0.03 amylase, 0.02, 0.02,-, 0.02,-,-second-phase ReSI-AMG, 0.01, 0.02, 0.04, 0.01, 0.1, 0.5 protease, 0.04, 0.04, 0.04, 0.04, 0.04, 0.04 amylase, 0.02, 0.02,-,-,-,-Se grain, 0.09, 0.09, 0.09, 0.09, 0.09, 0.09PEG, 4000, 0.33, 0.33, 0.33, 0.33, 0.33, 0.33 citric acid, 1.06, 1.06, 1.06, 1.06, 1.06, 1.06 bicarbonate, 2.87, 2.87, 2.87, 2.87, 2.87, 2.87 embodiment 13

Preparation is according to following laundry bars detergent composition of the present invention (content is to provide by weight, and enzyme is to represent by pure enzyme):

I, II, III, VI, V, III, VI, VLAS,-,-, 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,-,-,-,-,-,-Wessalith CS, 2.0, 1.25,-,-,-, 1.25, 1.25, 1.25 carbonate, 20.0, 3.0, 13.0, 8.0, 10.0, 15.0, 15.0, 10.0 calcium carbonate, 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 bentonite,-, 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 powder,-,-, 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, 0.4SRP, 1, 0.3, 0.3, 0.3, 0.3, 0.3, 0.3, 0.3, 0.3 amylase,-,-, 0.01,-,-,-, 0.002,-ReSI-AMG, 0.01, 0.1, 0.02, 0.002, 0.5, 0.01, 0.01, 0.002 amylopectase II,-,-,-, 0.001,-,-, 0.02,-protease,-, 0.004,-, 0.003, 0.003,-,-, 0.003 lipase,-, 0.002,-, 0.002,-,-,-,-cellulase,-, .0003,-,-, .0003, .0002,-,-PEO,-, 0.2,-, 0.2, 0.3,-,-, 0.3 spices, 1.0, 0.5, 0.3, 0.2, 0.4,-,-, 0.4 magnesium sulfate,-,-, 3.0, 3.0, 3.0,-,-,-brightening agent, 0.15, 0.1, 0.15,-,-,-,-, 0.1 photoactivated,-, 15.0, 15.0, 15.0, 15.0,-,-, 15.0 bleaching agent, (ppm) embodiment 14

Preparation is being washed the following granular fabric detergent composition that whole process provides soft effect according to of the present invention:

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

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

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

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

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

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

Coconut alkyl dimethyl 1.4 1.0

Hydroxyethyl ammonium chloride

Citrate trianion 5.0 3.0

Na-SKS-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

Proteinase-10 .02 0.01

Lipase 0.02 0.01

ReSI-AMG??????????????0.05???????????0.02

Amylase 0.03 0.005

Cellulase 0.001-

Silicate 3.0 5.0

Carbonate 10.0 10.0

Suds suppressor 1.0 4.0

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

Other and subsidiary to 100% embodiment 15

The fabric softener composition that preparation is added during according to following rinsing of the present invention:

DEQA(2)????????????????????????20.0

Cellulase 0.001

ReSI-AMG???????????????????????0.005

HCL????????????????????????????0.03

Defoamer 0.01

Blue dyestuff 25ppm

CaCl ₂?????????????????????????0.20

Spices 0.90

Other and water to 100%

Embodiment 16

The fabric conditioner composition that preparation is dosed according to following fabric softener of the present invention with when using moisture eliminator:

I II III IV VDEQA 2.6 19.0---DEQA (2)----52.0DTMAMS--stearic acid 0.3 of-26.0-SDASA--70.0 42.0 40.2IV=0----C45EO1-3--13.0--HCL 0.02 0.02---ethanol--1.0--spices 0.3 1.0 0.75 1.0 1.5Glycoperse S-20----15.4 glycerin monostearate---26.0-butanedioic acid spiceleaf alcohol ester--0.38--polysiloxane defoamers 0.01 0.01---

I II III IV V electrolyte-0.1---amylase-0.2-0.2 0.2ReSI-AMG 1.0 0.2 0.1 0.01 0.01 clays---3.0-dyestuff 10ppm 25ppm 0.01--water and adminicle 100% 100%---

Embodiment 17

Preparation is according to concentrating high-density (0.96Kg/l) dishwashing detergent composition below of the present invention:

I II III IV V VISTPP-51.0 51.0 - 44.3 Citrate 17.0 - Carbonate 17.5 14.0 50.0 40.2-33.6 20.0-8.0 Bicarbonate --- 26.0 - Silicate 15.0 15.0 8.0-25.0 3.6 biased silicon salt 2.5 4.5 4.5 --- PB1 10.0 8.0 8.0 --- PB4 --- 10.0-- percarbonate ---- 11.8 4.8 non-ionic 2.0 1.5 1.5 3.0 1.9 5.9TAED 2.0 - 4.0-1.4HEDP 1.0 ----- DETPMP 0.6 ----- MnTACN ---- 0.01-PAAC-0.01 0.01 --- paraffin 0.5 0.4 0.4 0.6 - protease 0.07 0.05 0.05 0.03 0.06 0.01 amylase 0.01 0.01 0.01 0.02 0.02 0.006ReSI-AMG 0.02 0.2 2.0 1.0 0.002 0.02 pullulanase II ----- 0.02 lipase-0.001-0.005--BTA 0.3 0.2 0.2 0.3 0.3 0.3 polycarboxylate 6.0 --- 4.0 0.9 perfume 0.2 0.1 0.1 0.2 0.2 0.2 pH 11.0 11.0 11.3 9.6 10.8 10.9 other sulfate and water to 100%

Embodiment 18

Preparation is the following granular dishwashing detergent composition of 1.02Kg/l according to tap density of the present invention:

I II III IV V VISTPP 30.0 33.5 27.9 29.6 33.8 22.0 30.5 30.5 30.5 23.0 34.5 Carbonate 45.0 12.6 13.3 Silicate 3.2 6.2 7.0 7.5-4.5---- metasilicate percarbonate ---- 4.0-PB1 4.4 4.5 4.3 --- NADCC --- 2.0-0.9 nonionic 1.0 0.7 1.0 1.9 0.7 0.5TAED 1.0 --- 0.9-PAAC-0.004---- paraffin 0.25 0.25 0.25 ---- protease 0.036 0.021 0.03-0.006 - Amylase 0.03 0.005 0.004-0.005-ReSI-AMG 0.2 0.02 2.0 2.0 0.02 0.005 ----- 0.002 pullulanase lipase 0.005-0.001-- BTA 0.15 0.15 - 0.2-perfume 0.2 0.2 0.05 0.1 0.2-pH 10.8 11.3 11.0 10.7 11.5 10.9 Others, sulfates, and water to 100% Example 19

By use standard 12 head rotating forming presses, at 13KN/cm ²Compressed granulate dishwashing detergent composition prepares according to following detergent compositions in tablet form of the present invention under the pressure:

I II III IV V VI VII VIIISTPP-48.8 54.7 38.2-52.4 56.1 36.0 20.0 --- 35.9 Citrate-- Carbonate 20.0 15.4 4.0 23.0 20.0 5.0 14.0 15.0 14.8 15.0 12.6 28.0 23.4 Silicate 2.9 4.3 4.2 Protease 0.042 0.072 0.023 0.023 0.029 0.042 0.031 0.052 amylase 0.012 0.012 0.012 0.007 0.015 0.003 0.017 0.002ReSI-AMG 0.02 0.01 0.002 0.5 0.008 0.002 1.0 0.02 pullulanase II 0.002 - 0.002 --- 0.02 lipase 0.005 ----- - PB1 14.3 7.8 11.7 12.2 - 6.7 8.5PB4 ---- 22.8-3.4-percarbonate ----- 10.4 - non-ionic 1.5 2.0 2.0 2.2 1.0 4.2 4.0 6.5PAAC - 0.02 0.009 - - MnTACN ---- 0 .007 --- TAED 2.7 2.4 --- 2.1 0.7 1.6HEDP 1.0 - 0.9-0.4 0.2-DETPMP 0.7 ------- paraffin 0.4 0.5 0.5 0.5 - 0.5-BTA 0.2 0.3 0.3 0.3 0.3 0.3 0.3 polycarboxylate 4.0 --- 4.9 0.6 0.8-PEG 4; 000 ------ 2.0-2.030, weight 20g 25g 20g 30g 18g 20g 25g 24gpH that 000 glycerine ----- 0.4 -0.5 spices --- 0.05 is 0.2 0.2 0.2 0.2 10.7 10.6 10.7 10.7 10.9 11.2 11.0 10.8 other, sulfate and water to 100% embodiment 20

Preparation is the following liquid dishwashing detergent composition of 1.40Kg/l according to density of the present invention:

I II III IVSTPP 17.5 17.2 23.2 23.1 carbonate-2.4--silicate 6.1 24.9 30.7 22.4NaOCl 1.1 1.1 1.1 1.2 thickener 1.0 1.1 1.1 1.0 nonionics-0.1 0.06 0.1NaBz 0.7---ReSI-AMG 0.005 1.0 0.005 0.02NaOH 1.9---KOH 3.6 3.0--spices 0.05---pH 11.7 10.9 10.8 11.0 water to 100%

Embodiment 21

Preparation is according to following sheet dishwashing compositions of the present invention (content is represented by g):

I II III IV V VI phase 1STPP 9.6 9.6 10.4 9.6 9.6 11.5 silicate 0.5 0.7 1.6 1.0 1.0 2.4SKS-6 1.5 1.50 2.30 2.25 carbonate 2.3 2.7 3.5 3.6 4.1 5.2HEDP 0.2 0.2 0.2 0.3 0.3 0.3PB1 2.4 2.4 2.4 3.7 3.7 3.7PAAC 0.002 0.002 0.002 0.003 0.004 0.004ReSI-AMG 0.01 0.02 0.05 0.002 0.001 1.0 amylopectase II--0.01--0.02

I II III IV V VI Amylase 0.002 0.001 0.001 0.002 0.002 0.004 0.002 0.003 0.003 0.003 0.003 Protease 0.003 Nonionic 0.4 0.8 0.8 1.2 1.2 1.2PEG 6000 0.4 0.3 0.3 0.4 0.4 0.4BTA 0.04 0.04 0.04-0.06 0.06 0.15 Paraffin 0.1 0.1 0.1 spice 0.02 0.02 0.15 0.15 0.01 0.01 0.02 0.01 0.5 0.05 2.3 --- sulfate phase 2RESI-AMG 0.003 0.003 0.002 0.01 0.01 0.01 amylase 0.006 0.0005 0.0005 0.0004 0.0005 0.009 0.0004 0.008 protease 0.009 0.008 0.01 0.01 0.3 0.3 0.3 0.30 citric sulfamate acid-0.3 - 0.3 bicarbonate 0.4 1.1 0.4 0.4 1.1 0.4 carbonate-0.5 - 0.5 - silicate - 0.6 - 0.6CaCl2-0.07 - 0.07-PEG 3000 0.06 0.06 0.06 0.06 0.06 0.06

By being prepared as follows the multi-phase tablets composition.The granular mixing with liquid components prepared 1 washing composition active composition mutually, send into then in the mould of conventional rotary forming press.This forming press comprises the suitable stamping machine of shape that forms mold.The cross section of this mould is approximately 30 * 38mm.Make said composition withstanding pressure 940kg/cm then ², rise stamping machine then, expose first phase of the sheet that contains mold on surface thereon.With similar method preparation 2 washing composition active compositions and sending in this mould mutually.Make this seed activity composition withstanding pressure 170kg/cm then ²Rise stamping machine, from this sheet forming press, evict multi-phase tablets from.The sheet that obtains dissolved in 12 minutes or decomposes in above-mentioned washing machine, and the phase 2 of this sheet was dissolved in 5 minutes.This sheet has excellent dissolving and cleans character, has good sheet integrity and intensity simultaneously.Embodiment 22

Preparation is according to following manual dishwashing composition of the present invention:

I II III IV V VI VII VIIIC12-14 betaine 2.0 5.0 2.1----4.0C12-14 glucamide 1.5 1.5 3.1-----C9-11E8-9 4.5 1 4.1 3.0 1.0 3.0-1.0 alkyl polyglycosides------12.0 3.0C1-20 MEA------1.5-DTPA-0.1 0 0-500 0-500 0-500 00

succinic ----- 0-4.5 ppm ppm ppm cumene sulfonate - 4.5 1 to 6-1 to 6 - Ca or Na xylene sulfonate-5.0 - 4.0-2.5-Mg salt (according to % Mg total) 0.5 0.7 0.5 0.04 0.6 0.04 0.3 01,3 bis (methylamino) --- 0.5-0.5-- cyclohexane NN-dimethylaminoethyl --- 0.2-0.2-- methacrylate --- citric acid homopolymer 0-3.5 0- 3.5 - - ethanol 6-85-86-94-10 7.0 4-10 4.0 4.0 protease --- 0-0.08-0-0.08--ReSI-AMG 0.05 .002 .005 0.01 0.4 0.05 0.002 0.01 0.04 0.05 amylase --- 0.002-0.005 carbonate ----- 2.5 - polypropylene glycol --- 0 to 2 ---- (MW2000-4000) pH 7-87-87-8 77 8.5-11 8.5-11 7-8 0.1-0.7 remaining fragrance (water and aids) to 100% Example 23

Preparation is according to following fabric of the present invention and hard surface cleaner composition:

Vitriol 18.5

Supercarbonate 18.6

Polycarboxylate 4.1

C18 alpha-olefin 0.2

Enzyme (lipase, proteolytic enzyme and/or cellulase) 0.004

Amylase 0.003

ReSI-AMG???????????????????????????0.05

Whitening agent 2 0.1

Photoactivated SYNTHETIC OPTICAL WHITNER 0.04

The SPC-D 45.0 of dressing

TAED???????????????????????????????8.8

Citric acid 2.5

Spices 0.1

Other and water to 100%

Claims

1. detergent composition, it comprises detergent components and retrograded starch degrading enzyme, is characterised in that retrogradation starch index (ReSI) is lower than about 4%.

2. according to the detergent composition of claim 1, wherein said retrograded starch degrading enzyme is characterised in that retrogradation starch index (ReSI) is lower than about 3%.

3. according to the detergent composition of claim 1, wherein said retrograded starch degrading enzyme, by the weight of total detergent composition, content is about 0.0002%-about 10% pure enzyme.

4. according to the detergent composition of claim 3, wherein said retrograded starch degrading enzyme, by the weight of total detergent composition, content is about 0.002%-about 2% pure enzyme.

5. according to the detergent composition of claim 4, wherein said retrograded starch degrading enzyme, by the weight of total detergent composition, content is about 0.002%-about 1% pure enzyme.

6. according to the detergent composition of claim 1, wherein said retrograded starch degrading enzyme is selected from amyloglucosidase EC3.2.1.3, α-Dian Fenmei EC3.2.1.1, βDian Fenmei EC3.2.1.2, isoamylase EC3.2.1.68, Starch debranching enzyme type i EC3.2.1.41, isopullulanase EC3.2.1.57, new Starch debranching enzyme EC3.2.1.135, the Starch debranching enzyme Type II, dextrin dextranase EC2.4.1.24, Maltose 4-glucosyltransferase EC2.4.1.19 and maltogenic alpha-amylase enzyme EC3.2.1.133 and/or its mixture.

7. according to the detergent composition of claim 1, wherein said retrograded starch degrading enzyme has or has been added the starch binding domains.

8. according to the detergent composition of claim 1, it also comprises enzyme and/or its mixture that is selected from lipase, proteolytic enzyme, conventional amylase, conventional starch degrading enzyme, conventional Starch debranching enzyme Type II.

9. according to the detergent composition of claim 1, wherein said detergent components is selected from anti redeposition agent, SYNTHETIC OPTICAL WHITNER, nonionogenic tenside and/or its mixture.

10. be characterised in that retrogradation starch index (ReSI) is lower than about 4% retrograded starch degrading enzyme is used for the hydrolytically condensable precipitated powder in detergent composition purposes.

11. according to the purposes of the retrograded starch degrading enzyme of claim 10, wherein said starch degrading enzyme is characterised in that retrogradation starch index (ReSI) is lower than about 3%.

12. the retrograded starch degrading enzyme according to claim 10 is used to keep the fabulous whiteness and the purposes of Fouling Cleaning.