CN1232491A - Detergent compositions comprising antibody controlled amylolytic activity - Google Patents
Detergent compositions comprising antibody controlled amylolytic activity Download PDFInfo
- Publication number
- CN1232491A CN1232491A CN97198586.3A CN97198586A CN1232491A CN 1232491 A CN1232491 A CN 1232491A CN 97198586 A CN97198586 A CN 97198586A CN 1232491 A CN1232491 A CN 1232491A
- Authority
- CN
- China
- Prior art keywords
- amylase
- detergent composition
- antibody
- composition
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/384—Animal products
- C11D3/3845—Antibodies
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Zoology (AREA)
- Detergent Compositions (AREA)
Abstract
The present invention relates to laundry detergent compositions comprising an amylase and an amylase-directed antibody in order to provide excellent cleaning performance and fabric care performance.
Description
The field of the invention
The present invention relates to laundry detergent composition, it contains amylase and the directed antibody of amylase, so that good washing effect and fabric nursing effect to be provided.
Background of the present invention
It is the humoral immunization system that the protection vertebrates is not subjected to the integral part of the system of bacterium and virus infection.The specialized cells that exists in marrow, Lymphoid tissue and blood produces immunoglobulin (Ig) (antibody), and it is along with the invasion of little or big allosome molecule occurs, and connection allosome structure causes its destruction.This class allosome molecule is called antigen.This antibody is at antigenic determinative or antigenic haptens, as part, glycan, lipopolysaccharides, glycoprotein, lipoprotein, the fat teichoic acid of aminoacid sequence, oligose.
The specific antibodies of Chan Shenging can combine with the antigen of inducing them to form and produce the Ag-Ab title complex by this way.Antibody molecule has tie point, and it is very specific and be replenishing of its to the antigenic constitutional features that guides its formation.
Have been found that the identification of this very specific Ag-Ab and in conjunction with having several purposes, for example in various fields, as identifier, wedding agent or the carrier agent of analytical chemistry, treatment processing, health care and beauty treatment fields.
EP4796000, EP453097 and EP450800 relate to employing antibody or its segment is transported to destination locations with active ingredient.EP481701 discloses the treatment compositions that is used for topical application, and it contains the microcapsule at destination locations sealing potent agent, and these microcapsule have antibody or antibody fragment or the Sugar receptors specific to the target location.
WO92/04380 has put down in writing the human body antibody of transformation or the human body antibody fragment of transformation, and it has special efficacy to the human body polymorphic epithelium Saliva Orthana that adopts in treatment for cancer or diagnosis.Use Epstein-Barr virus specific polypeptidase to produce antibody, and diagnosis and treat said disease and be disclosed in WO94/06470.
Contain the oral compositions that antibody is used for preventing decayed tooth or high iodine disease treatment and be documented in WO95/01155, WO95/00110, WO95/10612, EP140498, GB2151923, GB2176400, GB2167299, DE4324859, US5401723 and EP280576 widely.
EP673683 and EP542309 disclose composition of hair cosmetics, it contains a kind of antibody to hair or hair extract, it is from obtaining the yolk of hair or the immunity of hair extract or the poultry, with a kind of polymer emulsion, reduce hair damage, softness, moistening sensation peace slippery to provide, said composition only is absorbed into the specific part of hair.
Contain the factor that suppresses epidermis and change in quality growth antagonist (tyrphostin or antibody), be applicable to that the composition of treatment acne is documented in WO95/24896.
In whole washing scope, adopt antibody to be documented in UnileverResearchprijs " Molecule zoekt partner " 1992, wherein, advised and will be used for bleaching process at the improved antibody of specific colorants.
By adopting the vaccine that is produced by the E. intestinal bacteria to come the hyperimmunization Mammals, the method for producing antibody as ox is documented among the EP102831.EP400569 discloses a kind of method of producing vaccine composition, and this composition is used for carious tooth in nasal drop, and it contains by the proteantigen expressing gene being attached to the antigen that produces in the chromogene of streptococcus mutant body GS-5 bacterial strain.The big chain immunoglobulin (Ig) that WO94/25591 discloses by camelidae produces antibody or its functional pulsating method.
Present detergent composition contains the complex body that satisfies the following active ingredient of being combined with of some specific needs: surfactant system, provide and clean and enzyme, SYNTHETIC OPTICAL WHITNER, adjuvant system, froth suppressor, soil-suspending agent, soil releasing agent, white dyes, tenderizer, dispersion agent, inhibition dye transfer compound, abrasive, sterilant, the spices of fabric nursing effect, and their overall performance is being improved these years really.
Particularly existing detergent for washing clothes preparation generally contains detergent enzyme and more specific amylase.
But the matrix over-exposure is washed part in amylolytic activity and/or with the back master that amylolytic activity is transferred to cycles of washing, can produce unfavorable effect as cleaning, dehydration and/or drying step." residual or shift " amylolytic activity can be washed starch to the back master of laundering of textile fabrics and handle and have a negative impact.Starch for example can be used in the clean cycle process really or before flatiron, nurses fabric and/or weaken agent for ironing.
Unexpectedly found now to adopt the generation that can prevent undesirable residual starch degrading activity at diastatic antibody, kept the effect of the favourable enzyme of decontamination and cleaning simultaneously.Amylolytic activity can be controlled in the washing process process fully, can avoid unfavorable result's generation like this.
Therefore the purpose of this invention is to provide a kind of diastatic laundry detergent composition that contains, it has good cleaning effect, as wipes out a blot and/or dirt, cleans dirt, master behind any starch of fabric is not washed to handle simultaneously to have a negative impact.
The demand is by containing amylase and satisfying at the special efficacy laundry detergent composition of the antibody of said amylolytic enzyme.
Summary of the present invention
The present invention relates to contain the laundry detergent composition of a kind of amylase and a kind of antibody at this amylolytic enzyme, so that good cleaning effect and fabric nursing effect to be provided.
Detailed description of the present invention
Antibody
The fundamental of detergent composition of the present invention is a kind of antibody.
Immunoglobulin (Ig) is divided into five classes, is respectively: lgM, lgG, lgA, lgD and lgE.The preferred kind of immunoglobulin (Ig) is lgG and lgA.In human body, find by body fluid, for example the secretion slgA of milk, saliva, breathing and enteron aisle fluid secretion is in particular in said secretion existence and designs, they have the bonded feature of raising and can resist proteolysis.
Can be that mono-clonal or polyclonal antibody or antibody fragment can adopt ordinary skill in the art production, for example adopt recombinant DNA technology production to have the antibody variants of new property: the immunogenicity of reduction, the affinity of raising, the size that changes ... also can adopt specific combination.Monoclonal antibody preferably for the object of the invention is more preferably its segment.These segments can be passed through routine techniques similarly, for example with papoid and pepsic enzymic digestion or adopt recombinant DNA technology to produce.Antibody fragment also can produce by conventional recombinant DNA technology.Antibody and antibody fragment can be the people, for example at Meded.-FacLandbouwkd.Teogepast Biol.Wet (Univ.Gent) (1995), 60 (4a, Forumfor Applied Biotechnology, 1995, Part1), put down in writing among the 2057-63.
Constituting by constant and transformable domain structure really of heavy chain and light chain.Generating in the body of immunoglobulin (Ig) with its native state, the constant domain structure is very important concerning many functions, but concerning many purposes in commercial run and product, its changeable domain structure is just enough.Therefore, describe many methods and produced antibody fragment.
The antibody fragment that can adopt is that Fab, Fv, scFv or any other have similar segment in conjunction with character.Producing the preferred approach of antibody fragment is by recombinant DNA technology, so that this segment is represented with the gene switching mechanism.
It is the same with the antibody fragment that produces in vertebrates that the antibody that produces by recombinant DNA technology and antibody fragment do not need, have still however that their Km of identical usefulness, Ki and Kcat represent in conjunction with character.For example, they can comprise the sequence of amino acid and/or glycosylation, they with in the antibody that produces in another way, find different, the sequence of segment end particularly.More or less similarly be can be included in its terminal special acid sequence by the antibody fragment that recombinant DNA technology produces, it does not have counterpart in the antibody that otherwise produces.
A kind of relevant possibility is that to be used for wedding agent of the present invention be natural or the synthetic polymkeric substance, and it has reduced the particular combination activity of the auxiliary range of natural antibody.This base polymer be for example polypeptide or polymeric marker (Angew.Chem.Int.Ed.Engl.1995,34,1812-1832).
The ordinary method that is used to produce antibody can be used for corresponding antigen immunity Mammals or poultry.As the Mammals of wanting immunity, can use mouse, rabbit, goat, sheep, horse, ox etc.Antibody (immunoglobulin part) can separate according to the conventional antibody method of purification from antiserum(antisera), milk or egg, said method comprises salt analysis method, polson extraction, gel-filtering chromatogram, ion-exchange chromatography, affinity chromatography etc., adopt the salt analysis method of ammonium sulfate to produce precipitation, then will precipitate dialysis and separate the precipitation that obtains purifying as antibody with physiological saline.
The various antibody molecules and the antibody that can be mass-produced can be synthesized and make up to plant also, and as at Tibtech.Dec1995, Vol 13, pp522-527; Plant Mol.Biol., 26, pp1701-1710,1994 and Biotechnol, proj, 1991,7, pp455-461 and described in the US5202422.Antibody also can be prepared to microorganism by biofermentation method, as E.coli or S.cerevisiae, as illustrated in EP667394.
The technology that is used to prepare antibody fragment is known in the literature: .Science230 1350-54 (1985) such as Saiki; PNAS USA863833-7 (1989) such as Orlandi; WO89/09825; EP368684; WO91/08482 and WO94/25591.
The shortcoming that the activity of enzyme prolongs can effectively be controlled enzymic activity and avoids by adding specific corresponding antibodies.This antibody-like can be a polyclone-at whole enzymatic structure-or mono-clonal-at the specific antigen decision position of the enzymic activity span of control of enzymatic structure.Antibody at the special efficacy enzyme can be by being combined in antibody-antigen activity site or very near activity site enzyme being lost activity.The formation of this mixture causes enzyme to lose activity, and can be by changing three-dimensional structure and/or explaining in the steric hindrance at matrix breach place.Enzyme is lost activity also can be finished by precipitate compound antibody-antigen from washing soln.Because antibody-antigenic interaction has very high specificity and effect, can not influence the activity of other washing composition.
The directed antibody of the amylase preferably concentration in detergent composition of the present invention is that the 10E-6% of total composition is to 10E+1% weight.In some cases, have in conjunction with the very similar diastatic ability of other structure at a kind of specific diastatic antibody, cross reactivity is provided.In general, directed antibody of amylase and diastatic molecule ratio are 100: 1 or lower, preferred 50: 1 or littler.For monoclonal antibody or its segment, directed antibody of amylase and diastatic molecule ratio were generally 50: 1 or are lower, preferred 20: 1 or lower.
Can after stretch-out phase, be released in the washing soln at diastatic antibody, make amylase show premium properties, so that when washing finishes, obtain good effect.
Therefore, preferably with this antibodies in releasing agent, to control their time of releasing and speed in washing soln.The physical form that contains the releasing agent of antibody is applicable to the physical form of corresponding washing agent or additive.
For granular and powder detergent and cleaning product, antibody and releasing agent can be included in the saccharoid.Said antibody saccharoid can suitably contain various granulation aid, tackiness agent, filler, softening agent, lubricant, nucleator etc.Its example comprises Mierocrystalline cellulose (as cellulosic fibre or microcrystal form), derivatived cellulose (CMC, MC, HPC, HPMC), gelatin, starch, dextrin, sugar, Polyvinylpyrolidone (PVP), PVA, PEG, salt (as sodium sulfate, calcium sulfate), titanium dioxide, talcum, clay (kaolin or wilkinite) and nonionogenic tenside.Other related substances that can join in the saccharoid is documented among the EP304331.
Releasing agent can be for example a kind of coating, and said coating is protected said saccharoid for some time in wash environment.This coating generally can be with 1% to 50% weight (weight with the drying granular thing of uncoated be base), and the amount of preferred 5% to 40% weight is used for said saccharoid.The amount that is used for the coating of said saccharoid is somewhat dependent upon the character and the composition of required coating and depends on that said coating should provide the type of protection to said saccharoid.For example, the thickness that is used in said coating on any above-mentioned saccharoid or layered coating can determine to discharge the time of the content of said saccharoid.A kind of possible layered coating can be that a kind of snap-out release coating for example of wherein adopting is used for coating on the slow release coatings.
Also can be formed in the common saccharoid that skin contains detergent enzyme and rapid releasing agent, contains antibody and agent for slow releasing at kernel.
Suitable release coatings is the coating that discharges the content that contains the antibody saccharoid under the general condition in using its process.Therefore, for example contain the washing liq that washs washing composition and (generally contain when preparation of the present invention is incorporated into, the tensio-active agent of one or several types for example) in the time of in, this coating should be a kind of coating that can guarantee to discharge the content of said saccharoid when joining it in washing medium from releasing agent.
Preferred release coatings is water-fast basically coating.The release coatings that is suitable for washing medium can suitably contain and is selected from following material: the lipid acid in the tallow of Mierocrystalline cellulose and cellulase derivative, PVA, PVP, tallow, hydrogenant tallow, partial hydrolysis, natural and synthetic source and Fatty Alcohol(C12-C14 and C12-C18), long-chain fat acid glycerol one-, the Fatty Alcohol(C12-C14 and C12-C18) of two and three esters (as monostearin), ethoxylation, latex, fusing point be at 50～80 ℃ hydrocarbon and cured.The fusing coating reagent be preferred kind discharge coating reagent fast or slowly, it need not dilute with water and just can use.Can be with reference to Controlled Release Systems:FabricationTechnology, Vol.I, CRC Press, 1988, provide out of Memory to slow release coatings.
Coating can suitably further contain for example clay (as kaolin), titanium dioxide, pigment, salt materials such as (as lime carbonate).The experienced technical staff in the art knows other coating composition relevant with the present invention.
In liquid detergent composition, antibody can be used as the particle dispersion that contains the releasing agent except that antibody and adds.This antibody can exist with liquid or solid form.Suitable particle is made of porous hydrophobic material (is 500 dusts or higher silicon-dioxide as mean pore size), and this material contains the solution of antibody and tensio-active agent in the hole, as EP583512, put down in writing among the Surutzidis A etc.
This releasing agent can be that certain hour is protected said particulate coating in cycles of washing.This coating is the hydrophobic coating material preferably, as hydrophobicity (hydrophibic) liquid polymers.But said polymkeric substance can be organic silicone oil or a kind of high-molecular weight hydrocarbon or polymeric material water insoluble but permeate water, as carboxymethyl cellulose, PVA, PVP.The selection of polymer property wants to obtain antibody suitable release profile in washing soln.
Amylase
Amylolytic enzyme can be being 0.0001% to 2% of composition weight, and is preferred 0.00018% to 0.1%, and more preferably the amount of 0.00024% to 0.048% pure enzyme joins in the detergent composition of the present invention.
Amylase can be from any suitable source, for example by Mammals, plant, microorganism preparation.Raw material can further be mesophilic or extremophilic (have a liking for cold, psychrotrophic, thermophilic, have a liking for pressure, have a liking for alkali, have a liking for acid, have a liking for halogen etc.).Can adopt the purification body or the non-purification body of these enzymes.What also can comprise is the mutant of natural enzyme.Mutant can be for example albumen and/or genetically engineered, chemistry and/or physically modified by natural enzyme obtain.Generalized case is to express enzyme by the host microorganism that has wherein cloned and produced the corresponding genetic stew of this kind of enzyme.
Can comprise amylase (α and/or β) to remove the spot of carbohydrate-based.WO94/02597, Novo Nordisk A/S is disclosed on February 3rd, 1994, has put down in writing the detergent composition that adds mutant amylase.Also can be referring to WO95/10603, Novo NordiskA/S is disclosed in April 20 nineteen ninety-five.Other becomes known for amylase in the detergent composition and comprises α-and beta-amylase.α-Dian Fenmei is known in the art, and comprises and be disclosed in US5003257, EP252666, WO/91/00353, FR2676456, EP285123, EP525610, EP368341 and the English Patent 1296839 (Novo) those.Other suitable amylase is to have improved stable amylase, comprise and being documented among the WO94/18314, it is disclosed on August 18th, 1994 and WO96/05295, Genencor, it is disclosed in 22 days February in 1996 those, and the amylase variant that has other modification in the medium parent in the patent of the WO95/10603 that is disclosed in April, 95 of Novo Nordisk A/S.What also be suitable for is the amylase that is documented among EP277216, WO95/26397 and the WO96/23873 (all being NovoNordisk).
The example of industry α-Dian Fenmei product is the Purafect OxAm that is provided by Genencor
And Termamyl
, Ban
, Fungamyl
And Duramyl
, they all are to be provided by NovoNordisk A/S Denmark.WO95/26397 has put down in writing other suitable amylase: be characterised in that its specific activity in 25 to 55 ℃ scope and pH at 8 to 10 scope internal ratio Termamyl
The α-Dian Fenmei of specific activity big at least 25%, specific activity is to pass through Phadebas
αDian Fenmei activity analysis method is measured.The suitable variant of above-mentioned enzyme is documented in WO96/23873 (Novo Nordisk).Other has is having the starch fermentoid that improves character to be documented in WO95/35382 aspect activity and linkage heat stability and the greater activity.
Detergent component
Detergent composition of the present invention also can contain other detergent component.The definite character of these other components and its are sneaked into the situation that concentration depends on the physical form of said composition and uses its washing operation.
Detergent composition of the present invention can be liquid, pasty state, gel, piece, sheet, powder or saccharoid.Granular composition also can be " compacting " body, and liquid composition can also be " concentrating " body.
Composition of the present invention can be mixed with hand washing and machine washing use laundry detergent composition, and it comprises that the laundry additive component soaks and/or fabric that pre-treatment is made dirty the component of the added fabric softener component of rinsing with being suitable for use in.This based composition can give clean fabric, removes dirt, keeps whiteness, softening, color outward appearance and dye transfer suppress.
When being mixed with the composition that is applicable to washing machine washing method, composition of the present invention preferably contains tensio-active agent and auxiliary compound and another or several detergent component and sanitas that is preferably selected from organic polyhydroxyl compound, SYNTHETIC OPTICAL WHITNER, additional enzymes, froth suppressor, dispersion agent, lime soap dispersing agent, soil-suspending agent and anti-redeposition agent.Laundry composition also can contain tenderizer as additional detergent component.
Composition of the present invention also can be used as the washing composition that contains the directed antibody of amylase and add product, and can be added into conventional washing composition and contain in the diastatic composition.This washing composition additive also can contain the directed antibody of amylase and amylase.The purpose of this interpolation product is to replenish or strengthen the effect of conventional detergent composition, and preferably contains 50% the antibody that mostly is total composition most.
If desired, the density range of laundry detergent composition of the present invention is to be determined as 400 to 1200g/l at 20 ℃, preferred 600 to 950g/l composition.
The most handy density meter of " compacting " body of the present composition shows, for composition, shows with the scale of inorganic salt filler; The inorganic salt filler is the conventional component of powdered detergent composition; In conventional detergent composition, filling salt generally is that 17～35% weight of total composition exist with sizable amount.
In compacted compositions, filling salt preferably is no more than 10% to be no more than 15% of total composition, and the amount that is most preferably not exceeding 5% weight exists.
The inorganic salt filler is selected from the vitriol and the muriate of basic metal and alkaline-earth metal as the inorganic salt filler of indication in said composition.
Preferred filling salt is a sodium sulfate.
Liquid detergent composition of the present invention also can be " concentrating " body, and in this case, liquid detergent composition of the present invention contains the water of comparing less amount with the conventional liq washing composition.
In general, the water content of concentrated liquid detergent is more preferably less than 30% preferably less than 40%, most preferably less than the detergent composition of 20% weight.
Surfactant system
Detergent composition of the present invention contains the surfactant system that tensio-active agent wherein is selected from nonionic and/or negatively charged ion and/or positively charged ion and/or both sexes and/or zwitter-ion and/or semi-polar tensio-active agent.
The content that tensio-active agent is general is 0.1% to 60% weight of detergent composition of the present invention.Preferred add-on is 1% to 35% weight of detergent composition of the present invention, most preferably 1% to 30% weight.
This tensio-active agent preferably be mixed with can with the enzyme component compatibility that is present in the said composition.In liquid or gelatinous composition, this tensio-active agent most preferably is mixed with it is promoted, perhaps is not reduced in the stability of all enzymes in these compositions at least.
The preferred surfactant system that adopts according to the present invention contains nonionic that one or several the present invention put down in writing and/or anion surfactant as tensio-active agent.
The alkylphenol condenses of polyethylene oxide, polyoxytrimethylene and polyoxybutylene is applicable to the nonionogenic tenside as surfactant system of the present invention, and polyethylene oxide condensation compound is preferred.These compounds comprise having and contain about 6 to 14 carbon atoms, preferred about 8 to about 14 carbon atoms, become straight chain with oxyalkylene or prop up the condensation product of alkylphenol of the alkyl of chain configuration.In a preferred embodiment, the amount that oxyethane exists equals every mole of alkylphenol about 2 to about 25 moles, more preferably from about 3 to 15 moles oxyethane.The industrial available ionic surfactant pack of this class is drawn together lgepal
TMCO-630, commercially available by GAFCorportion; And Triton
TMX-45, X-114, X-100 and X-102, all are all by Rohm﹠amp; Haas Company is commercially available.These tensio-active agent general designation alkylphenol alkoxides (as the alkylphenol b-oxide).
Primary and secondary Fatty Alcohol(C12-C14 and C12-C18) and about 1 condensation product to about 25 moles of ethylene oxide are applicable to the nonionogenic tenside as nonionic surfactant system of the present invention.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be straight chain or collateralization, uncle or secondary and generally contain and have an appointment 8 to about 22 carbon atoms.Preferably have and contain about 8 to about 20 carbon atoms, more preferably from about 10 arrive the condensation product of about 10 moles of ethylene oxide to the alcohol of the alkyl of about 18 carbon atoms and every mol of alcohol about 2.Every mol of alcohol exists about 2 to about 7 moles of ethylene oxide, most preferably 2 to 5 moles of ethylene oxide in said condensation product.The example of the industrial available nonionogenic tenside of this class comprises Tergitol
TM15-S-9 (C
11-C
15The condensation product of linear 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, its narrow molecular weight distribution), the two is commercially available by Union Carbide Corporation, Neodol
TM45-9 (C
14-C
15The condensation product of linear alcohol and 9 moles of ethylene oxide), Neodol
TM23-3 (C
12-C
13The condensation product of linear alcohol and 3.0 moles of ethylene oxide), Neodol
TM45-7 (C
14-C
15The condensation product of linear alcohol and 7 moles of ethylene oxide), by the commercially available Neodol of ShellChemical Company
TM45-5 (C
14-C
15The condensation product of linear alcohol and 5 moles of ethylene oxide), by The Procter﹠amp; The Kyro that Gamble Company is commercially available
TMEOB (C
13-C
15The alcohol and the condensation product of 9 moles of ethylene oxide) and by Hoechst commercially available Genapol LA030 or 050 (C
12-C
14The condensation product of alcohol and the oxyethane of 3 moles or 5 moles).The preferable range of HLB is 8～11 in these products, most preferably 8-10.
The nonionogenic tenside that also can be used as surfactant system of the present invention is an alkyl polysaccharide, it is disclosed in US4565647, Llenado, on January 21st, 1986 is open, and it has and contains about 6 to about 30 carbon atoms, preferred about 10 hydrophobic grouping and glycan to about 16 carbon atoms, as poly-glycosides, have an appointment 1.3 to about 10 with containing, preferred about 1.3 to about 3, most preferably from about 1.3 hydrophilic groups to about 2.7 sugar units.Any reducing sugar that contains 5 or 6 carbon atoms that can adopt, partly replace glucosyl group part (randomly hydrophobic group is connected on the positions such as 2-, 3-, 4-, glucose or semi-lactosi that generation is relative with glucoside or galactoside) as glucose, semi-lactosi and galactosyl.Interior sugared key can be on a position between additional sugar unit and 2-, 3-, 4-and/or the 6-position at previous sugar unit.
Preferred alkylpolyglycosides has following general formula:
R
2O (C
nH
2nO)
t(glycosyl)
xR wherein
2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and their mixture, wherein alkyl contains and has an appointment 10 to about 18, and preferred about 12 to about 14 carbon atoms; N is 2 or 3, preferred 2; T from 0 to about 10, preferred 0; X is about 1.3 to 10, and is preferred about 1.3 to 3, most preferably from about 1.3 to about 2.7.This glycosyl is preferably produced by glucose.In order to prepare these compounds, at first prepare alcohol or alkyl polyethoxye alcohol, again with the raw material reaction of glucose or glucose, generate glycosides (being connected 1).Then other glycosyl units can be connected their the 1-position and 2-, 3-, 4-and/or the 6-position of front glycosyl units, preferably mainly is the position between the 2-position.
The oxyethane that condensation reaction by propylene oxide and propylene glycol generates and the condensation product of hydrophobic base also are applicable to as additional nonionic surfactant system of the present invention.The molecular weight of the hydrophobic part of these compounds preferably is about 1500 to about 1800, and water insoluble.The polyoxyethylene of addition on this hydrophobic part partly has the whole water miscible trend of the molecule of raising, and the fluid characteristics of product is about 50% o'clock of condensation product total amount at polyoxyethylene content and keeps to some extent, and this is equivalent to and mostly is about 40 moles ethylene oxide condensation most.The example of this compounds comprises that some are by the commercially available industrial available Plurafac of BASF
TMLF404 and Pluronic
TMTensio-active agent.
Also be applicable to condensation product as the product that to be oxyethane generate with reaction by propylene oxide and ethylene diamine of the nonionogenic tenside of nonionic surfactant system of the present invention.The hydrophobic part of these products comprises the reaction product of ethylene diamine and excessive oxidation propylene, and molecular weight is about 2500 to about 3000 usually.This hydrophobic part and ethylene oxide condensation contain to have an appointment to condensation product and 40% are about the degree of 5000 to 11000 condensation product to the polyoxyethylene of about 80% weight and molecular weight.The example of this class nonionogenic tenside comprises the industrial available Tetronic that some are provided by BASF
TMCompound.
The nonionogenic tenside that is preferably used as surfactant system of the present invention is polyethylene oxide condensation product, primary and secondary Fatty Alcohol(C12-C14 and C12-C18) and about 1 condensation product, alkyl polysaccharide and their mixture to about 25 moles of ethylene oxide of alkylphenol.The C that most preferably has 3 to 15 oxyethyl groups
8-C
14Alkylphenol b-oxide and the C that has 2 to 10 oxyethyl groups
8-C
18Alcohol b-oxide (preferred average out to C
10) and their mixture.
Nonionogenic tenside very preferably is a polyhydroxy fatty acid amide surfactant, and its general formula is as follows:
R wherein
1Be H, perhaps R
1Be C
14Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R
2Be C
5-31Alkyl, Z are to have to contain polyhydroxy alkyl or its alkoxy derivative that at least 3 hydroxyls directly are connected the linear hydrocarbyl chain on the chain.Preferably, R
1Be methyl, R
2It is straight chain C
11-15Alkyl or C
16-18Alkyl or alkenyl chain, as coconut alkyl or their mixture, Z is from reducing sugar, generates in reductive amination process as glucose, fructose, maltose, dextrose.
Adoptable suitable anion surfactant is linear alkyl benzene sulfonate, alkyl sulfonate surfactants, and it comprises C
8-C
20The ol ester of carboxylic acid (as lipid acid), it is according to " The Journal of the American Oil Chemists Society ", 52 (1975), pp323～329 gaseous state SO
3Carry out sulfonation.Proper raw material comprises the natural fat material, as being produced by tallow, palm wet goods.
Preferred alkyl sulfonate surfactants, especially for the alkyl sulfonate surfactants that contains of laundry purposes, its general structure is as follows:
R wherein
3Be C
8-C
20Alkyl, preferred alkyl or their combination, R
4Be C
1-C
6Alkyl, preferred alkyl or their combination, M are the positively charged ions that forms water-soluble salt with the alkyl ester sulphonate.Suitable salt-forming cation comprises metal, as ammonium cation sodium, potassium and lithium and replacement or unsubstituted, as Monoethanolamine MEA BASF, diethanolamine and trolamine.R preferably
3Be C
10-C
16Alkyl, R
4Be methyl, ethyl or sec.-propyl.Particularly preferably be methyl ester sulfonate, wherein R
3Be C
10-C
16Alkyl.
Other suitable anion surfactant comprises alkyl sulfate surfactant, is following water-soluble salt of general formula or acid: ROSO
3M, wherein R C preferably
10-C
24Alkyl preferably contains C
10-C
20The alkyl of moieties or hydroxyalkyl more preferably are C
12-C
18Alkyl or hydroxyalkyl, M is H or positively charged ion, as alkali metal cation (as sodium, potassium, lithium), perhaps the ammonium ion of ammonium ion or replacement (as methyl-, dimethyl-and trimethyl ammonium positively charged ion and quaternary ammonium cation, as tetramethylammonium cation and lupetidine positively charged ion with by alkylammonium, quaternary ammonium cation that produces as ethylamine, diethylamide, triethylamine and their mixture or the like).In general, C
12-C
16Alkyl chain be preferred for lower wash temperature (as being lower than about 50 ℃), and C
16-C
18Alkyl chain is preferred for higher wash temperature (as being higher than about 50 ℃).
Other anion surfactant that can be used for washing purpose also can be included in the detergent composition of the present invention.They comprise soap salt (comprise for example ammonium salt of sodium, potassium, ammonium and replacement, as one-, two-and triethanolamine salt), C
8-C
20Uncle or secondary alkyl sulfonate, C
8-C
24The sulfonated poly carboxylic acid of alkene sulfonate, the preparation of the pyrolysis product by the sulfonation alkaline earth metal citrate, as in English Patent 1082179 put down in writing C
8-C
24Alkyl gathers glycol ether sulfate (contain and mostly be 10 moles oxyethane most); Alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol vitriol, alkylphenol oxyethane ether sulfate, paraffin sulfonate, alkylphosphonic, different thiosulphate are as the different thiosulphate of acyl group, N-acyl taurine salt, dialkyl succinylsuccinate acid amides and sulfosuccinate, sulfo-succinic acid one ester (particularly saturated and undersaturated C
12-C
18One ester) and sulfo-succinic acid diester (particularly saturated and undersaturated C
6-C
12Diester), the vitriol of acyl sarcosinate, alkyl polysaccharide, as the vitriol (the not Sulfated compound of nonionic as described below) of alkylpolyglycosides, the primary alkyl sulphates and the alkyl polyethoxye carboxylate salt of collateralization, be RO (CH as general formula
2CH
2O)
k-CH
2COO-M+, wherein R is C
8-C
22Alkyl, k are 1 to 10 integers, and M is the solubility salt-forming cation.Resinous acid and hydrogenant resinous acid also are suitable for, as exist in the tallol or by rosin, staybelite and resinous acid and the hydrogenant resinous acid of its generation.
Other example is documented in " Surface Active Agents and Detergents " (I and II volume come from Schwartz, Perry and Berch).A large amount of these class tensio-active agents are disclosed in US3929678 usually, and on December 30th, 1975, Laughlin etc. are at the 23rd hurdle the 58th row (combination in the present invention for your guidance) in the 29th hurdle the 23rd row.
When laundry detergent composition of the present invention contained them, said composition contains usually had an appointment 1% to about 40%, preferred about 3% this analog anion surfactants to about 20% weight.
Anion surfactant very preferably comprises alkyl alkoxylated sulfate surfactant, and following water-soluble salt of general formula or acid: RO (A) are wherein arranged
mSO
3M, wherein R is unsubstituted C
10-C
24Alkyl or contain C
10-C
24The hydroxyalkyl of alkyl component, preferred C
12-C
20Alkyl or hydroxyalkyl, more preferably C
12-C
18Alkyl or hydroxyalkyl, A is oxyethyl group or propoxy-unit, m is greater than zero, generally between about 0.5 to 6, more preferably between about 0.5 to about 3, M is H or positively charged ion, and they can be the ammonium cations of metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium ion or replacement for example.Can consider the vitriol and the propenoxylated vitriol of alkyl of alkyl ethoxylated in the present invention.The object lesson of the ammonium cation that replaces comprise methyl-, dimethyl-, trimethylammonium-ammonium cation and quaternary ammonium cation, as tetramethyl-ammonium and lupetidine positively charged ion, with those by alkylamine, as ethylamine, diethylamide, triethylamine, their mixture etc. produce etc.Exemplary surfactants is C
12-C
18Alkyl gathers b-oxide (1.0) vitriol (C
12-C
18E (1.0) M), C
12-C
18Alkyl gathers b-oxide (2.25) vitriol (C
12-C
18E (2.25) M), C
12-C
18Alkyl gathers b-oxide (3.0) vitriol (C
12-C
18E (3.0) M) and C
12-C
18Alkyl gathers b-oxide (4.0) vitriol (C
12-C
18E (4.0) M), wherein M generally is selected from sodium and potassium.
Detergent composition of the present invention also can contain positively charged ion, amphoteric, zwitter-ion and semi-polar tensio-active agent, and put down in writing in the present invention those outside nonionic and/or anion surfactant.
Be applicable to that the cationic detersive tensio-active agent in the detergent composition of the present invention has a long chain hydrocarbon groups.The example of this cationoid tensio-active agent comprises ammonium surfactant, as alkyl trimethyl ammonium halogenide with have the tensio-active agent of following general formula:
[R
2(OR
3)
y] [R
4(OR
3)
y]
2R
5N+X-is R wherein
2Be on alkyl chain, to contain about 8 alkyl or alkyl benzyls, 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 their mixture; 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 any hexose or molecular weight less than about 1000 hexose polymkeric substance and the hydrogen when y is not 0; R
5With R
4Identical or R wherein
2Add R
5The total number of carbon atoms be not more than about 18 alkyl chain; Y is from 0 to about 10, and the y value add up to 0 to 15, X is any suitable negatively charged ion.
Be applicable to that quaternary ammonium surfactant of the present invention has following logical formula I:
Formula I wherein R1 is short-chain alkyl (C
6-C
10) or the alkylamide alkyl of general formula following (II):
The formula II
Y is 2～4, and is preferred 3,
Wherein R2 is H or C
1-C
3Alkyl,
Wherein x is 0～4, and is preferred 0～2, most preferably 0,
Wherein R3, R4 are identical with R5 or different, and can be short-chain alkyl (C
1-C
3) or alkoxylated alkyl group, its general formula is (III),
Wherein X-is opposite ion, and preferred halogen ion is as chlorion or Methylsulfate.
The formula III
R6 is C
1-C
4, z is 1 and 2.
The formula I of preferred quaternary ammonium surfactant, wherein
R
1Be C
8, C
10Perhaps their mixture, x=0
R
3, R
4=CH
3And R
5=CH
2CH
2OH.
The cats product very preferably that can be used for the present composition is the water-soluble quaternary ammonium compound with following general formula:
R
1R
2R
3R
4N
+X
-(ⅰ) R wherein
1Be C
8-C
16Alkyl, R
2, R
3And R
4Be respectively C
1-C
4Alkyl, C
1-C
4Hydroxyalkyl, benzyl and-(C
2H
40)
xH, wherein x is 2 to 5, X is a negatively charged ion.R
2, R
3Or R
4In maximum one be benzyl.Preferred R
1The length of alkyl chain is C
12-C
15, especially when alkyl be the mixture of chain lengths that produces by coconut or palm kernel fat, or by alkene pure synthetic generation of synthetic or OXO the time.R
2R
3And R
4Preferred group be methyl and hydroxyethyl, negatively charged ion X can be selected from halogen ion, metilsulfate, acetate and phosphate anion.
Can be used for general formula of the present invention for the example of (ⅰ) suitable quaternary ammonium ion compound is:
Coconut trimethyl ammonium chloride or brometo de amonio;
Coconut 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;
Coconut dimethyl hydroxyethyl ammonium chloride or brometo de amonio;
Myristyl trimethyl ammonium Methylsulfate;
Lauryl dimethyl benzyl ammonium chloride or brometo de amonio;
Lauryl dimethyl (vinyloxy group)
4Ammonium chloride or brometo de amonio; Cholinesterase (compound of general formula (ⅰ), wherein R
1Be
Alkyl, R
2R
3R
4Be methyl).
Dialkylimidazolium quinoline [compound of general formula (ⅰ)].
Can be used for other cats product of the present invention and be documented in US4228044, Cambre is in 14 days October in 1980 and in the European patent application EP 000224.
When detergent composition of the present invention contained them, said composition generally contained 0.2% to about 25%, preferred about 1% this cationoid tensio-active agent to about 8% weight.
Amphoterics also is applicable in the detergent composition of the present invention.These tensio-active agents are recited as the fat derivant of the second month in a season or tertiary amine widely, the perhaps fat derivant of the secondary and tertiary amine of heterocycle, and fatty group wherein can be chain straight chain or collateralization.A fatty substituting group contains at least about 8 carbon atoms, and general about 8 to about 18 carbon atoms, and at least one contains the anionic water solubilization radical, as carboxyl, sulfonic group, sulfate.Referring to US3929678, Laughlin etc., on December 30th, 1975, the 19th hurdle, 18-35 is capable, exemplifies amphoterics.
When detergent composition of the present invention contained them, said composition generally contained 0.2% to about 15%, preferred about 1% this class amphoterics to about 10% weight.
Zwitterionics also is applicable to detergent composition.These tensio-active agents can be described as the derivative of derivative, the heterocycle second month in a season and tertiary amine of secondary and tertiary amine or quaternary ammonium, season phosphine or the derivative of uncle's sulfonium compound widely.Referring to US3929678, Laughlin etc., on December 30th, 1975, the 19th hurdle the 38th row exemplifies zwitterionics to the 22nd hurdle the 48th row.
When detergent composition of the present invention contained them, said composition generally contained 0.2% to about 15%, preferred about 1% this class zwitterionics to about 10% weight.
Semi-polar nonionic surfactants is the nonionogenic tenside of a particular variety, and it comprises that containing one contains to have an appointment and 10 be selected to contain to the moieties of about 18 carbon atoms and 2 and have an appointment 1 to the alkyl of about 3 carbon atoms and the water-soluble amine oxides of hydroxyalkyl part; Contain one about 10 and be selected from about 1 to the alkyl of about 3 carbon atoms and the water soluble oxidized phosphine of hydroxyalkyl part to the moieties of about 18 carbon atoms and 2; With contain one about 10 and be selected from about 1 to the alkyl of about 3 carbon atoms and the water-soluble sulfoxide of hydroxyalkyl part to the moieties of about 18 carbon atoms and 1.
Semi-polarity nonionic detergent tensio-active agent comprises the amine oxide surfactant with following general formula:
R wherein
3Be to contain have an appointment alkyl, hydroxyalkyl or the alkyl phenyl of 8 to 22 carbon atoms or their mixture; R
4Be alkylidene group or the hydroxy alkylidene that contains 2 to 3 carbon atoms of having an appointment, perhaps their mixture; X is 0 to about 3; R
5Be alkyl or the hydroxyalkyl that contains 1 to 3 carbon atom of having an appointment, perhaps contain the polyethylene oxide group of 1 to 3 ethylene oxide group of having an appointment.R
5Group mutually combines, and as by Sauerstoffatom or nitrogen-atoms, forms ring structure.
These amine oxide surfactants can be particularly including C
10-C
18Alkyl dimethyl amine oxide and C
8-C
12Alkoxyethyl dihydroxy ethyl amine oxide.
When detergent composition of the present invention contained them, said composition generally contained 0.2% to about 15%, preferred about 1% this class semi-polar nonionic surfactants to about 10% weight.
Detergent composition of the present invention can further contain a kind of cosurfactant, and it is selected from primary amine or tertiary amine.Can be used for suitable primary amine of the present invention and comprise the amine with following general formula: R
1NH
2, R wherein
1Be C
6-C
12, preferred C
6-C
10Alkyl chain or R
4X (CH
2)
n, X is-O-,-C (O) NH-or-NH-, R
4Be C
6-C
12Alkyl chain, n are 1 to 5, preferred 3.R
1Alkyl chain can be straight chain or side chain, and can mostly be 12 most, preferably is less than 5 ethylene oxide moieties and interrupts.According to the preferred amine of above-mentioned general formula of the present invention is positive alkylamine.Can be used for suitable amine of the present invention and can be selected from 1-hexyl amine, 1-octyl amine, 1-decyl amine and lauryl amine.Other preferred primary amine comprises C
8-C
10Oxygen propyl group amine, octyl group oxygen propyl group amine, 2-ethylhexyl oxygen propyl group amine, lauryl amido propyl amine and amido propyl amine.
Can be used for suitable tertiary amine of the present invention and comprise the tertiary amine with following general formula: R
1R
2R
3N, 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 be-O-,-C (O) NH-or-NH-, R
4Be C
4-C
12, n is 1 to 5, preferred 2-3, R
5Be H or C
1-C
2Alkyl, x are 1 to 6.
R
3And R
4It can be linear or collateralization; R
3Alkyl chain can mostly be 12 most, preferably interrupts less than 5 ethylene oxide 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.Amido amine further preferably, its general formula is as follows:
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-octyl amine, 1-hexyl amine, 1-decyl amine, 1-lauryl amine, C
8-10Propoxy-amine, N coconut 1-3 diaminopropanes, coconut alkyl dimethyl amine, lauryl dimethyl amine, lauryl two (hydroxyethyl) amine, coconut two (hydroxyethyl) amine, 2 moles of propoxides of lauryl amine, 2 moles of propoxides of octyl amine, lauryl amido propyl dimethyl amine, C
8-10Amido propyl dimethyl amine and C
10The amido propyl dimethyl amine.
Being used for the most preferred amine of the present composition is 1-hexyl amine, 1-octyl amine, 1-decyl amine, 1-lauryl amine.What need especially is dodecyl dimethyl amine and dihydroxy ethyl coconut alkylamine and 7 times of b-oxides of oleyl amine, lauryl amido propyl amine and coconut monoethanolamide propyl group amine.
Conventional detergent enzyme
Detergent composition can further contain the enzyme that one or several have washing effect and/or fabric nursing effect.
Said enzyme comprises and is selected from hemicellulase, peroxidase, proteolytic enzyme, glucoamylase, amylase, zytase, lipase, Phospholipid hydrolase, esterase, at (cutinases), polygalacturonase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, ligninase, Starch debranching enzyme, tannase, pentosanase, malanases, beta-glucanase, arabinose enzyme (arabinosidases), Unidasa, chondroitinase, laccase and their mixture.
Preferred combination is a kind of conventional enzyme that uses that contains, for example proteolytic enzyme, amylase, lipase, at and/or cellulase with one or several plant cell-wall degrading enzymes bonded adulterant detergent composition.
Can be used for cellulase of the present invention and comprise bacterium or mould cellulase.Preferred their ideal pH scopes are 5 to 9.5.Suitable cellulase is disclosed in US4435307, Barbesgoard etc., and it discloses the mould cellulase by Humicola insolens preparation.Suitable cellulase also is disclosed in GB-A-2075028, GB-A-2095275 and DE-OS-2247832.
The example of the plain enzyme of this fibrid is the cellulase by strain DSM 1800 generations of the bacterial strain, particularly Humicola of Humicola insolens (Humicola griseavar.thermoidea).
Other suitable cellulase is that to be about 50KDa, iso-electric point be 5.5 and contain cellulase that 415 amino acid whose Humicola insolens produce and produced～the 43kD endo-dextranase by DSM1800, Humicola insolens with cellulase activity by molecular weight; The aminoacid sequence of preferred endo-dextranase component is disclosed among the PCT patent application WO91/17243.Shi Yi cellulase is the cellulase with protection colour characteristics especially.Other suitable cellulase is the EG III cellulase that is got by Trichoderma longibrachiatum, and it is documented in WO94/21801, and Genencor is disclosed on September 29th, 1994.The example of the plain enzyme of this fibrid is the cellulase that is documented in record in european patent application on November 6th, 91202879.2,1991 (Novo).
Peroxidase can with the oxygen raw material, be used in combination as percarbonate, perborate, persulphate, hydrogen peroxide etc.They can be used for " solution bleaching ", prevent in washing operation that promptly dyestuff or pigment from transferring on other matrix washing soln from matrix.Peroxidase is well known in the art, and it comprises for example horseradish peroxidase, ligninase and halo peroxidase, as chloro-and bromo-peroxidase.
The detergent composition that contains peroxidase for example is disclosed in PCT International Application No. WO 89/099813 and in European patent application EP in 6,91202882.6,1991 on November.Other suitable oxydase is laccase, adopts oxygen or hydrogen peroxide as main matrix.
Said cellulase and/or peroxidase generally join in the detergent composition with the amount of the organized enzyme of 0.0001% to 2% weight of detergent composition.
Other preferred enzyme that can be included in the detergent composition of the present invention comprises lipase.The suitable lipase that is used for the washing composition purposes comprises the microorganism by Rhodopseudomonas, for example Pseudomonas stutzeri ATCC19.154 produce those, as be documented in the English Patent 1372034.Suitable lipase comprises the lipase that has with the position of the antibody generation immunological cross-reaction of lipase, and it is produced by microorganism Pseudomonas fluorescent IAM1057.This lipase is by Amano PharmaceuticalCo.Ltd., Nagoya, and Japan provides with the trade mark of Lipase P " Amano " (in this article referring to " Amano-P ").Other suitable industrial available lipase comprises Amano-CES, lipase by Chromobacter viscosum generation, as by Toyo JozoCo., Tagata, the Chromobacter viscosum var.lipolyticumNRRLB3673 that Japan provides, US Biochemical Corp., USA and Disoynth Co., Chromobacter viscosum lipase that TheNetherlands provides and the lipase that produces by Pseudomonas gladioli.Especially effectively lipase is such as following lipase: Ml Lipase
RAnd Lipomax
R(Gist-Brocades) and Lipolase
RWith Lipolase Ultra
R(Novo), have been found that they are effective especially when being used for composition of the present invention.
That also be suitable for is at [EC3.1.1.50], and they can be considered as the lipase of particular types, and so-called lipase does not need interfacial activity.Other at of detergent composition has been documented in for example WO-A-88/09367 (Genencor).
Lipase and/or at are generally being that the amount of 0.0001% to 2% weight organized enzyme of detergent composition joins in the detergent composition.
Suitable proteolytic enzyme is subtilysin, and it is the specified genus preparation by Bacillus subtillis and lichenoid form bacillus (subtilysin BPN and BPN ').A kind of useful proteases be by the pH scope of maximum activity in 8～12 Bacillaceae preparation, this Bacillaceae by the NovoIndustries A/S (this paper is " Novo ") of Denmark with ESPERASE
Exploitation is also sold.The preparation of this kind of enzyme and similar enzyme is documented among the GB1243784 of Novo.The ALCALASE that is provided by Novo is provided other useful proteases
, DURAZYM
And SAVINASE
With the MAXATASE that provides by Gist-Brocades
, MAXACAL
, PROPERASE
And MAXAPEM
The albumen fermentoid also comprises the bacterial serine proteolytic enzyme of modification, as be documented in european patent application 87303761.8, in on April 28th, 1987 (particularly the 17th, 24 and 98 page), it is called as " proteolytic enzyme B " in the present invention, with at european patent application 199404, Venegas is disclosed on October 29th, 1986, and it is meant the bacterial serine proteolytic enzyme of the modification that is called as " protease A " at this paper.Most preferably alleged in the present invention " proteolytic enzyme C ", it is the variant from the alkaline serine protease of Bacillus, wherein 27 replace arginine in the position at Methionin, tyrosine is 104 replacement Xie Ansuans in the position, Serine is 123 replacement aspartic acids in the position, and L-Ala is 274 replacement Threonines in the position.Proteolytic enzyme C is documented among the EP90915958.4, is WO91/06637 accordingly, is disclosed on May 16th, 1991.The variant of gene modification, particularly proteolytic enzyme C is also contained among the present invention.Also can be referring to the high pH proteolytic enzyme of the WO93/18140A that is documented in Novo from bacillus NCIMB40338.The enzyme washing composition that contains proteolytic enzyme, one or more other enzymes and reversible proteinase inhibitor is documented among the WO92/03529A of Novo.When needing, can adopt Procter﹠amp; The reduction of putting down in writing among the WO95/07791 of Gamble absorbs and improves the proteolytic enzyme of hydrolysis.The proteolytic enzyme that is used for the recombinant chou Trypsin enzyme of washing composition of the present invention is documented in the WO94/25583 of Novo.
More particularly, the proteolytic enzyme that is called as " proteolytic enzyme D " is the variant with carbonylic hydrolase of the undiscovered aminoacid sequence of nature, it is by being equal at said carbonylic hydrolase+position of 76 positions by the precursor carbonylic hydrolase, also preferred combination one or several be equal to be selected from according to the layout of bacillus amyloliquefaciens subtilysin sequence+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+274 amino acid residue position, sequence according to the bacillus amylolyticus subtilysin, replace a plurality of amino-acid residues to prepare with different amino acid, as WO95/10591 and at C.Ghosh etc. described in the US08/322677 of " BleachingCompasitions Comprising Protease Enzymes ", register in October 13 nineteen forty-four.Be applicable to that also of the present invention is to be documented in the proteolytic enzyme among EP251446 and the WO91/06637 and to be documented in proteolytic enzyme BLAP among the WO91/02792
Proteolytic enzyme also can be according to the present invention being that the amount of 0.0001% to 2% organized enzyme of composition weight joins in the said composition.
Above-mentioned enzyme can be from any suitable source, and for example vegetables, animal, bacterium, mould and yeast are originated.Raw material can further be mesophilic or extremophilic (have a liking for cold, psychrotrophic, thermophilic, have a liking for pressure, have a liking for alkali, have a liking for acid, have a liking for halogen etc.).Can adopt the purification body of these enzymes or the body of not purifying.What also can clearly comprise is the mutant of natural enzyme.Mutant can be for example protein and/or genetically engineered, chemistry and/or physically modified by natural enzyme obtain.Generalized case is to represent enzyme by wherein having cloned with the main body biology of producing the corresponding genetic stew of enzyme.Said enzyme is generally being that the amount of organized enzyme of 0.0001% to 2% weight of this detergent composition joins in the detergent composition.Enzyme can add with the form of isolating independent component (containing a kind of ball, particle of enzyme, stable liquid etc.) or with the form of the mixture of two kinds or more of enzymes (as particle altogether).
Other suitable detergent ingredients that can add is the oxydasis scavenging agent, and it is documented in european patent application on January 31st, 92870018.6,1992 of common pending trial.The example of this fermentoid oxidizing decontamination agent is four ethylidene polyamine of ethoxylation.
The scope of enzyme material and their methods in the synthetic detergent composition of joining are disclosed in the US3553139 of the WO8908694A of the WO9307263A of Genencor International and WO9307260A, Novo and McCarty etc., on January 5th, 1971.Enzyme further is disclosed in US4101457, Place etc., on July 18th, 1978 and at US4507219, Hughes, on March 26th, 1985.The method that can be used for the enzyme material in the liquid detergent preparation and they are joined in this class preparation is disclosed in US4261868, Hora etc., on April 14th, 1981.The enzyme that is used for washing composition can be by various consistent.The enzyme stabilization technique is at US3600319, and on August 17th, 1971, Gedge etc. disclose and give exemplifying on October 29th, 1986, Venegas among EP199405 and the EP200586.The enzyme stabilising system for example also is documented among the US3519570.The effective Bacillussp.AC13 that produces proteolytic enzyme, zytase and cellulase also is documented among the WO9401532A of Novo.
The color protection effect
Also can comprise the technology that one type color protection effect is provided.The example of these technology is that metal catalyst is used to keep color.This metalloid catalyzer is documented in the european patent application 92870181.2 of common pending trial.
SYNTHETIC OPTICAL WHITNER
Detergent composition of the present invention can further contain SYNTHETIC OPTICAL WHITNER, and for example hydrogen peroxide, PB1, PB4 and granularity are 400～800 microns percarbonate.These bleaching components comprise one or several oxygen bleaching agents, and according to one or several bleach activators of selected SYNTHETIC OPTICAL WHITNER.When having the oxygen bleaching component, its general content is about 1% to about 25%.
Be used for bleaching components of the present invention and can be any SYNTHETIC OPTICAL WHITNER that can be used for containing the detergent composition of oxygen bleaching agent and other SYNTHETIC OPTICAL WHITNER known in the art.Be applicable to that SYNTHETIC OPTICAL WHITNER of the present invention can be activatory or non-activated SYNTHETIC OPTICAL WHITNER.
The oxygen bleaching agent that one class can adopt comprises percarboxylic acids SYNTHETIC OPTICAL WHITNER and its salt.The suitable example of this class reagent comprise magnesium a peroxide m-phthalic acid hexahydrate ,-magnesium salts of chlorine peroxybenzoic acid, 4-nonyl amino-4-oxygen Perbutyric Acid and diperoxy dodecanedioic acid.This class SYNTHETIC OPTICAL WHITNER is disclosed among US4483781, USA740446, european patent application 0133354 and the US4412934.SYNTHETIC OPTICAL WHITNER very preferably comprises that also 6-nonyl amino-6-oxo crosses oxy hexanoic acid, as is documented in US4634551.
The another kind of SYNTHETIC OPTICAL WHITNER that can adopt comprises the halogen SYNTHETIC OPTICAL WHITNER.The example of hypohalite SYNTHETIC OPTICAL WHITNER comprises sodium salt and sylvite and the N-chlorine and the N-bromine alkane sulfo group acid amides of TCCA (Trichloroisocyanuric acid) and dichloro and the acid of cyanogen urea.Generally to be 0.5～10% weight of final product, the amount of preferred 1～5% weight adds this class material.
The hydrogen peroxide releasing agent can be used for combining with bleach activator; for example tetra-acetylated ethylene diamine (TAED), nonanoyl oxygen benzene sulfonate (NOBS; be documented among the US4412934), 3; 5-trimethyl hexanol oxygen benzene sulfonate (SONOBS; be documented among the EP120591) or the sulfophenylate (NACA-OBS of penta ethanoyl glucose (PAG) or N-nonanoyl-6-aminocaprolc acid; be documented among the WO94/28106); it is crossed hydrolysis and is generated peracid as active albic material, thereby improves bleaching effect.Also the promoting agent of Shi Yonging is the citrate of acylations, as is disclosed in the european patent application 91870207.7 of common pending trial.
Effective SYNTHETIC OPTICAL WHITNER, comprise peroxy acid that is used for detergent composition of the present invention and the bleach system that contains bleach activator and peroxy bleaching agent compound, they are documented among application USSN08/136626, PCT/US95/07823, WO95/27772, WO95/27773, WO95/27774 and the WO95/27775 of our common pending trial.
Hydrogen peroxide also can exist by adding the enzyme system (being enzyme and its a kind of matrix) that can produce hydrogen peroxide in the beginning of washing and/or cleaning step or process.This kind of enzyme system was disclosed in 9,91202655.6,1991 on October of EP patent application.
The containing metal catalyzer that can be used in the bleaching composition comprises cobalt-containing catalyst, five amine cobaltous acetates (III) and contain Mn catalyst for example, for example they are documented among EPA549271, EPA549272, EPA458397, US5246621, EPA458398, US5194416 and the US5114611.Containing the bleaching composition of peralcohol, manganiferous bleaching catalyst and sequestrant is documented in the patent application 94870206.3.
SYNTHETIC OPTICAL WHITNER except oxygen bleaching agent also is known in the art, and can use in the present invention.The non-oxygen bleaching agent that one class has special-effect comprises photosensitive bleaching agent, as sulfonated phthalein mountain valley with clumps of trees and bamboo zinc and/or phthalein mountain valley with clumps of trees and bamboo aluminium.These materials are deposited on the matrix in washing process.By using rayed, exist under the situation of oxygen, as dry by clothing being suspended under the daylight, sulfonated phthalein mountain valley with clumps of trees and bamboo zinc is activated, and matrix is bleached.Preferred phthalein mountain valley with clumps of trees and bamboo zinc and photosensitive bleaching method are documented among the US4033718.In general, detergent composition contains the 0.025% sulfonation phthalein mountain valley with clumps of trees and bamboo zinc to about 1.25% weight of having an appointment.
Adjuvant system
Composition of the present invention can further contain a kind of adjuvant system.Be applicable to that all conventional adjuvant system of the present invention comprise aluminosilicate, silicate, polycarboxylate, alkyl-or alkenyl Succinic Acid and lipid acid, for example ethylene diaminetetraacetic acid salt, diethylenetriamine pentamethylene acetate, metal ion chelation agent, as amino poly-phosphate, the material of ethylene diamine tetramethylene phosphoric acid and diethylenetriamine pentamethylene phosphoric acid particularly.Phosphate builder also can be used for the present invention.
Proper auxiliary agent can be a mineral ion exchange material, generally is the aluminosilicate material of inorganic hydration, and the synthetic zeolite of hydration more especially is as zeolite A, X, B, HS or the MAP of hydration.
Another kind of suitable inorganic assistant agent material is a layered silicate, as SKS-6 (Hoechst).SKS-6 is by water glass (Na
2Si
2O
5) the crystal layered silicate that constitutes.
The suitable polycarboxylate that contains a carboxyl comprises lactic acid, oxyacetic acid and its ether derivant, as is disclosed in belgian patent 831368,821369 and 821370.The polycarboxylate that contains two carboxyls comprises the water-soluble salt of Succinic Acid, propanedioic acid, (ethylenedioxy) oxalic acid, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid; and be documented in German Offenlegenschrift2446686 and 2446687 and US3935257 in ether carboxylate and be documented in sulfinyl carboxylate salt in the belgian patent 840623.The polycarboxylate that contains three carboxyls is particularly including water miscible Citrate trianion, aconitate and citraconate, and succinate derivative, for example be documented in carboxymethyl oxygen succinate in the English Patent 1379241, be documented in lactoyl succinate (lactoxysuccinates) and oxygen polycarboxylate material in the HOII P 7205873,2-oxo-1 for example, 1,3-tricarballylic acid salt, as be documented in the English Patent 1387447.
The polycarboxylate that contains four carboxyls comprises oxygen two succinates, 1,1,2 that are disclosed in the English Patent 1261829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent polycarboxylate of sulfo group comprise be disclosed in English Patent 1398421 and 1398422 and US3936448 in sulfosuccinate derivant, and be documented in sulfonated pyrolytic Citrate trianion in the English Patent 1082179, be disclosed in the English Patent 1439000 and contain the substituent polycarboxylate of phosphino-.
Alicyclic ring and heterocyclic polycarboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene penta carboxylate salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4,5,6-hexane-hexacarboxylic acid salt and polyhydroxy-alcohol is as the carboxyl methyl-derivatives of sorbyl alcohol, mannitol and Xylitol.The fragrance polycarboxylate comprises mellitic acid, petroleum benzene pregnancy acid and phthalic acid derivatives, is disclosed in the English Patent 1425343.
Wherein preferred polycarboxylate is the hydroxycarboxylate, it every mole contain maximum three carboxyls, more especially Citrate trianions.
The preferred adjuvant system that can be used in the present composition comprises water-insoluble aluminosilicate auxiliary agent, for example zeolite A or layered silicate (SKS-6) and water-soluble carboxylate sequestrant, for example mixture of citric acid.The preferred promoter system that can be used for liquid detergent composition of the present invention is soap and polycarboxylate.
The suitable sequestrant that can join in the detergent composition of the present invention is ethylene diamine-N, the ammonium salt of N '-two Succinic Acid (EDDS) or basic metal, alkaline-earth metal, ammonium or its replacement, perhaps their mixture.Preferred EDDS compound is free acid and its sodium salt or magnesium salts.The sodium salt of the preferred EDDS of this class comprises Na
2EDDS and Na
4EDDS.The example of the magnesium salts of the preferred EDDS of this class comprises MgEDDS and Mg
2EDDS.Magnesium salts is most preferably to join in the composition according to the present invention.
Preferred adjuvant system comprises water-fast aluminosilicate auxiliary agent, as zeolite A and water-soluble carboxylate sequestrant, as the mixture of citric acid.
Other auxiliary agent of a part that can be configured for the adjuvant system of particulate composition comprises inorganic substance, as alkaline carbonate, supercarbonate, silicate and organic substance, as organic phosphoric acid salt, amino poly-inferior hydrocarbon phosphoric acid salt and aminopolycarboxylic salt.
Other suitable water-soluble organic salt is acid homopolymerization or copolymerization or their salt, and wherein poly carboxylic acid contains the carbon atom carboxyl separated from one another that at least two quilts are no more than two.This base polymer is disclosed among the GB-A-1596756.The example of this class salt is that MW is the multipolymer of 2000～5000 polyacrylate and they and maleic anhydride, and the molecular weight of this analog copolymer is 20000 to 70000, particularly about 40000.
The content that detergent builder salt is general is 5% to 80% of composition weight, and is preferred 10% to 70%, most preferably 30% to 60%.
Froth suppressor
Another kind of optional component is a froth suppressor, is typically siloxanes and silicon-dioxide-mixture of siloxanes.Siloxanes generally can be represented with alkylating polysiloxane material, and silicon-dioxide generally adopts with very thin dispersion form, is aerosil and xerogel and various types of hydrophobic silica typically.These materials can add with particle form, and froth suppressor joins releasedly advantageously that water soluble or water are dispersible not to be had in the surface-active washing composition opacity carrying agent basically in particle.Optional is that froth suppressor can dissolve or be dispersed in the liquid vehicle, and uses by disperseing to be used for one or several other components.
A kind of preferred silicone foam control agent is disclosed among the US3933672 of Bartollota etc.Other effective especially froth suppressor is the siloxane foams inhibitor of self-emulsifying, and it is documented among the German patent application DTOS2646126, and it is disclosed on April 28th, 1977.The example of this compounds is DC-544, is provided by Dow Corning, and it is the multipolymer of siloxanes-glycol.Particularly preferred froth suppressor is the froth suppressor system that contains the mixture of silicone oil and 2-alkyl-alkanol.Suitable 2-alkyl-alkanol is 2-butyl-octanol, and it provides industrial with trade mark Isofol12R.
This class A foam A inhibitor system is documented among the common european patent application N92870174.7 in a review, on November 10th, 1992.
Particularly preferred silicone foam control agent is documented among the common european patent application N92201649.8 in a review.Said composition contains the siloxanes/silica mixture with the atresia silica bound of being fuming, as Aerosil
R
Above-mentioned froth suppressor generally to be 0.001% to 2% weight of composition, use by the amount of preferred 0.01% to 1% weight.
Other
Can adopt other to can be used for component in the detergent composition, for example soil-suspending agent, soil releasing agent, white dyes, anti-wear agent, sterilant, gloss inhibitor, tinting material and/or sealing or do not have the spices of sealing.
The material of particularly suitable sealing is water miscible capsule, and it is made of the matrix of glycan and polyol, as is documented among the GB1464616.
Other suitable water-soluble sealing substance contains the dextrin that is produced by the not gelling starches acid of the dicarboxylic acid that replaces-ester, as is documented among the US3455838.These acid-ester dextrin is preferably by starch, as wax shape corn, wax shape Chinese sorghum, sago, tapioca (flour) and potato.The suitable example of said sealing substance comprises the N-Lok that is produced by National Starch.The N-Lok sealing substance is made of the W-Gum and the glucose of modification.Starch is by adding the substituting group of monofunctional, carrying out modification as the octenyl Succinic anhydried.
Be applicable to that antiredeposition of the present invention and dirt suspension reagent comprise derivatived cellulose, as poly carboxylic acid methylcellulose gum, carboxymethyl cellulose and Natvosol and homopolymerization or copolymerization or their salt.This base polymer comprises that the front mentions polyacrylate and the copolymer of maleic anhydride and acrylic acid as auxiliary agent, and the multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid, and maleic anhydride constitutes the multipolymer of at least 20 moles of %.The general consumption of these materials is 0.5% to 10% weight of composition, more preferably 0.75% to 8%, and 1% to 6% weight most preferably.
The feature of preferred white dyes is anionic, its example is 4,4 '-two (2-diethanolamino-4-aniline-s-triazine-6-base is amino) Stilbene-2:2 ' disulfonic acid disodium, 4,4 '-two (2-morpholinoes-4-aniline-s-triazine-6-base amino-Stilbene-2:2 '-disulfonic acid disodium, 4,4 '-two (2,4-pentanoic-s-triazine-6-base is amino) Stilbene-2:2 '-disulfonic acid disodium, 4 '; 4 "-two (2,4-pentanoic-s-triazine-6-base is amino) Stilbene-2-disulfonic acid one sodium, 4,4 '-two (2-aniline-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)-and Stilbene-2,2 '-disulfonic acid disodium, 4,4 '-two (2-aniline-4-(1-methyl-2-hydroxyethylamino)-s-triazine-6-base is amino) Stilbene-2,2 '-disulfonic acid disodium, 2 (Stilbene base-4 "-(naphthols-1 '; 2 ': 4,5)-1,2; 3-triazole-2 "-sodium sulfonate and 4,4 '-two (2-sulfo group styryl) biphenyl.Whitening agent very preferably is the special efficacy whitening agent of common European patent in a review 95201943.8.
Other effective polymeric material is a polyoxyethylene glycol, and particularly molecular weight is 1000～10000, more especially 2000 to 8000, most preferably be about 4000.They are with 0.20% to 5%, and more preferably the amount of 0.25% to 2.5% weight adopts.Polycarboxylate these polymkeric substance and above-mentioned homopolymerization or copolymerization can improve whiteness persistence, fabric dust deposit and removing dust, protein effectively and have the effect of the oxidable dirt under the transition metal impurity situation.
The soil releasing agent that can be used for the present composition effectively generally is terephthalic acid and ethylidene glycol and/or propylene glycol unit multipolymer or the trimer with various arrangements.The example of this base polymer be disclosed in common transfer US4116885 and 4711730 and european patent application 0272033 in.Have following general formula according to the particularly preferred polymkeric substance of EP-A-0272033:
(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)
0.75
Wherein PEG is-(OC
2H
4) O-, PO be (OC
3H
6O) and T be (pcOC
6H
4CO).
Very effective is the polyester of modification, as dimethyl terephthalic acid ester, dimethyl sulfo group isophthalic acid ester, ethylene pure and mild 1, the random copolymers of 2-propylene glycol, end group mainly are made of sulfosalicylic acid ester, next monoesters by ethylidene glycol and/or propylene glycol.Purpose is that the end capped polymkeric substance of sulfosalicylic acid ester is used in acquisition at two ends, and " mainly " in this article refers to the said multipolymer of most of the present invention is with sulfosalicylic acid ester group end-blocking.Therefore but some multipolymers do not have whole end-blockings, and their end group can be by ethylidene glycol and/or the third-1, and the monoesters of 2-glycol constitutes, therefore " secondly " constitute by these materials.
The selected polyester of the present invention contains the dimethyl terephthalic acid of 46% weight of having an appointment, the third-1,2 glycol of about 16% weight, the ethylidene glycol of about 10% weight, the dimethyl methyl yl benzoic acid of about 13% weight and the sulfoisophthalic acid of about 15% weight, and molecular weight about 3000.Polyester and their preparation method are documented in EPA311342.
Known in the art is that free chlorine in tap water loses activity the enzyme that is included in the detergent composition fast.Therefore, in preparation, adopt 0.1% chlorine scavenging agent, for example perborate, ammonium sulfate, S-WAT or polyethylene imine basedly can improve the stability of detergent enzyme in washing process greater than composition weight.The composition that contains the chlorine scavenging agent is documented in european patent application on January 31st, 92870018.6,1992.
Oxyalkylated polycarboxylate for example can be used for the present invention so that additional degrease effect to be provided by those of polyacrylate preparation.This class material is documented in WO91/08281 and PCT90/01815, is p.4 waiting, and they in this combination as a reference.On chemical ingredients, these materials contain the polyacrylic ester that has an oxyethyl group side chain on per 7～8 acrylic acid units.The general formula of side chain is-(CH
2CH
2O)
m(CH
2)
nCH
3, wherein m is 2～3, n is 6～12.Side chain is connected on the polyacrylic ester " main chain " by ester-mode of connection, so that the structure of " honeycomb " polymer class to be provided.Molecular weight can change, but generally arrives in about 50000 scopes about 2000.The oxyalkylated polycarboxylate content of this class is that about 0.05% of composition arrives about 10% weight.
Tenderizer
Fabric softener also can join in the laundry detergent composition of the present invention.These reagent can be inorganic or organic types.The representative of inorganic tenderizer is the green clay that is disclosed among GB-A-1400898 and the USP5019292.The organic fabric tenderizer comprises water-fast tertiary amine, as is disclosed among GB-A-1514276 and the EP-B0011340, and they and a C
12-C
14The combination of quaternary ammonium salt is disclosed among EP-B-0026527 and the EP-B-0026528, and two long-chain acid amides are disclosed among the EP-B-0242919.The effective organic constituent of other of fabric-softening system comprises high-molecular weight polyethylene oxide material, as is disclosed in EP-A-0299575 and 0313146.
The content of green clay is generally with 2% to 20%, and the more preferably amount of 5% to 15% weight, and the material that will add joins in the remaining ingredient of preparation as doing mixed component.The organic fabric tenderizer, for example water-fast tertiary amine or two long-chain acid amides material are with 0.5% to 5% weight, the amount that is generally 1% to 3% weight adds, and with high-molecular weight polyethylene oxide material and water-soluble cationic material with 0.1% to 2%, the amount that is generally 0.15% to 1.5% weight adds.These materials generally join in the composition of jet drying, although it is to mix the adding of particulate form to do more easily in some cases, perhaps they are sprayed onto in other component of composition as melt liquid.
Dispersion agent
Detergent composition of the present invention also can contain dispersion agent.Suitable water-soluble organic salt is acid or their salt homopolymerization or copolymerization, and wherein poly carboxylic acid contains the carboxyl that carbon atom that at least two quilts are no more than two is separated from each other.The open GB-A-1596756 of this base polymer.The example of this class salt is that MW is 2000～5000 polyacrylate, and the multipolymer of they and maleic anhydride, and the molecular weight of this analog copolymer is 1000～100000.
Especially the multipolymer of acrylate and methacrylic ester, for example molecular weight is that 4000 480N can join in the detergent composition of the present invention with the amount of 0.5% to 20% weight of composition.
The present composition can contain calcium soap solation compound, and it has lime soap dispersing power (LSDP), and definition is no more than 8 hereinafter, preferably is no more than 7, is most preferably not exceeding 6.Calcium soap solation compound preferred content is 0% to 20% weight.
The data determination of calcium soap colloidal sol effect is provided by the lime soap dispersing power (LSDP) that adopts the calcium soap distributed test to determine, as is documented in the article of H.C.Borghetty and C.A.Bergman, J.Am.Oil.Chem.Soc., the 27th volume, the 88th～90 page (1950).The method person of being operated of this calcium soap distributed test is widely used in this area, reference example such as following article: W.N.Linfield, Surfactant science Series, the 7th volume, page 3; W.N.Linfield, Tenside surf.det., the 27th volume, the 159th～163 (1990); And M.K.Nagarajan, W.F.Masler, Cosmetics and Toiletries, the 104th volume, 71-73, (1989).LSDP is that dispersion agent is 333ppm CaCO with disperseing by 0.025 gram sodium oleate 30 milliliters of equivalent hardness
3(Ca: Mg=3: the weight percent of the sodium oleate that the calcium soap settling that forms in the water 2) is required.
Tensio-active agent with good calcium soap colloidal sol ability comprises the alcohol of some amine oxides, trimethyl-glycine, sultaine, alkyl ethoxy sulfate and ethoxylation.
Spendable LSDP is no more than 8 typical surface promoting agent and comprises C according to the present invention
16-C
18The average degree of dimethyl oxidation amine, ethoxylation is 1～5 C
12-C
18Alkyl ethoxy sulfate, particularly degree of ethoxylation are the C of 3 (LSDP=4)
12-C
15Alkyl ethoxy sulfate surfactant and ethoxyquin degree are the C of 12 (LSDP=6) or 30
14-C
15The alcohol of ethoxylation, it is provided by BASF GmbH with Lutensol AO12 and Lutensol AO30 respectively.
Be applicable to that polymeric calcium soap colloidal sol of the present invention is documented at Cosmetics and Toiletries, the 104th volume, the M.K.Nagarajan of the 71st～73 (1989) middle publication, the article of W.F.Masler.
Hydrophobicity SYNTHETIC OPTICAL WHITNER, for example amino caproyl of 4-[N-capryloyl-6-] Phenylsulfonic acid, the amino caproyl of 4-[N-nonanoyl-6-] Phenylsulfonic acid, the amino caproyl of 4-[N-decanoyl-6-] Phenylsulfonic acid and their mixture; Can be used as calcium soap solation compound with nonanoyl oxygen Phenylsulfonic acid together with hydrophilic/hydrophobic SYNTHETIC OPTICAL WHITNER preparation.
Dye transfer inhibitor
Detergent composition of the present invention also can contain and is useful on the dyestuff that prevents dissolved and suspension in the fabric washing operating process that comprises DYED FABRICS and transfers to compound on the another kind from a kind of fabric.
The polymeric dye transfer inhibitor
Detergent composition of the present invention also contains 0.001% to 10%, and is preferred 0.01% to 2%, most preferably the polymeric dye transfer inhibitor of 0.05% to 1% weight.Said polymeric dye transfer inhibitor generally will join in the detergent composition, transfers on the fabric that will wash from DYED FABRICS to suppress dyestuff.These polymkeric substance have cooperation or the unstable dyestuff of absorption from being with the dyestuff fabric to wash off before this dyestuff has an opportunity to adhere on other fabric that is in the suds.
Specially suitable polymeric dye transfer inhibitor is multipolymer, polyvinylpyrrolidonepolymers polymers, Ju Yi Xi oxazolidinone and polyvinyl imidazol, perhaps their mixture of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole.
Add this base polymer and also can improve the performance of enzyme of the present invention.
A) polyamine N-oxide pllymers
The polyamine N-oxide pllymers that is suitable for adopting contains the unit with following general structure:
Wherein P is polymerisable unit, can connect the R-N-O group on it, and perhaps wherein the R-N-O group constitutes the part of polymerizable unit or the two is comprehensive.
A is
X is 0 or 1;
R is fat, fat, fragrance, heterocycle or the alicyclic group of ethoxylation or their any combination, can connect the nitrogen of N-O group on it, and perhaps wherein the nitrogen of N-O group is the part of these groups.
The N-O group can replace with following formula:
Wherein R1, R2 and R3 are fat group, fragrance, heterocycle or alicyclic group or their combination, and x and/or y and/or z are 0 or 1, and can connect the nitrogen on the N-O group on it, and perhaps wherein the nitrogen on the N-O group constitutes the part of these groups.
The N-O group can be the part of polymerizable unit (P) or can be connected on the polymer main chain or the combination of the two.
Wherein the suitable polyamine N-oxide of a N-O group formation polymerizable unit part contains polyamine N-oxide, and wherein R is selected from fat, fragrance, alicyclic ring or heterocyclic group.
The said polyamine N-oxide of one class contains the group of polyamine N-oxide, and wherein the nitrogen of N-O group constitutes the part of R-group.Preferred polyamine N-oxide compound is that wherein R is a heterocyclic group, for example pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, bifurcation pyridine and their derivative.
Another kind of said polyamine N-oxide contains the nitrogen of N-O group wherein and is connected one group of polyamine N-oxide on the R group.
Other suitable polyamine N-oxide is that wherein N-O group is connected the polyamine oxide compound on the polymerizable unit.
The preferred kind of these polyamine N-oxide is such polyamine N-oxide, and it has logical formula I, and wherein R is fragrance, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is the part of said R group.The example of these kinds is such polyamine oxide compounds, and wherein R is a heterogeneous ring compound, as piperidines, pyrroles, imidazoles and their derivative.
Another kind of preferred polyamine N-oxide compound is the polyoxygenated amine with logical formula I, and wherein R is fragrance, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is connected on the said R group.
The example of these kinds is that wherein the R group can be fragrant, for example the polyoxygenated amine of phenyl.
Can adopt any main polymer chain,, and have the character that suppresses dye transfer as long as the amine oxide polymers that forms is water-soluble.The example of suitable polymer main chain is polyethylene kind, polyolefine, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and their mixture.
The ratio of common amine of amine n-oxide polymkeric substance of the present invention and amine n-oxide is 10: 1 to 1: 1,000,000.But the amount that is present in the amine oxide group in the polyoxygenated amine polymer can change by suitable copolymerization or the N-oxidizing reaction by suitable degree.Preferably the ratio of amine and amine n-oxide is 2: 3 to 1: 1000,000, and more preferably be 1: 4 to 1: 1,000,000, most preferably 1: 7 to 1: 1,000,000.In fact polymkeric substance of the present invention comprises random copolymers or segmented copolymer, and one of them monomer type is an amine n-oxide, and another monomer type is or is not amine n-oxide.The unitary PKa of the amine oxide of polyamine N-oxide＜10, preferred PKa＜7, most preferably PKa＜6.
The polyamine oxide compound can be with the almost polymerization acquisition of any degree.Extent of polymerization is not crucial, as long as material has required water-soluble and dye suspension ability.
In general, molecular-weight average is 500 to 1,000,000; Preferred 1000 to 50,000, more preferably 2,000 to 30,000, most preferably in 3,000 to 20,000 scopes.
B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole
The molecular-weight average that can be used for N-vinyl imidazole N-vinyl pyrrolidone polymer of the present invention is 5000～1000000, preferred 5000～200000.
The polymkeric substance very preferably that can be used for detergent composition of the present invention contains the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, wherein the molecular-weight average of said polymkeric substance is 5000 to 50000, more preferably 8000 to 30000, most preferably 10000 to 20000.
Average molecular weight range passes through determination of light scattering, as is documented in Barth H.G. and MaysJ.W.Chemical Analysis the 113rd volume, " Modern Methods of PolymerCharaterization ".
The scope of the molecular-weight average of N-vinyl imidazole N-vinylpyrrolidone copolymer very preferably is 5000 to 50000; More preferably 8000 to 30000; Most preferably 10000 to 20000.
Be characterised in that the N-vinyl imidazole N-vinylpyrrolidone copolymer with said average molecular weight range has good inhibition dye transfer effect, can influence the washing effect of the detergent composition that adopts its preparation simultaneously sharply.
The molar ratio of N-vinyl imidazole and N-vinyl pyrrolidone is 1 to 0.2 in the N-vinyl imidazole N-vinyl pyrrolidone of the present invention, more preferably 0.8 to 0.3, most preferably 0.6 to 0.4.
C) Polyvinylpyrolidone (PVP)
Detergent composition of the present invention can also adopt molecular-weight average to be about 2500 to 400000, and preferred about 5000 to about 200000, and more preferably from about 5000 to 50000,5000 to about 15000 Polyvinylpyrolidone (PVP) (" PVP ") most preferably from about.Suitable Polyvinylpyrolidone (PVP) can be by ISP Corporation, New York, NY and Montreal, Canada is with name of product PVP K-15 (viscosity molecular weight is 10000), PVP K-30 (molecular-weight average is 40000), PVP K-60 (molecular-weight average is 160000) and industrial the providing of PVP K-90 (molecular-weight average is 360000).Other the suitable Polyvinylpyrolidone (PVP) that is provided by BASF Corperation comprises Sokalan HP165 and Sokalan HP12; Polyvinylpyrolidone (PVP) known to the skilled (referring to for example EP-A-262897 and EP-A-256696) at detergent applications.
D) Ju Yi Xi oxazolidinone:
Detergent composition of the present invention also can adopt Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.The molecular-weight average of said Ju Yi Xi oxazolidinone is about 2500 to 400000, and preferred about 5000 to about 200000, and most preferably from about 5000 to about 50000, most preferably from about 5000 to about 15000.
E) polyvinyl imidazol
Detergent composition of the present invention also can adopt polyvinyl imidazol as the polymeric dye transfer inhibitor.The molecular-weight average of said polyvinyl imidazol is about 2500 to 400000, and preferred about 5000 to about 200000, and most preferably from about 5000 to about 50000, most preferably from about 5000 to about 15000.
F) crosslinked polymkeric substance:
Crosslinked polymkeric substance is the interconnected to a certain extent polymkeric substance of its main chain; These crosslinked available be chemistry or physical condition, can have active group at main chain or on side chain; Crosslinked polymkeric substance has been documented in Journal of Polymer Science, the 22nd volume, 1035-1039 page or leaf.
In one embodiment, crosslinked polymkeric substance is so that the mode that they constitute three-dimensional rigid structure prepares, and it can be enclosed in dyestuff in the hole of three-dimensional structure formation.In another embodiment, crosslinked polymkeric substance is caught dyestuff by swelling.
The crosslinked polymkeric substance of this class is documented in the co-pending patent application 94870213.9.
Washing methods
Composition of the present invention can be used for nearly all washing or cleaning method, and these methods comprise pickling process, method for pretreating and wherein can add the method for the rinse step that helps detergent composition in addition.
In the present invention method of record comprises fabric is contacted with washing soln with ordinary method, and its example is as follows.
Method of the present invention is carried out in cleaning course easily.Cleaning method preferably at 5 ℃ to 95 ℃, particularly carries out to 60 ℃ at 10 ℃.The pH of treatment soln is preferably 7 to 11.
The following examples are meant the typical composition of the present invention, but do not limit the scope of the present invention or other explanation.
In detergent composition, the concentration of enzyme is used based on the pure enzyme of total composition and is represented, unless other explanation is arranged, detergent component is represented with the gross weight of composition.The component symbol of abbreviation has following implication: LAS: linear C
12Sodium alkyl benzene sulfonate TAS: tallow alkyl sodium sulfate CXYAS: C
1X-C
1YSodium alkyl sulfate 25EY: with the C of average Y moles of ethylene oxide condensation
12-C
15Mainly
Be linear primary alconol CXYEZ: with the C of average Z moles of ethylene oxide condensation
1X-C
YMainly be
Linear primary alconol XYEZS: every mole of C with average Z moles of ethylene oxide condensation
1X-C
1Y
Sodium alkyl sulfate QAS: R
2.N
+(CH
3)
2(C
2H
4OH), R
2=C
12-C
14Soap: the tallow by 80/20 and the mixture of Oleum Cocois produce
Linear alkyl carboxylic acid sodium TFAA: C
16-C
18Alkyl N-methyl glucose amide TPKFA: C
12-C
14The lipid acid DEQA of whole cuts of topping: two-(tallow-oxygen-ethyl) alkyl dimethyl ammonium chloride SDASA: 1: 2 stearyl dimethyl amine: triple pressed stearic acid Neodol45-13: C
14-C
15The linear primary alcohol b-oxide is by Shell
Chemical CO. sells silicate: amorphous sodium silicate (SiO
2: Na
2O ratio=2.0) NaSKS-6: general formula δ-Na2Si
2O
5Crystalline layered silicate carbonate: granularity is 200 microns to 900 microns an anhydrous sodium carbonate supercarbonate: granularity is 400 microns to 1200 microns a Carbon Dioxide hydrogen
Sodium STPP: anhydrous sodium tripolyphosphate MA/AA: 1: 4 toxilic acid/acrylic acid multipolymer, molecular-weight average
Be about 80000 polyacrylic ester: poly-propionic ester homopolymer, molecular-weight average is 8000, by
BASF GmbH provides zeolite A with the trade(brand)name of PA30: general formula is Na
12(AlO
2SiO
2)
12.27H
2The hydration sial of O
Acid sodium, basic granularity is 0.1 to 10 micron Citrate trianion: citrate trisodium dihydrate, activity are 86.4%, grain
Degree is distributed as 425 microns to 850 microns citric acids: Citric Acid, usp, Anhydrous Powder PB1: anhydrous sodium perborate monohydrate SYNTHETIC OPTICAL WHITNER, general formula is
NaBO
2.H
2O
2PB4: anhydrous sodium perborate tetrahydrate percarbonate: anhydrous SPC-D SYNTHETIC OPTICAL WHITNER, general formula are 2Na
2CO
3.3H
2O
2TAED: tetra-acetylated ethylene diamine NOBS: the nonanoyl oxygen Phenylsulfonic acid photosensitization SYNTHETIC OPTICAL WHITNER of sodium-salt form: the sulfonated attitude that in dissolving in the polymkeric substance of dextrin, seals
Phthalein mountain valley with clumps of trees and bamboo zinc antibody: the Anti-that provides by Novo Nordisk A/S
Termamyl ERT860418 (500/150 μ l) and
anti-BANPPY1747(200μl)。Amylase: be documented among WO94/18314 and the WO96/05295 by
Genencor is with trade(brand)name Purafact Ox Am
RSell
The starch fermentoid; Termamyl
, Ban
And Duramyl
,
All provide by Novo Nordisk A/S, and record
In WO95/26397 those.Proteolytic enzyme: by Novo Nordisk A/S with trade(brand)name Savinase,
That Alcalase, Durazym sell and by Gist-
Brocades sells with trade(brand)name Maxacal, Maxapem
The albumen fermentoid and be documented in WO91/06637 and/or
The albumen of putting down in writing among WO95/10591 and/or the EP251446
Enzyme.Lipase: by Novo Nordisk A/S with trade(brand)name Lipolase,
The fatty fermentoid that Lipolase Ultra sells.Cellulase: by Novo Nordisk A/S with trade(brand)name Carezyme,
The cellulose family that Celluzyme and/or Endolase sell
Enzyme.CMC: Xylo-Mucine.HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid.DETPMP: diethylenetriamine five (methylene phosphonic acid), by
Monsanto sells, and trade mark is Dequest2060.PVNO: poly-(4-vinylpridine)-N-oxide compound PVPVI: poly-(the 4-second of vinyl-imidazoles and vinyl-pyrrolidinone
The thiazolinyl pyridine)-N-oxide compound/multipolymer.Whitening agent 1: 4,4 '-two (2-sulfo group styryl) biphenyl disodium.Whitening agent 2: 4,4 '-two (4-anilinos-6-morpholine-1,3,5-triazines-2-
Base) Stilbene-2,2, the disulfonic acid disodium.Polysiloxane foam preventer: contain siloxanes-oxyalkylene copolymers as dispersion agent
The polydimethylsiloxane Foam Control, said foam control
The ratio of preparation and said dispersion agent is to arrive at 10: 1
100∶1。Granular suds suppressing agent: 12% siloxanes/silicon-dioxide, 18% Stearyl alcohol, 70
% pearl starch SRP1: the sulfo group that contains ethylene oxide oxygen and terephthaloyl main chain
Benzoyl end-blocking ester SRP2: poly-(1, the 2 propylene terephthalate) of diethoxyization
The disconnected polymkeric substance vitriol of short embedding: anhydrous sodium sulphate.HMWPEO: high molecular weight polyethylene oxide.PEG: polyoxyethylene glycol.The perfume particle of sealing: adopt zeolite 13x, spices and dextrose/glycerine to condense sticking
The soluble spices diffusion technique of mixture.
Embodiment 1:
The production of antibody
Give the 1mg/mlTermamyl of 1 milliliter of chicken chest muscle injection
Perhaps Ban
Emulsion.The amylolysis emulsion is to adopt Freunds to finish auxiliary (Freund and McDermott, 1942; Freund1956) by violent equivalent volumes Termamyl
Perhaps Ban
Solution (2mg/ml) and Freunds finish auxiliary and prepare.
The immunity step is to adopt with Freunds not finish the auxiliary injection, and collects egg and finish after 4 weeks in the time in a week.The extraction of carrying out from egg yolk is according to being documented in Immunological Investigation19,1990, and the Polson extracting method carries out among the pp253-258.
Diastatic inactivation reaction
Termamyl
Perhaps Ban
Material solution is at Tutofusin tris buffered soln (5 * 10
-2The M Tutofusin tris, 25mMNaCl, pH=8) middle preparation, concentration is 0.05% organized enzyme.Phosphate buffer soln (0.05MKH
2PO
4, pH6.8) contain antibody (0.18mg/ml).The interaction of starch fermentoid (final concentration is 0.004%)/antibody is (to be 0.8% in tap water containing Ariel liquid, pH8.5) and Ariel ColorFutur (0.8% in tap water, obtains in following 15 minutes at 40 ℃ in industrial available detergent solution pH9.5).
Measure starch zymoid residual activity, and in 5 minutes, successfully block diastatic enzymic activity.
Embodiment 2
Prepare following laundry detergent composition according to the present invention:
Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ ⅥLAS 8.0 8.0 8.0 8.0 8.0 8.0C25E3 3.4 3.4 3.4 3.4 3.4 3.4QAS-0.8 0.8-0.8 0.8A 18.1 18.1 18.1 18.1 18.1 18.1 13.0 13.0 13.0 27.0 27.0 27.0 1.4 1.4 1.4 3.0 3.0 3.0 26.1 26.1 26.1 26.1 26.1 26.1PB4 9.0 9.0 9.0 9.0 9.0 9.0TAED 1.5 1.5 1.5 1.5 1.5 1.5DETPMP 0.25 0.25 0.25 0.25 0.25 0.25HEDP 0.3 0.3 0.3 0.3 0.3 0.3 0.0026 0.0026 0.0026 0.0026 0.0026 0.0026 0.002 0.05 0.0009 0.0003 0.0009 0.01 0.01 0.5 0.005 0.0001 0.05 0.09MA/AA 0.3 0.3 0.3 0.3 0.3 0.3CMC 0.2 0.2 0.2 0.2 0.2 0.2 15 15 15 15 15 15 ( ppm ) 1 0.09 0.09 0.09 0.09 0.09 0.09 0.3 0.3 0.3 0.3 0.3 0.3 0.5 0.5 0.5 0.5 0.5 0.5/ 850 850 850 850 850 850100％g/l
Embodiment 3
Prepare the granular laundry detergent compositions that following tap density is 750g/l according to the present invention:
Ⅰ Ⅱ ⅢLAS 5.25 5.61 4.76TAS 1.25 1.86 1.57C45AS-2.24 3.89C25AE3S-0.76 1.18C45E7 3.25-5.0C25E3-5.5-QAS 0.8 2.0 2.0STPP 19.7--A-19.5 19.5NaSKS-6/-10.6 10.6 ( 79∶21 ) 6.1 21.4 21.4-2.0 2.0 6.8-- 39.8-14.3PB4 5.0 12.7-TAED 0.5 3.1-DETPMP 0.25 0.2 0.2HEDP-0.3 0.3 0.0009 0.005 0.09 0.0002 0.0008 0.005 0.0026 0.0085 0.045 0.003 0.003 0.003 0.00064 0.00064 0.00064MA/AA 0.8 1.6 1.6CMC 0.2 0.4 0.4 ( ppm ) 15ppm 27ppm 27ppm1 0.08 0.19 0.192 0.04 0.04 0.3 0.3 0.3 0.5 2.4 2.4/100％4
Detergent formulations below produced according to the present invention, wherein I is the phosphorated detergent composition, and II is the detergent composition that contains zeolite, and III is the detergent composition of compacting:
I II III blowing powder STPP 24.0-24.0 Wessalith CS-24.0-C45AS 9.0 6.0 13.0MA/AA 2.0 4.0 2.0LAS 6.0 8.0 11.0TAS 2.0--silicate 7.0 3.0 3.0CMC 1.0 1.0 0.5 brightening agents 2 0.2 0.2 0.2 soap 1.0 1.0 1.0DETPMP 0.4 0.4 0.2 spray sodium sulphate 3.0 3.0 5.0 balances (moisture or impurity) 100.0 100.0 100.0 density (g/l) 630 670 670 embodiment 5 that C45E7 2.5 2.5 2.0C25E3 2.5 2.5 2.0 silicone suds suppressors 0.3 0.3 0.3 spices 0.3 0.3 0.3 dry additive carbonate 6.0 13.0 15.0PB4 18.0 18.0 10.0PB1 4.0 4.0 0TAED 3.0 3.0 1.0 photosensitive bleaching agents 0.02 0.02 0.02 proteinase-10 .01 0.01 0.01 lipase 0.009 0.009 0.009 amylase 0.002 0.0004 0.01 antibody 0.007 0.005 0.1 is dry mixed
Prepare the detergent formulations that does not contain SYNTHETIC OPTICAL WHITNER that band look clothing is washed in following being used in particular for according to the present invention:
I II III blowing powder
Zeolite A 15.0 15.0-
Sodium sulfate 0.0 5.0-
LAS 3.0 3.0 -
DETPMP 0.4 0.5 -
CMC 0.4 0.4 -
MA/AA 4.0 4.0 -
Agglomerate
C45AS - - 11.0
LAS 6.0 5.0 -
TAS 3.0 2.0 -
Silicate 4.0 4.0-
Zeolite A 10.0 15.0 13.0
CMC - - 0.5
MA/AA - - 2.0
Carbonate 9.0 7.0 7.0
Spray
Spices 0.3 0.3 0.5
C45E7 4.0 4.0 4.0
C25E3 2.0 2.0 2.0
Dry additive
MA/AA - - 3.0
NaSKS-6 - - 12.0
Citric acid 10.0-8.0
Supercarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0
PVPVI/PVNO 0.5 0.5 0.5
Proteinase-10 .026 0.016 0.047
Lipase 0.009 0.009 0.009
Cellulase 0.004 0.004 0.004
Amylase 0.01 0.005 0.0003
Antibody 0.1 0.05 0.001
Silicone suds suppressor 5.0 5.0 5.0
Dry additive
Sodium sulfate 0.0 9.0 0.0
Balance (moisture and impurity) 100.0 100.0 100.0
Density (g/l) 700 700 700
Embodiment 6
Detergent formulations below produced according to the present invention:
Ⅰ Ⅱ Ⅲ Ⅳ
LAS 20.0 14.0 24.0 22.0
QAS 0.7 1.0 - 0.7
TFAA - 1.0 - -
C25E5/C45E7 - 2.0 - 0.5
C45E3S - 2.5 - -
STPP 30.0 18.0 30.0 22.0
Silicate 9.0 5.0 10.0 8.0
Carbonate 13.0 7.5-5.0
Supercarbonate-7.5--
DETPMP 0.7 1.0 - -
SRP1 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Proteinase-10 .008 0.01 0.026 0.026
Lipase 0.004 0.002 0.004 0.002
Cellulase 0.0004 0.0001--
Amylase 0.004 0.0003 0.002 0.007
Antibody 0.01 0.005 0.01 0.08
Photosensitization SYNTHETIC OPTICAL WHITNER 70ppm 45ppm-10ppm (ppm)
Whitening agent 1 0.2 0.2 0.08 0.2
PB1 6.0 2.0 - -
NOBS 2.0 1.0 - -
Balance (moisture and assorted 100 100 100 100 matter)
Embodiment 7
Prepare following detergent formulations according to the present invention:
I II III IV blowing powder
Zeolite A 30.0 22.0 6.0 6.7
NaSKS-6 - - - 3.3
Polycarboxylate---7.1
Sodium sulfate 19.0 5.0 7.0-
MA/AA 3.0 3.0 6.0 -
LAS 14.0 12.0 22.0 21.5
C45AS 8.0 7.0 7.0 5.5
Positively charged ion---1.0
Silicate-1.0 5.0 11.4
Soap--2.0-
Whitening agent 1 0.2 0.2 0.2-
Carbonate 8.0 16.0 20.0 10.0
DETPMP-0.4 0.4-injection
C45E7 1.0 1.0 1.0 3.2 dry additives
PVPVI/PVNO 0.5 0.5 0.5 -
Antibody 0.1 0.005 0.001 0.1
Amylase 0.02 0.0008 0.0004 0.02
Proteinase-10 .052 0.01 0.01 0.01
Lipase 0.009 0.009 0.009 0.009
Cellulase 0.0002 0.0002 0.0002 0.0002
NOBS - 6.1 4.5 3.2
PB1 1.0 5.0 6.0 3.9
Sodium sulfate-6.0-to balance
Balance (moisture and assorted 100 100 100 matter)
Embodiment 8
High-density below produced according to the present invention and the detergent composition that contains SYNTHETIC OPTICAL WHITNER:
I II III blowing powder
Zeolite A 15.0 15.0 15.0
Sodium sulfate 0.0 5.0 0.0
LAS 3.0 3.0 3.0
QAS - 1.5 1.5
DETPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
MA/AA 4.0 2.0 2.0
Agglomerate
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray
Spices 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 - -
Dry additive
Citrate trianion 5.0-2.0
Supercarbonate-3.0-
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PB1 14.0 7.0 10.0
MW is 5,000,000--0.2 polyethylene oxide
Bentonite clay--10.0
Antibody 0.07 0.03 0.009
Amylase 0.02 0.005 0.0005
Proteinase-10 .01 0.01 0.01
Lipase 0.009 0.009 0.009
Cellulase 0.004 0.004 0.004
Silicone suds suppressor 5.0 5.0 5.0 dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (moisture and impurity) 100.0 100.0 100.0
Density (g/l) 850 850 850 embodiment 9 following high density detergent agent formulations produced according to the present invention:
I II agglomerate
C45AS 11.0 14.0
A 15.0 6.0 boils
Carbonate 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DETPMP 0.4 0.4 sprays
C25E5 5.0 5.0
Spices 0.5 0.5
Dry additive
HEDP 0.5 0.3
SKS6 13.0 10.0
Citrate trianion 3.0 1.0
TAED 5.0 7.0
Percarbonate 20.0 20.0
SRP1 10.3 0.3
Antibody 0.5 0.03
Amylase 0.05 0.005
Proteinase-10 .014 0.014
Lipase 0.009 0.009
Cellulase 0.001 0.001
Silicone suds suppressor 5.0 5.0
Whitening agent 1 0.2 0.2
Whitening agent 2 0.2-
Balance (moisture and impurity) 100 100
Density (g/l) 850 850
Embodiment 10
Prepare following granular detergent composition according to the present invention:
Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ
LAS 21.0 25.0 18.0 18.0 -
Coco?C12-14AS - - - - 21.9
AE3S - - 1.5 1.5 2.3
Decyl dimethyl hydroxyl-0.4 0.7 0.7 0.8 ethyl n H
4+ Cl
Nonionic 1.2-0.9 0.5-CocoC12-14 Fatty Alcohol(C12-C14 and C12-C18)----1.0
STPP 44.0 25.0 22.5 22.5 22.5
Zeolite A 7.0 10.0--8.0
MA/AA - - 0.9 0.9 -
SRP1 0.3 0.15 0.2 0.1 0.2
CMC 0.3 2.0 0.75 0.4 1.0
Carbonate 17.5 29.3 5.0 13.0 15.0
Silicate 2.0-7.6 7.9-
Antibody 0.005 0.05 0.006 0.5 1.0
Amylase 0.0008 0.004 0.001 0.04 0.1
Proteinase-10 .005 0.04 0.007 0.09 0.15
Lipase 0.003 0.003 0.003--
Cellulase-0.001 0.001 0.001 0.001
NOBS - - - 1.2 1.0
PB1 - - - 2.4 1.2
Diethylidene three---0.7 1.0
Triamine pentaacetic acid
Diethylenetriamine five--0.6--methyl-phosphorous acid
Sal epsom--0.8--
Photosensitive bleaching agent 45ppm 50ppm 15ppm 45ppm 42
Whitening agent 1 0.05-0.04 0.04 0.04
Whitening agent 2 0.1 0.3 0.05 0.13 0.13
Water and minor component maximum 100%
Embodiment 11
Liquid detergent preparation below produced according to the present invention:
Ⅰ Ⅱ Ⅲ Ⅳ Ⅴ Ⅵ Ⅶ Ⅶ
ⅠLAS 10.0 13.0 9.0-25.0---C25AS 4.0 1.0 2.0 10.0-13.0 18.0 15.0C25E3S 1.0--3.0-2.0 2.0 4.0C25E7 6.0 8.0 13.0 2.5--4.0 4.0TFAA---4.5-6.0 8.0 8.0QAS----3.0 1.0--TPKFA 2.0-13.0 2.0-15.0 7.0 7.0---5.0--4.0 4.0/ 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 4.0 2.0 1.0-1.0--- 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.01,2- 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.0---5.0--9.0 9.0--8-----NaOH ( pH ) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 0.5-0.5 0.2--0.4 0.3DETPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0-SRP2 0.3-0.3 0.1--0.2 0.1PVNO-------0.10 0.09 0.0005 0.005 0.5 0.005 0.5 0.008 0.005 0.02 0.0002 0.0008 0.04 0.002 0.05 0.005 0.0004 0.005 0.005 0.004 0.003 0.08 0.005 0.003 0.006-0.002-0.0002--0.003 0.003---0.0001--0.0004 0.0004 0.1 0.2-2.0 1.0 1.5 2.5 2.5--1.0------0.015-0.01--------4.0 4.0------0.6 0.3--SD3 100％：12
Granular fabric cleaning composition with " by washing ramollescence " produced according to the present invention:
Ⅰ Ⅱ
45AS - 10.0
LAS 7.6 -
68AS 1.3 -
45E7 4.0 -
25E3 - 5.0
Coconut-alkyl-dimethyl hydroxyl 1.4 1.0
Base-ethyl 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
Green clay 10.0 10.0
HMWPEO - 0.1
Antibody 0.1 0.002
Amylase 0.03 0.0005
Proteinase-10 .02 0.006
Lipase 0.02 0.01
Cellulase 0.001-
Silicate 3.0 5.0
Carbonate 10.0 10.0
Granular foam inhibitor 1.0 4.0
CMC 0.2 0.1
Water/impurity reaches 100% embodiment 13
Rinsing below produced according to the present invention adds the composition of fabric softener:
Tenderizer activity 20.0
Antibody 0.009
Amylase 0.001
Cellulase 0.001
HCL 0.03
Froth suppressor 0.01
Blue dyestuff 25ppm
CaCl
2 0.20
Spices 0.90
Water/impurity reaches 100% embodiment 14
Fabric softener composition below produced according to the present invention:
Ⅰ Ⅱ Ⅲ
DEQA 2.60 19.00 -
SDASA - - 70.0
The stearic acid 0.30 of IV=0--
Neodol45-13 - - 13.0
Spirit of salt 0.02 0.02-
Ethanol--1.0
PEG - 0.60 -
Antibody 0.06 0.0004 0.05
Amylase 0.01 0.0005 0.008
Proteolytic enzyme-0.0008-
Cellulase 0.001 0.001-
Spices 1.00 1.00 0.75
Succinic Acid two geranyl esters--0.38
Silicone suds suppressor 0.01 0.01-
Ionogen-600ppm-
Dyestuff 100ppm 50ppm 0.01
Water and impurity 100% 100%-embodiment 15
Synthetic detergent piece clean fabric composition produced according to the present invention:
I II III IV C26AS 20.00 20.00 20.00 20.00CFAA, 5.0 5.0 5.0 5.0LAS (C11-13) 10.0 10.0 10.0 10.0 sodium carbonate 25.0 25.0 25.0 25.0 sodium pyrophosphates 7.0 7.0 7.0 7.0STPP 7.0 7.0 7.0 7.0 Wessalith CS 5.0 5.0 5.0 5.0CMC, 0.2 0.2 0.2 0.2 polyacrylate (MW1400) 0.2 0.2 0.2 0.2 coconuts one glycollic amide 5.0 5.0 5.0 5.0 antibody 0.06 0.03 0.09 0.0009 amylase 0.01 0.001 0.002 0.0003 proteinase-10 .08 0.01 0.005 0.001 brightening agents, spices 0.2 0.2 0.2 0.2CaSO41.0 1.0 1.0 1.0MgSO
41.0 1.0 1.0 1.0 water 4.0 4.0 4.0 4.0
Filler
*: equilibrate to 100%
*Can be selected from and make things convenient for material, CaCO
3, talcum, clay (kaolin, terre verte), silicate etc.Embodiment 16
Detergent additives produced according to the present invention:
I II III LAS-5-STPP, 30-30 Wessalith CSs-35-PB1,20 15 20TAED, 10 8 10 protease-0.3-amylase, 0.4 0.2-antibody 525
Claims (15)
1. detergent composition, it contains amylase and the directed antibody of amylase.
2. the detergent composition of claim 1, the content of the directed antibody of wherein said amylase are that the 10E-6% of total composition is to 10E+1% weight.
3. the detergent composition of claim 1 to 2, wherein amylase is selected from α-Dian Fenmei [EC3.2.1.1].
4. the detergent composition of claim 3, wherein said amylase is from mould or bacterium.
5. the detergent composition of claim 1 to 4, wherein diastatic content is 0.0001% to 2% of total composition, and is preferred 0.00018% to 0.1%, more preferably the pure enzyme of 0.00024% to 0.048% weight.
6. the detergent composition of claim 1 to 5, directed antibody of wherein said amylase and diastatic molecular ratio were equal to or less than 100: 1, preferably were equal to or less than 50: 1.
7. the detergent composition of claim 1 to 6, the directed antibody of wherein said amylase is single clone antibody, preferably its fragment.
8. the detergent composition of claim 7, directed antibody of wherein said amylase and diastatic molecular ratio were equal to or less than 50: 1, preferably were equal to or less than 20: 1.
9. the detergent composition of any one claim of front wherein joins the directed antibody of said amylase in the releasing agent.
10. the detergent composition of any one claim of front comprises that further one or several are selected from the component of negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionic tensio-active agent, auxiliary agent, bleach system, froth suppressor, soil release polymers, lime soap dispersing agent, soil-suspending agent and anti redeposition agent, green clay and/or their mixture.
11. the detergent composition of any one claim of front, wherein it is liquid, particle, powder, gel, mashed prod or piece.
12. a detergent additives, it contains the directed antibody of amylase.
13. the detergent additives of claim 12 further contains a kind of amylase.
14. the directed antibody of amylase is used to control the purposes of amylase activity in detergent composition.
15. the purposes of the directed antibody of the amylase of claim 14, it is used for laundry detergent composition so that fabric nursing effect to be provided.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/US1996/013367 WO1998007818A1 (en) | 1996-08-16 | 1996-08-16 | Detergent compositions comprising antibody controlled amylolytic activity |
| WOPCT/US96/13367 | 1996-08-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1232491A true CN1232491A (en) | 1999-10-20 |
Family
ID=22255628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97198586.3A Pending CN1232491A (en) | 1996-08-16 | 1997-08-13 | Detergent compositions comprising antibody controlled amylolytic activity |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0918838A1 (en) |
| CN (1) | CN1232491A (en) |
| AR (1) | AR009258A1 (en) |
| AU (2) | AU6953696A (en) |
| BR (1) | BR9712079A (en) |
| CA (1) | CA2263427A1 (en) |
| WO (2) | WO1998007818A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19824688A1 (en) * | 1998-06-03 | 1999-12-09 | Henkel Kgaa | Detergents and cleaning agents containing amylase and percarbonate |
| DE19824705A1 (en) * | 1998-06-03 | 1999-12-09 | Henkel Kgaa | Detergents and cleaning agents containing amylase and protease |
| EP3004313A1 (en) * | 2013-05-30 | 2016-04-13 | Novozymes A/S | Particulate enzyme composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2056108T3 (en) * | 1987-07-07 | 1994-10-01 | Hybrisens Ltd | USE OF ANTIBODY / ANTIGEN INTERACTIONS TO PROTECT OR MODULATE BIOLOGICAL ACTIVITY. |
| DK547589D0 (en) * | 1989-11-02 | 1989-11-02 | Novo Nordisk As | PROCEDURE FOR MAKING ORGANIC COMPOUNDS |
| JPH09503916A (en) * | 1993-10-08 | 1997-04-22 | ノボ ノルディスク アクティーゼルスカブ | Amylase variant |
-
1996
- 1996-08-16 AU AU69536/96A patent/AU6953696A/en not_active Abandoned
- 1996-08-16 WO PCT/US1996/013367 patent/WO1998007818A1/en active Application Filing
-
1997
- 1997-08-13 WO PCT/US1997/011543 patent/WO1998007822A1/en not_active Application Discontinuation
- 1997-08-13 BR BR9712079A patent/BR9712079A/en unknown
- 1997-08-13 EP EP97936030A patent/EP0918838A1/en not_active Withdrawn
- 1997-08-13 AU AU38798/97A patent/AU3879897A/en not_active Abandoned
- 1997-08-13 CA CA002263427A patent/CA2263427A1/en not_active Abandoned
- 1997-08-13 CN CN97198586.3A patent/CN1232491A/en active Pending
- 1997-08-15 AR ARP970103729A patent/AR009258A1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CA2263427A1 (en) | 1998-02-26 |
| EP0918838A1 (en) | 1999-06-02 |
| AR009258A1 (en) | 2000-04-12 |
| BR9712079A (en) | 1999-08-24 |
| AU3879897A (en) | 1998-03-06 |
| WO1998007818A1 (en) | 1998-02-26 |
| WO1998007822A1 (en) | 1998-02-26 |
| AU6953696A (en) | 1998-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1329659A (en) | Cloth-washing detergent and/or fabric care composition | |
| CN1321168A (en) | Laundry detergent and/or fabric care compositions comprising modified antimicrobial protein | |
| CN1094516C (en) | Detergent compositions containing specific lipolytic enzymes | |
| CN1306566A (en) | Detergent compsns. comprising mannanase and percarbonate | |
| CN1217742A (en) | Detergent compositions comprising improved amylases | |
| CN1172498A (en) | Detergent compositions containing lipase and protease | |
| CN1308672A (en) | Laundry detergent and/or fabric care compositions comprising a modified transferase | |
| CN1308638A (en) | Fabric care compositions comprising cellulose binding domains | |
| CN1374999A (en) | Detergent compositions comprising a retrograded starch degrading enzyme | |
| CN1382204A (en) | Detergent compositions comprising raw starch degrading enzyme | |
| CN1229428A (en) | Detergent compositions comprising improved amylase for dingy fabric clean-up | |
| CN1261400A (en) | Laundry and cleaning compositions containing xyloglucanase enzymes | |
| CN1340096A (en) | Detergent compositions comprising a pectatelyase and a specific surfactant system | |
| CN1216575A (en) | Cleaning compositions comprising endo-dextranase | |
| CN1391606A (en) | Mimic cellulose binding domain | |
| CN1233279A (en) | Detergent compositions comprising antibody controlled lipolytic activity | |
| CN1233278A (en) | Detergent compositions comprising antibody controlled enzymatic activity | |
| CN1225674A (en) | Detergent composition contg. odour removing composition | |
| CN1232491A (en) | Detergent compositions comprising antibody controlled amylolytic activity | |
| CN1268162A (en) | Cleaning compositions comprising an oxidoreductase | |
| CN1307635A (en) | Laundry detergent and/or fabric care composition comprising modified cellulase | |
| CN1233277A (en) | Detergent compositions comprising oxidation-reduction enzyme antibody | |
| CN1232492A (en) | Detergent compositions comprising antibody controlled cellulolytic activity | |
| CN1307634A (en) | Laundry detergent and/or fabric care composition comprising modified cellulase | |
| CN1233280A (en) | Detergent compositions comprising antibody controlled proteolytic activity |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |