CN1336952A - Detergent compositions comprising pectate lyase and a blench system - Google Patents
Detergent compositions comprising pectate lyase and a blench system Download PDFInfo
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- CN1336952A CN1336952A CN 00802789 CN00802789A CN1336952A CN 1336952 A CN1336952 A CN 1336952A CN 00802789 CN00802789 CN 00802789 CN 00802789 A CN00802789 A CN 00802789A CN 1336952 A CN1336952 A CN 1336952A
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Abstract
The present invention relates to detergent compositions comprising a pectate lyase, a bleaching system selected from: a combination of a peroxygen source and a colour-safe bleach booster, a metal bleach catalyst, and/or a diacyl peroxide; for providing superior cleaning performance, especially on plant-, dirt-based stains, highly coloured food soils/stains and body soils.
Description
Invention field
The present invention relates to detergent composition, it contains a kind of pectate lyase and a kind of bleach system, and bleach system is selected from binding substances, metal bleach catalyst and/or the diacyl peroxide of colour stable bleaching secondary accelerator and peroxygen source.
Background of invention
The performance of Betengent product identifies that by several factors these factors comprise the ability of removing dirt in the cleaning, and prevent the reppd ability of dirt, or destroys the ability of the dirt product on the article.Therefore, detergent composition comprises the combination of activeconstituents complexity now, with the particular requirement that realizes determining.Particularly, present detergent formulation generally comprises tensio-active agent and detergent enzyme cleaning to be provided and to safeguard the advantage of fabric.
Removal is the stain that basic dirt, muddy dirt and fruit grows by plant, trees, earth, is especially to trend towards one of clean up task the arduousest under the low cleaning temperature today.These stains typically comprise complicated main mixture based on carbohydrate and derivative thereof: fiber and cell wall constituent.The plant base dirt is again with amylose starch, sugar and their derivative.Usually the food dirt is difficult to remove from the matrix of polluting effectively.The removal of the dirt of dark or " drying " that is produced by fruit and/or vegetables juice is challenging especially.The example of the dirt that some is such comprises orange juice, Tomato juice, banana, mango or cabbage dirt.Really, the pectin polymkeric substance is the important composition of plant cell wall.Pectin is a kind of mixing-polysaccharide, and its main chain is made up of equal polygalacturonic acid of alternative (smooth region) and phammogalacturonane (crinosity zone).Smooth region is 1, and 4-connects the linear polymer of α-D-galacturonic acid.First-esterification to some extent on the carboxyl of this galacturonic acid residue has by the polygalacturonic acid fragment of complete first-esterification with non--irregular form usually.The matrix that general discovery contains the pectin stain can be fiber, tableware or hard surface.
In addition, also be the challenging especially dirt that to remove by dirt dark or " drying " as fruit and/or vegetables juice generation.These colored stains contain the dark compound based on carotinoid compounds or porphyrin, carotinoid compounds such as α-, β-and gamma carotene and Lyeopene and xanthein (zeaxanthin or capsanthin), porphyrin such as chlorophyll and and flavonoid pigment and dye component.The one group of natural flavone radical dye component in back contains based on pelargonidin, anthocyanidin, delphisine and their methyl ester with from the dark anthocyanin dyestuff and the pigment of xanthin.These compounds are origins of occur in the fruit most of orange, red, purple and Lan Se, and at whole berries, cherry, red and fruit in season black, natsudaidai, passion fruit, orange, lemon, apple, pears, pomegranate, red wild cabbage, red beet and spend in content abundant.The carotenoid dirt sources is from Radix Dauci Sativae and tomato and contain any converted products of these compositions, also has tropical fruit and Stigma Croci.
Washing the dish scope especially, these colored food dirts can be transferred to the washing soln from the article that pollute, and deposit to from washing soln on other article that just are being in the suds then again, or deposit to the inside of dishwasher again.Significantly, comprise by the article of food pollution that this food contains the dichroic dye molecule that has of suitable level, as when comprising tamato sauce and curry powder, this problem is noticeable when cleaning thing.
The applicant finds plastic article, and is in the cleaning zone of the dishwasher inside of being made by plastic material, very sensitive to stain/stain especially, especially stain/the stain to being caused by colored food dirt on the tableware.Said dirt can generate the stain of the extremely difficult removal of possibility with the plastics substrate surface interaction.
Many applicants' common pending trial european patent application proposes to solve the scheme that machine is washed coloured deposition of dye in the dish method.For example, EP 692 947 provides and has been used for the effective dye migration composite inhibiting that machine is washed the dish method.Said composition contains a kind of enzyme system, combines with some metal-based catalyst and can produce hydrogen peroxide.EP 740 521 has described use diacyl peroxide and four acyl peroxide SYNTHETIC OPTICAL WHITNER classes, but is used to suppress the migration of bleaching of food dirt, and improves from their ability of plastics substrate removal.
In addition, typically at the pillow place, the T-shirt, the every day of finding on collar and the socks " health " dirt complex nature, the challenge of thorough cleaning continuously washing composition has been proposed.These dirts are difficult to remove fully, partly are because the interaction of the pectin composition of original cell walls in the cotton fiber that they and the contained cotton of fabric contain, and resistates often accumulates in and causes dirty and flavescence look on the fabric.And the body fluid stain as bloodstain and menstrual fluid, often is to be difficult to remove from the place of making dirty effectively, especially after stain is worn out.Also find the health dirt in toilet and surface, kitchen every day, as bathtub, water closet and tableware.
This area described widely be used to bleach these plants-, dirt base stain, the dark stain and the bleaching composition of dirt and health dirt.Suitable SYNTHETIC OPTICAL WHITNER normally discharges the peralcohol of hydrogen peroxide in the aqueous solution, as peroxidation hydrate, perborate, percarbonate, perpyrophosphate, persilicate, urea peroxide etc.Understood the application of using organic bleach-activating agent or peracid precursors can improve these peralcohol.Also understand these bleaching compositions and can remove various stains effectively.Recently, contain the product of bleaching catalyst, particularly the manganese bleaching catalyst is paid close attention to very much.
In addition, the oxygen bleaching agent popular that becomes in the product that family and individual use in recent years is to make things convenient for the removal of stain and dirt.The cleaning of their stain-removal, slovenly fabric, bleach and the sanitary measure characteristic aspect need SYNTHETIC OPTICAL WHITNER especially.Find that oxygen bleaching agent is especially in laundry service product such as washing composition, liked in washing the dish product automatically and in hard surface cleaner.Yet oxygen bleaching agent is restricted slightly on its efficient.Some shortcomings that often run into comprise the rubber hose that fabric color damage and laundry utensil damage, especially these utensils may comprise.In addition, oxygen bleaching agent tends to the temperature speed dependence very much.Like this, use their solution cold more, the efficient of bleaching action is low more.For making in the solution oxygen bleaching agent effective, typically require temperature to surpass 600 ℃.
Under the low temperature water condition, carried out the test of development bleach system.People's such as Madison United States Patent (USP) 5,360,568, people's such as Madison United States Patent (USP) 5,360,569 and people's such as Madison United States Patent (USP) 5,370,826 all relate to positively charged season inferior amine salt makes the catalyzer of peralcohol transfer activity oxygen, and declares to have increased in comprising the water temp scope of low temperature more the activity of peralcohol.Yet these positively charged season inferior amine salts are also not exclusively satisfied in the laundry service bleaching is used.Particularly disclosed positively charged season inferior amine salt combines with peralcohol in these documents, causes that the level of fabric color damage is unacceptable.
Therefore, still need particularly to plant-, dirt base stain, dark stain and dirt and health dirt can provide the detergent composition of effective bleaching.When providing the color of improvement-security profile and/or prevent that tableware from being got stain/stain by dark composition, this requirement is when lower water temp even stronger.Detergent composition of the present invention meets these requirements, and said composition contains pectate lyase and bleach system, and bleach system is selected from: bleaching secondary accelerator and peroxygen source, metal bleach catalyst and/or diacyl peroxide a kind of composition.
Be surprisingly found out that selected bleach system can improve the cleaning efficiency of pectate lyase the biglyyest.Also be surprised to find because the synergism of selected bleach system, the detergent composition that contains pectate lyase and selected bleach system provides good cleaning capacity, this bleach system provides cleaning, stain to remove and safeguard in the whiteness of laundry scope, and the pectate lyase degrade the pectin composition of these dirts and/or in the laundry scope may with pectin fraction on these dirt bonded fabrics.These selected bleach system-enzyme mixed systems have given significant cleaning effect, especially to food coloring stain and health dirt.And when the composite formula manufacturing of safeguarding by laundry and/or fabric, the present composition also provides the synergic whiteness to safeguard.
Do not wish to be bound by theory, think that natural pectin absorbs and maintenance dirt residue, particularly dark dirt composition, this natural pectin is in a lot of common fruits and vegetables base dirt and in the former wall of cotton fiber discovery is arranged all.Removing pectin fraction with the pectate lyase makes these coloured objects be exposed to bleach system.Think that synergism is because this bleach system makes the food stain that be difficult for to remove and the color component decolouring of health dirt, and pectate lyase degrade this dirt and/or the pectin composition in the laundry scope.The pectin composition of this fabric combines with these dirts or interacts, and makes that said dirt is difficult to remove.
Be surprisingly found out that particularly the present invention contains the detergent composition of diacyl peroxide; provide effective stain to remove; especially Shen Se stain and dirt, special stain and dirt on plastic ware, and prevent that further tableware from being got stain/stain by the composition of dark color.In addition, also be surprisingly found out that the combination of the bleaching secondary accelerator of pectate lyase and selected bleach system,, improved cleaning capacity, especially the cleaning capacity under low wash temperature by improving the overall efficiency of bleach system.Add the bleaching secondary accelerator and make oxygen-Ji bleach system under low wash temperature, to bleach coloured object of these exposures more up hill and dale, thereby cause both improving the removal of stain, improve whiteness again.
Having understood when being used to clean with clean operation pectin degrading enzyme can provide the benefit of removal dirt/stain, and plant and the fruit based stain of removing broad range and the health dirt clean-up performance that improves detergent composition particularly are provided.Here pectin degrading enzyme has been meant any enzyme that destroys pectin substance and the effect of pectin related substance.Pectin degrading enzyme can be classified according to they preferential substrates, and substrate is divided into the pectin of height methyl-esterification or the pectin and the polygalacturonic acid (pectic acid) of low methyl-esterification, and classifies according to their reaction mechanisms, is divided into β-elimination or hydrolysis.Pectin degrading enzyme can mainly be interior-effect type, and the optional position cuts off the mixture that polymkeric substance provides oligomer in chain; Or they can be outer-effect types, from an end attack of polymkeric substance, generate monomer or dimer.Comprise several pectinase activities that act on the pectin smooth region in the classification of the enzyme that provides by enzyme nomenclature (1992), for example pectate lyase (EC 4.2.2.2), pectin lyase (EC 4.2.2.10), polygalacturonase (EC 3.2.1.15), circumscribed-polygalacturonase (EC 3.2.1.67), circumscribed-the polygalacturonic acid lyase (EC 4.2.2.9) and circumscribed-poly--α galacturonic acid Glycosylase (EC 3.2.1.82).Pectin degrading enzyme is the natural mixture of above-mentioned enzymic activity.
Various types of pectin degrading enzymes all have Substratspezifitaet, the activity and stable of unique types under different hardness, pH, temperature, tensio-active agent and other detergent ingredients matrix conditions.Pectin degrading enzyme is oriented to particularly plant cell wall of depolymerized pectin material clearly.Particularly, the pectate lyase is according to directed α-D-(1, the 4)-glycosidic link that divides in depolymerization-D-galacturonic acid of mechanism of β-elimination.These pectate lyase also help removal to contain pectin substance and other composition blended stain/dirts.Yet, may hinder the accessibility of pectin substance to the insensitive dirt/stain of pectate lyase such as non--pectin carbohydrate, lipid, protein and their derivative, and need stronger detergent ingredients enzyme.
This area has recognized that uses pectin degrading enzyme in washing composition.Recognize that also (US 4,710,313-J60196724) into the cleaning contact lenses uses polygalacturonase.Having narrated the enzyme that pectinase activity is arranged in DE 36 35 427 increases washing composition and removes that inorganic foulants is the ability of mud on the clothes, this laundry does not have fibre-tendering and nondiscoloration and allows to use zeolite and polycarbonate washing assistant, and this washing assistant disperses the ability of inorganic materials to be lower than phosphoric acid salt.WO95/25790 recognizes in detergent formulation, in particular for the prescription that is used for doing washing, washing dish and household cleaning operational design, uses the benefit of polygalacturonase.JP 60226599 has described the detergent composition that contains conventional washing composition activeconstituents and cellulase and lytic enzyme, cellulase and lytic enzyme such as hemicellulase, polygalacturonase, amylase or proteolytic enzyme.The combination of declaring cellulase and lytic enzyme provides the effect of the good inorganic filth of washing with the activity of enzyme.WO95/09909 has described a kind of preparation of enzyme, and this kind of enzyme contains the modifying enzyme that is selected from amylase, lipase, oxydo-reductase, polygalacturonase or hemicellulase; Because chemically modified or aminoacid replacement, the surfactivity of resulting alkaline pI and/or increase has made improved performance that this modifying enzyme has.Use polygalacturonase and/or pectin decomposing enzyme and/or half-cellulolytic enzyme and/or lipolytic enzyme of modifying in the paper industry easily, reach laundry service or wash amylase and/or the lipase that application is modified in the dish.
Particularly, the pectate lyase can never belong to the bacterial clone of class, bacterium such as Erwinia, pseudomonas, Klebsiella, streptomycete, Penicillium notatum, bacterioide, thermophilic unit cell daughter bacteria, Fusarium, Aspergillus and Xanthomonas campestris together.Report is arranged by subtilis people such as ((1993) FEBS 335:319-326) Nasser and genus bacillus bacterial classification YA-14 people such as ((1994) Biosci.Biotech.Biochem.58:947-949) Kim clone's pectate lyase.Bibliographical information at pH8～the highest pectate lyase of 10 scope activity, these enzymes are by bacillus pumilus (Dave and Vaughn (1971) J.Bacteriol.108:166-174), poly-viscosity bacillus (Nagel and Vaughn (1961) Arch.Biochem.Biophys.93:344-352), bacillus stearothermophilus (Karbassi and Vaughn (1980) Can.J.Microbiol.26:377-384), genus bacillus bacterial classification (Hasegawa and Nagel (1966) J.Food Sci.31:838-845) and genus bacillus bacterial classification RK9 (Kelly and Fogarty (1978) Can.J.30 Microbiol.24:1164-1172) produce.WO 98/45393 discloses the detergent composition that contains protopectinase the dirt of many mud has been had outstanding detergent action.
Diacyl peroxide is widely used as polymerization starter, solidifying agent and SYNTHETIC OPTICAL WHITNER.United States Patent (USP) 5,334,326 that described a kind of liquid or pasty states disperse thing, and it contains the alkyl benzoate of two aroly peroxides, a kind of liquid and the water of 0～40 weight %, and wherein the alkyl of alkyl benzoate has 8～12 carbon atoms.Said two aroly peroxides are 0.3: 1～7: 1 to the ratio of said alkyl benzoate.United States Patent (USP) 4,255,277 described a kind of non--isolated catalyzer paste, it contains diacyl peroxide, the water than small proportion, fine dispersive lime carbonate, the quantity of lime carbonate will be enough to prevent the component physical sepn of composition.United States Patent (USP) has been described the SOLID ORGANIC peroxide compositions, and it contains SOLID ORGANIC superoxide such as dibenzoyl superoxide and a kind of liquid and the solid desensitizing agent mixture of 50～70 weight %.United States Patent (USP) 3,723,336 disclose a kind of non--release compositions that 20～60 parts of dibenzoyl superoxide are arranged.WO96/27586 relates to the solid diacyl organic peroxide prescription of liquid or paste form, and it has improved thermostability.WO95/33817 has described a kind of wax of packing into-capsular particulate with core particle or core particle aggregate, and core particle is selected from the organic peracid of the tensio-active agent of 0.01～5 weight %, diacyl peroxide, inorganic peroxy compounds, bleaching catalyst, peroxide bleaching precursor and/or their mixture.The bleaching composition that GB 1 538 477 relates to contains tensio-active agent, builder salt and SYNTHETIC OPTICAL WHITNER, and it is ROOR that SYNTHETIC OPTICAL WHITNER contains chemical general formula
1Diacyl peroxide, wherein R is the phenyl-diformyl base, and R
1It is acyl group.The bleaching composition that EP 257 700 relates to contains peralcohol and at least two kinds of mixtures that were selected from the acid blanching precursor.
Metal bleach catalyst is known in the de-sludging field.Present technology comprises the laundry composition that WO98/36403 describes, and it contains the transition metal bleach catalyzer, and this catalyzer comprises the complex compound of transition metal and the large-scale many ring parts of intersection-bridge-type.The laundry composition that WO98/39405 relates to contains bleach-activating agent and/or organic percarboxylic acids and transition metal bleach catalyzer, and catalyzer contains the complex compound of transition metal and the large-scale many ring parts of intersection-bridge-type.The bleaching composition that WO97/36991 relates to comprises the amino tricarboxylic acid of containing metal-bleaching catalyst, oxygen-release bleach system and a kind of special chemical formula.The disclosed bleaching composition of WO97/34985 comprises containing metal-bleaching catalyst, oxygen-release bleach system and cellulase.WO97/29174 has described the bleaching catalyst particulate that is used for detergent composition.The dish composition of washing automatically that WO97/22681 relates to contains metal bleach catalyst, hydrogen peroxide cource, phosphate builders and washes the dish composition.
Yet; the synergy of never recognizing pectate lyase and selected bleach system in the past is in conjunction with making detergent composition that good clean-up performance be arranged, and selected bleach system is selected from binding substances, metal catalyst and/or the diacyl peroxide of bleaching secondary accelerator and peroxygen source.
Summary of the invention
The present invention relates to laundry, wash dish or hard-surface cleaning detergent composition, it contains pectate lyase and bleach system, and bleach system is selected from: bleaching secondary accelerator and peroxygen source composition, metal bleach catalyst and or diacyl peroxide.
These compositions especially to plant-, dirt-Ji stain, dark food dirt/stain and health dirt provide good clean-up performance.Such scouring agent composition also provides good whiteness to safeguard.In addition, these contain the composition of color-safe secondary accelerator, when improved color-safety performance is provided, also provide clean-up performance good under lower water temp.In addition, the composition that these contain diacyl peroxide provides the effective especially dark stain on plastic ware and the removal of dirt, and prevents that further tableware from being formed stain/stain by dark composition.Detailed Description Of The Invention
Detergent composition of the present invention contains pectate lyase and the bleach system as fundamental, and bleach system is selected from: bleaching secondary accelerator and peroxygen source composition, metal bleach catalyst and/or diacyl peroxide.
The all kinds pectin degrading enzyme all has Substratspezifitaet, the activity and stable of unique types under different hardness, pH, temperature, tensio-active agent and other detergent ingredients matrix conditions.Pectin degrading enzyme is oriented to particularly plant cell wall of depolymerized pectin material clearly.Particularly, α-(1, the 4)-glycosidic link of the polygalacturonic acid of finding in the pectate lyase decompose pectin material forms two keys between C4 and C5.The pectate lyase also helps to remove the mixing stain/dirt that contains pectin substance and other compositions.Yet, to the insensitive dirt/stain of pectate lyase such as non--pectin carbohydrate, lipid, protein and their derivative or the dark material related with pectin, may hinder the accessibility of pectin substance, and need stronger detergent ingredients enzyme.
Be surprisingly found out that the selected SYNTHETIC OPTICAL WHITNER of the present invention can improve the cleaning efficiency of pectate lyase to greatest extent.Selected bleach system is that the known stain of good cleaning and dark stain that can provide is removed, and in the whiteness nursing and the especially removal of fats/oils stain of laundry service and/or fabric maintenance span.Do not wish to be retrained, think that the decomposition of pectate lyase combines the dirt of color object and chromophore and the pectin fraction of stain by theory.The enzyme liberating of pectin composition makes color object and chromophore be exposed to bleach system, and they are removed effectively.Find that this combination causes the performance synergism in dirt and stain cleaning, especially to colored food stain/dirt and health dirt.
Particularly well known reduction clean-up performance along with temperature also reduces.Performance this point to the removal of pectin-Ji stain/dirt and oxygen bleaching system is especially correct.Do not wish to be retrained by theory, think that the pectate lyase is by the clean-up performance under the catalytic hydrolysis pectin help major tuneup low temperature, pectin is at a lot of dirt/stains with in clothes-washing environment, all have discovery in the former wall of residual cotton fiber, it can capture and keep coloured object in its surface.The hydrolysis of pectin makes the easier removal dirt of remaining detergent ingredients.Improve to remove the pectin composition of high chroma food stain and from the pectin of cotton fiber, make the chromophore of dirt be exposed to oxygen bleaching system in the detergent formulation.The bleaching secondary accelerator has improved the low temperature performance of oxygen bleaching system.In the detergent formulation that contains the oxygen bleaching system, the combination of pectate lyase and bleaching secondary accelerator provides effectively and has removed the method for high chroma food dirt from tableware and fabric face, and removes the method for the health dirt of fabric face effectively in the laundry scope.Pectate lyase enzyme
The fundamental of detergent composition of the present invention is a pectate lyase enzyme.
The pectate lyase is listed in EC4.2.2.2 in the enzyme classification that enzyme nomenclature (1992) provides.Said enzyme is the α-(1 of the galacturonic acid that exists in the known decompose pectin material, 4)-glycosidic link, and between C4 and C5, form two keys, substantially the pectin degrading activity that does not contain other, promptly have other pectin degrading enzymic activitys by weight less than 25%, preferably, be more preferably less than 5% enzyme compound less than 15%.
Pectate lyase clone belongs to class from different bacteriums, and bacterium belongs to class such as Erwinia, pseudomonas, Klebsiella, streptomycete, Penicillium notatum, bacterioide, thermophilic unit cell daughter bacteria, sickle spore bacterium, Aspergillus and Xanthomonas campestris.There is report narration to clone the pectate lyase by subtilis people such as ((1993) FEBS335:319-326) Nasser and genus bacillus bacterial classification YA-14 people such as ((1994) Biosci.Biotech.Biochem.58:947-949) Kim.Publication has reported that at the highest pectate lyase of pH 8～10 scope activity these enzymes are by bacillus pumilus (Dave and Vaughn (1971) J.Bacteriol.108:166-174), poly-viscosity bacillus (Nagel and Vaughn (1961) Arch.Biochem.Biophys.93:344-352), bacillus stearothermophilus (Karbassi and Vaughn (1980) Can.J.Microbiol.26:377-384), genus bacillus bacterial classification (Hasegawa and Nagel (1966) J.Food Sci.31:838-845) and genus bacillus bacterial classification RK9 (Kelly and Fogarty (1978) Can.J.30 Microbiol.24:1164-1172) produce.WO 98/45393 discloses the detergent composition that contains protopectinase the dirt of many mud has been had outstanding detergent action.
Described in WO98/45393, further being suitable for pectate lyase of the present invention has protopectinase, when using polygalacturonic acid to make substrate the pH of its optimum response 7.0 or more than; And the pectate lyase, it has aminoacid sequence is SEQ no 1 among the EP 870 843, perhaps have one or more amino acid deleted, be increased or substituted aminoacid sequence.
The preferred pectate lyase of in the common co-pending application PCT/DK98/00515 in the world, narrating, this application was submitted on November 24th, 1998, and open with WO 99/27084:
-a kind of pectate lyase, the amino acid primary sequence that it contains is by seven (7) individual amino acid
Residue is formed, and has following sequence: Asn-Leu-Asn-Ser-Arg-Val-Pro
(NLNSRVP)；
-a kind of pectate lyase, it is:
I) peptide species is given birth to by sticking agar genus bacillus NCIMB 40482 or DSM 8721
Produce, or by a kind of its 16SrDNA sequence and sticking agar genus bacillus DSM 8721 tools
The genus bacillus bacterial classification production of at least 99% homology is arranged, or
An ii) peptide species, it contains among the PCT/DK98/00515 SEQ ID NO:2 at 27-
The aminoacid sequence of 359 demonstrations, or
Iii) by i) or the ii) analogue of polypeptide of definition, wherein with said polypeptide have to
Few 45% homology, or
Iv) be substituted, delete, increase by one or several amino acid by said polypeptide and
Deutero-is just at 240 arginine with randomly in addition at 245 smart ammonia
Acid keeps, and this polypeptides derived and said polypeptide have at least 42% same
Source property, or
V) immunology is arranged with the polyclonal antibody that produces with respect to the purified form of said polypeptide
Reaction;
-a kind of pectate lyase, it is:
I) peptide species has by Bacillus licheniformis ATCC 14580 or by a kind of institute
16S rDNA sequence and Bacillus licheniformis ATCC 14580 have at least 99% with
The genus bacillus kind of source property is produced, or
An ii) peptide species, it contains among the PCT/DK98/00515 SEQ ID NO:4 at 28-341
The aminoacid sequence that the position shows, or
Iii) by i) or the ii) analogue of polypeptide of definition, wherein with said polypeptide have to
Few 45% homology, or
Iv) be substituted, delete, increase by one or several amino acid by said polypeptide and
Derive, just at 233 arginine with randomly in addition at 238 arginine
Keep, and this polypeptides derived and said polypeptide have at least 42% homology
The property, or
V) immunological response is arranged with the polyclonal antibody that produces with respect to the purified form of said polypeptide;
-a kind of pectate lyase, it is:
I) peptide species is produced by a kind of genus bacillus bacterial classification, and this genus bacillus kind has
The 16S rDNA sequence of SEQ ID NO:14 among the PCT/DK98/00515; Or by one
Kind of bacillus kind produces, the 16S rDNA sequence that this genus bacillus kind has with
SEQ ID NO:14 has the homology more than 97.3% among the PCT/DK98/00515,
Or
An ii) peptide species, the SEQ ID NO:6 that it contains among the PCT/DK98/00515 exists
The aminoacid sequence that the 181-509 position shows, or
Iii) by i) analogue of polypeptide of definition, wherein have at least 50% with said polypeptide
Homology, or
Iv) be substituted, delete, increase by one or several amino acid by said polypeptide and
Derive, just at 390 arginine with randomly in addition at 395 arginine
Keep, and this polypeptides derived and said polypeptide have at least 44% homology
The property, or
V) the polyclonal antibody that produces with the said polypeptide of purified form has immunological response;-a kind of pectate lyase, it is:
I) peptide species is produced by bacterial classification salt tolerant genus bacillus, or
An ii) peptide species, it contains among the PCT/DK98/00515 SEQ ID NO:8 at 42-348
The aminoacid sequence that the position shows, or
Iii) by i) or the ii) analogue of polypeptide of definition, wherein with said polypeptide have to
Few 45% homology, or
Iv) be substituted, delete, increase by one or several amino acid by said polypeptide and
Derive, as long as at 240 arginine with randomly in addition at 245 arginine
Keep, and this polypeptides derived and said polypeptide have at least 40% homology
The property, or
V) the polyclonal antibody that produces with the said polypeptide of purified form has immunological response;-a kind of pectate lyase, it is:
I) peptide species is produced by a kind of bacillus kind, and this genus bacillus kind has
The 16SrDNA sequence of SEQ ID NO:13 among the PCT/DK98/00515, or by a kind of
The genus bacillus kind is produced, the 16S rDNA sequence that this genus bacillus kind has with
SEQ ID NO:13 has the homology more than 98.1% among the PCT/DK98/00515,
Or
An ii) peptide species, it contains among the PCT/DK98/00515 SEQ ID NO:10 at 25-
The aminoacid sequence of 335 demonstrations, or
Iii) by i) analogue of polypeptide of definition, or itself and said polypeptide have at least 45%
Homology, or
Iv) be substituted, delete, increase by one or several amino acid by said polypeptide and
Derive, just at 227 arginine with randomly in addition at 232 arginine
Keep, and this polypeptides derived and said polypeptide have at least 41% homology
The property, or
V) the polyclonal antibody that produces with the said polypeptide of purified form has immunological response.
The pectate lyase of same preferred common co-pending application PCT/DK98/00514 narration in the world, this application was submitted on November 24th, 1998, and published with WO 99/27083, and this enzyme is:
I) peptide species is produced by Bacillus licheniformis ATCC 14580, or
An ii) peptide species, it contains among the PCT/DK98/00514 SEQ ID NO:4 at 28-221
The aminoacid sequence that the position shows, or
Iii) by i) or the ii) analogue of polypeptide of definition, it and said polypeptide have at least 60%
Homology, or
Iv) be substituted, delete, increase by one or several amino acid by said polypeptide and
Deriving, is to protect at 133 and 155 Methionin and the arginine that reaches at 158 just
Stay, and SEQ ID NO:4 position among this polypeptides derived and the PCT/DK98/00514
Put 60-158 and have at least 66% homology, or
V) the polyclonal antibody with the said polypeptide generation of purified form has immunological response.
The pectate lyase that more preferably o'clock has optimum activity in the present invention in pH＞7.0, they derive from streptomyces fradiae, nitrated spiral shell streptomycete, carrot soft rot Erwinia, the spherule genus bacillus, brown is thermophilic unit cell daughter bacteria, Solanaceae pseudomonas, bacteroides thetaiotaomicron, fusarium solanae fungi, xanthomonas campestris, sticking agar genus bacillus and/or Bacillus licheniformis.
For the most preferred pectate lyase of target of the present invention be the pectate lyase of self-adhesion agar genus bacillus NCIMB 40482 or DSM 8721.
Mix the level of pectate lyase in the detergent composition of the present invention and count preferred 0.0001%～2%, more preferably 0.0005%～0.1%, most preferably 0.001%～0.02% pure enzyme with composition weight.
Pectate lyase of the present invention except the enzyme core contains the catalysis region, also can contain cellulose binding domain (CBD), and the cellulose binding domain of enzyme operationally is connected with enzyme core (catalytic activity zone).Cellulose binding domain (CBD) can exist with the integral part of the enzyme that is encoded, also the CBD that originates from addition can be introduced in the enzyme, cause a kind of enzyme to mix kind like this.In context, the implication of term " Mierocrystalline cellulose-calmodulin binding domain CaM " is understood that the contained definition in " Mierocrystalline cellulose-calmodulin binding domain CaM: classification and character " by people such as Peter Tomme, this article is published in " insoluble carbohydrase falls and subtracts " book, this book is edited by John N.Saddler and Michael H.Penner, American Chemical Society's discussion series was published in 618,1996 years.This definition will be included into 10 classes (I-X) more than 120 kinds of Mierocrystalline cellulose-calmodulin binding domain CaMs, and prove and find CBD in plurality of enzymes, these enzymes such as cellulase, zytase, mannase, arabinofuranosidase, acetylase and chitinase.In algae, also find CBD,, consult in the books that the people drew such as Tomme as the polysaccharide-conjugated protein of non--hydrolysis in the red algae Porphyra laver.Yet most of CBD are from cellulase and zytase.At proteinic N and C end or its inner CBD that finds.This area has been understood enzyme and has been mixed kind, consult as WO 90/00609 and WC 95/16782, it is that DNA construct is converted into host cell that enzyme mixes the preparation of planting, this DNA construct contains the fragment of at least one dna encoding Mierocrystalline cellulose-calmodulin binding domain CaM, it combines with the pectate lyase of dna sequence encoding, this combination can have or not be with the connection portion, makes the host cell growth to express the gene that merges.Enzyme mixes kind available following chemical formula to be described: CBD-MR-X wherein CBD be at least with the N-end or the C-end regions of cellulose binding domain amino acid sequence corresponding; MR is region intermediate (connection portion), and can be a chemical bond, or a weak point linking group, this group preferably approximately 2～about 100 carbon atoms, more preferably 2～40 carbon atoms, or preferably approximately 2～about 100 amino acid, more preferably 2～40 amino acid; And X is the N-end or the C-end regions of pectate lyase of the present invention.
Above-mentioned enzyme can be from any suitable source, as originating with zymic of vegetables, animal, bacterium, fungi.This external source can be have a liking for temperature or have a liking for extreme environment (psychrophilic, suitable cold, thermophilic, have a liking for pressure, that have a liking for alkali, have a liking for acid, happiness salt etc.).Can use the purifying of these enzymes or not-purified form.Now, in order to make their effectiveness of performance optimizings in detergent composition of the present invention, convention is to modify the enzyme of wild-type by protein/gene engineering usually.For example, design variable makes enzyme and the consistency of these composition components of running into usually increases.Perhaps design variable is fit to special cleaning applications so that repair best pH, bleaching or sequestrant stability, the catalytic activity etc. of this enzyme variants.
Particularly, should concentrate on the amino acid to oxidation-sensitive the bleach stability attention, and should concentrate on the surface charge the surfactant compatibility attention.Can revise the iso-electric point of these enzymes by replacing some charged amino acid, can help to improve consistency with anion surfactant as increasing iso-electric point.Increase sequestrant stability by creating other salt bridge and reinforcement metal binding site, further improve the stability of enzyme.Bleach system
Detergent composition of the present invention further contains bleach system as second kind of fundamental, and bleach system is selected from: composition, metal bleach catalyst and/or the diacyl peroxide of bleaching secondary accelerator and peroxygen source.The diacyl peroxide bleach system
The bleach system that the present composition comprises can be diacyl peroxide (or DAP).Said diacyl peroxide can be a liquid and preferably mix liquid detergent composition with this form, or said diacyl peroxide can be contained in the particulate and preferably adds in the granular detergent composition with this form.
DAP can be selected from two aliphatics superoxide, two aromatic series superoxide, aliphatic-aromatic superoxide or their mixture, and has chemical general formula:
R-C (O)-O-O-(O) C-R
1Wherein, R and R
1Can be identical or different, be selected from the aliphatics or the aromatic group of 6～20 carbon atoms.
DAP of the present invention is selected from two aliphatics superoxide, two aromatic series superoxide, aliphatic-aromatic superoxide or their mixture.
As R and/or R
1Be aliphatic group, this group can be a side chain, but preferred straight chain.The preferred aliphat group has 8～14 carbon atoms, most preferably 10～twelve carbon atoms.Particularly preferred two aliphatics superoxide comprise two sim peroxides, didecyl acyl peroxide, two bay acyl peroxides, two cardamom acyl peroxides or their mixture.Two bay acyl peroxides can adopt the commodity of Akzo Nobel company commodity Laurox by name, and the lauroyl superoxide can adopt the commodity of Akzo Nobel company commodity Perkadox SE10 by name.
Preferred DAP is the aliphatic-aromatic superoxide, and wherein any one is that aliphatics and another are aromatic series among R or the R '.In this class, the preferred benzoyl of aromatic series part.In a selective embodiment, the fragrant same clan can be the benzoyl that replaces, and wherein substituting group preferably has the alkyl of 1～20 carbon atom.Aliphatic portion preferably contains 8～14 carbon atoms, more preferably 10～12 carbon atoms, although and this group can be side chain, straight chain preferably.
The suitable example of diacyl peroxide is dibenzoyl superoxide, benzoyl glutaryl-superoxide, benzoyl succinyl superoxide, two-(2-methyl benzoyl) superoxide, hexichol diformyl superoxide, two sim peroxides, didecyl acyl peroxide, two bay acyl peroxides, two cardamom acyl peroxides, benzoyl lauroyl superoxide, the benzoyl lauroyl superoxide of replacement and their mixture.Preferred diacyl peroxide is that dibenzoyl superoxide, hexichol diformyl superoxide and their mixture and preferred diacyl peroxide are the dibenzoyl superoxide.
More preferably two bay acyl peroxides, dibenzoyl superoxide and/or their mixture in the present invention.
In example; DAP is included in the detergent composition of the present invention with particulate form; this particulate calculates by the weight of said particulate, contains 1～80% water-insoluble diacyl peroxide and 0.01%～95% stabilization additives, and diacyl peroxide does not dissolve in additive.Suitable example additives is inorganic salt, transition metal chelator, antioxidant, tackiness agent, coating-forming agent and/or their mixture.
Term " diacyl peroxide does not dissolve " the definition here is meant that this diacyl peroxide does not dissolve under particulate processing conditions and/or washing composition condition of storage in stabilization additives.Term " water-insoluble " the definition here is meant limited water-soluble, promptly less than 1%, preferably water-soluble less than 0.5%.Term " stabilization additives " the definition here is meant a kind of compound or multiple compound; prevent that diacyl peroxide from being decomposed by other compositions; other compositions are diacyl peroxide dissolved composition therein especially, and when in product, storing diacyl peroxide will with the composition of its reaction.
Said particulate provides stability in storage, and the protection diacyl peroxide in composition not with other interaction between component, and along with the time in the past and decomposed.In the particulate stabilization additives be particulate weight about 0.1%～about 95%, be preferably about 10%～about 95%, more preferably about stabilization additives of 40%～about 95%.
Preferred stabilization additives temperature or be lower than 100 °F, preferred 120 °F be difficult for down with composition in other compositions miscible.In an especially preferred embodiment, stablizer will be dissolved in washing soln.
Inorganic salt as stabilization additives include but not limited to alkali-metal vitriol, citric acid and boric acid and their salt, alkaline carbonate, supercarbonate and silicate and their mixture.Preferred inorganic salt are sodium sulfate and citric acid, because their right and wrong-alkalescence, prevented the alkaline hydrolysis of product.
Tackiness agent and coating-forming agent include but not limited to the undissolved therein water-soluble polymers of some diacyl peroxide, have the ethoxylation C of enough oxyethyl group groups for preventing the diacyl peroxide dissolving
16-C
20Alcohols, aliphatic fatty acid class, aliphatics aliphatic alcohols, Star Dri 5, dextrin, starch, gel, fusing point be higher than 100 polyoxyethylene glycol, polyvinyl alcohol and sorbyl alcohol.Polymkeric substance comprises that molecular-weight average is about 1,000～about 10,000 polyacrylic ester and acrylate/maleic acid ester or acrylate/fumarate multipolymer, the molecular-weight average of multipolymer is about 2,000～about 80,000, and acrylate is about 30: 1～about 1: 2 to maleic acid ester or the segmental ratio of fumarate.With undersaturated list-and the dicarboxylic ester monomer mixture be that the example of based copolymers is open in the european patent application of publishing December 15 nineteen eighty-two 66,915, this patent is incorporated herein by reference.Other suitable multipolymers are acrylate copolymers of modifying, and at United States Patent (USP) 4,530, open in 766 and 5,084,535, the two is all incorporated herein by reference as.
Spendable transition metal chelator is selected from sodium, potassium, lithium, ammonium and the substituted ammonium salt of polyacetic acid salt and multi-carboxy acid salt washing agent such as ethylenediamine tetraacetic acid (EDTA), ethylenediamine disuccinic acid (S especially, the S-type), nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxygen di-succsinic acid, the carboxymethyl oxysuccinic acid, mellitic acid, benzene polycarboxylic acid's sodium salt; Nitrilo three (methylene phosphonic acid), diethylidene three nitrilos five (methylene phosphonic acid), 1-hydroxy ethylene-1, the 1-di 2 ethylhexyl phosphonic acid, other phosphine acid salt chelators (as derive from Monsanto Dequest series product), ethylidene-N, N '-two (neighbour-hydroxy phenyl glycine), pyridine dicarboxylic acid and their mixture.
Antioxidant (free radical scavenger, free-radical scavengers or free free radical inhibitors) also can be the stabilization additives that suits.Even these compounds also make reaction slow down or stop existing in a small amount.It is considered herein that antioxidant will catch or remove because the free radical that the peroxide bridge thermolysis forms.This will prevent that free radical from further reacting or diffuse to form other free radical (from-accelerate decomposition).Because the quantity that these materials use is very little, roughly can not damage all round properties of detergent composition in particulate.Suitable antioxidant includes but not limited to citric acid, phosphoric acid, BHT, BHA, alpha-tocopherol, Irganox series C (Ciba Giegy), Tenox series (Kodax) and their mixture.
Can point out that stabilization additives listed above not only is used as stabilization additives in Betengent product, other benefits (be pH control, carbonate/silicate is disperseed) also may be provided.Therefore these compositions also can be added respectively by particulate, and for example, agglomerate form of the present invention can use here the aqueous solution of polyacrylic ester discussed above to make agglomerate as liquid-containing binder.
It is about 400 μ m～about 1000 μ m, more preferably about 600 μ m～about 800 μ m that formed diacyl peroxide particulate preferably has average particle size, only is less than 1% diacyl peroxide particulate greater than 1180 μ m (Tyler 14 sieve meshes) be less than 1% particulate and be less than or equal to 214 μ m (Tyler 65 sieve meshes).
Typically, diacyl peroxide by composition weight meter with 0.01%～20%, preferred 0.5%～10%, more preferably 0.2%～3% level joins in the detergent composition of the present invention.When diacyl peroxide is impregnated in particulate, contain 0.1%～30% by the composition weight meter present composition, preferred 1%～15%, more preferably 1.5%～10% diacyl peroxide particulate.
As narrating in EP 257 700, prefabricated diacyl peroxide is also within the scope that the present invention considers.Suitable also just like at United States Patent (USP) 5,334, narration has two aroly peroxides that improved chemical stability in 326, and in WO 96/27856 disclosed solid diacyl organic peroxide dispersions.Metal bleach catalyst
The bleach system that is included in the detergent composition of the present invention can have metal bleach catalyst.As mentioned below, when detergent composition of the present invention contains metal bleach catalyst, will preferably contain peroxygen source (being also referred to as oxygen source or oxygen bleaching source), and be illustrated with bleach system.
Suitable bleaching catalyst type is the catalyzer that contains heavy metal cation, assistant metal positively charged ion and sequestrant, and this heavy metal cation has the bleach catalyst activity that defines, as copper, iron positively charged ion; This assistant metal positively charged ion has seldom or does not have the bleach catalyst activity, as zinc or aluminium cations; Sequestrant has defined stability constant, particularly ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and their water-dissolubility salt to catalytic and auxiliary metallic cation.United States Patent (USP) 4,430,243 disclose such catalyzer.
Preferred bleaching catalyst type comprises United States Patent (USP) 5,246,621 and United States Patent (USP) 5,244,594 in disclosed manganese-base complex.These catalyzer preferred examples comprise Mn
IV 2(u-O)
3(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2-(P
F6)
2, Mn
III 2(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2-(ClO
4)
2, Mn
IV 4(u-O)
6(1,4, the 7-7-triazacyclononane)
4-(ClO
4)
2, Mn
IIIMn
IV 4(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2-(ClO
4)
3With their mixture.In european patent application publication number 549,272, stating of other.Other parts of suitable this purposes comprise 1,5,9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and their mixture.
The useful bleaching catalyst of this composition also can be selected from suitable bleaching catalyst, consults United States Patent (USP) 4,246, and 612 and United States Patent (USP) 5,227,084.Also consult United States Patent (USP) 5,194,416, it has lectured monokaryon manganese (IV) complex compound such as Mn (1,4,7-trimethylammonium-1,4,7-three azepines-cyclononane) (OCH
3)
3-(PF
6).
The bleaching catalyst of another type, as at United States Patent (USP) 5,114,606 is disclosed, is manganese (III) and/or (IV) and the water-solubleness complex of part, and part is the non--carboxylated polyol with at least three continuous C-OH groups.Preferred part comprises sorbyl alcohol, iditol, melampyrum, N.F,USP MANNITOL, Xylitol, arabitol, adonitol, meso-tetrahydroxybutane, meso-inositol, lactose and their mixture.
United States Patent (USP) 5,114,611 describe other suitable bleaching catalysts, it contains the complex compound of transition metal, comprise Mn, Co, Fe or Cu and a kind of non--(greatly) encircle part.Said part has chemical formula:
Wherein, R
1, R
2, R
3And R
4Can respectively be selected from H, substituted alkyl and aryl, make each R
1-N=C-R
2And R
3-C=N-R
4Form one five yuan or six-ring.Said ring can further be substituted.B is an abutment, and it is selected from O, S, CR
5R
6, NR
7And C=O, wherein R
5, R
6And R
7Can respectively be H, alkyl or aryl, comprise replacement or unsubstituted group.Preferred part comprises pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles and triazole ring.Said ring can at random be substituted base and replace substituting group such as alkyl, aryl, alkoxyl group, halogeno-group and nitro.Particularly preferably be part 2,2 '-two pyridine amine.Preferred bleaching catalyst comprises Co, Cu, Mn, Fe's-two pyridine methane and-two pyridine amine complexes.Catalyzer very preferably comprises Co (2,2 '-two pyridine amine) Cl
2, the two pyridine amine-cobalts of two (isothiocyanatos) (II), terpyridyl amine-cobalt (II) perchlorate, Co (2, the two pyridine amine of 2-)
2O
2ClO
4, two (2,2 '-two pyridine amine) copper (II) perchlorate, three (two-2-pyridine amine) iron (II) perchlorate and they mixture.
Preferred examples comprises the complex compound of double-core Mn and four-N-dentate and two-N-dentate part, comprises N
4Mn
III(u-O)
2Mn
IVN
4)
+[Bipy
2Mn
III(u-O)
2Mn
IVBipy
2]-(ClO
4)
3
Other bleaching catalysts are for example at European patent 408,131 (cobalt complex catalysts), european patent application publication number 384,503, with 306,089 (metal-porphyrin catalyst), the U.S. 4,728,455 (manganese/polygamy position ylidene ligands catalyzer), US4,711,748 and european patent application publication number 224,952 (manganese is absorbed on the aluminosilicate catalyzer), the U.S. 4,601,845 (manganese and zinc or magnesium salts prop up the aluminosilicate that carries), the U.S. 4,626,373 (manganese/ligand catalysts), the U.S. 4,119,557 (iron complex catalyzer), German patent specification 2,054,019 (cobalt chelating catalyst), Canada's 866,191 (transition metal-saliferous) and the U.S. 4, in 430,243 (sequestrant and manganese positively charged ion and the non--catalytic metal positively charged ions) explanation is arranged.Catalyzer very preferably is the catalyzer (gluconic acid Mn catalyst) of narration in the U.S. 4,728,455.
The suitable Mn catalyst example that contains organic ligand is at US-A-4, and 728,455, US-A-5,114,606, US-A-5,153,161, US-A-5,194,416, US-A-5,227,804, US-A-5,246,612, US-A-5,246,621, US-A-5,256,779, US-A-5,274,147, US-A-5,280,117 and EP-A-544,440, EP-A-544 has explanation in 490, EP-A-549,271, EP-A-549,272.These catalyzer preferred examples comprise Mn
VI 2(u-O)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(PF
6)
2, Mn
III 2(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7 7-triazacyclononanes)
2(ClO
4)
2, Mn
VI 4(u-O)
6(1,4,7-trimethylammonium-1,4,7 7-triazacyclononanes)
4(ClO
4)
4, Mn
IIIMn
VI 4(u-O)
1(u-OAc)
2(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)
2(ClO
4)
3, Mn
VI(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH
3)
3(PF
6) and their mixture.Other metals-Ji bleaching catalyst is included in US-A-4, disclosed catalyzer in 430,243 and US-A-5,114,611.
Here the iron of aminocarboxylic acid and manganese salt generally are useful, and it comprises being applied to of being disclosed the photograph iron bleached in the color treatment technology and the amino-carboxylate salt of manganese.A kind of useful especially transition metal salt is any complex compound institute deutero-by ethylenediamine disuccinic acid and this part and iron or manganese.
The bleaching catalyst of other types, disclosed in 114,606 as at US-A-5, be manganese (II), (III) m and/or (IV) and the water soluble complex of part, these part right and wrong-carboxylated polyol with at least three continuous C-OH groups.Preferred part comprises sorbyl alcohol, iditol, melampyrum, N.F,USP MANNITOL, Xylitol, arabitol, adonitol, meso-tetrahydroxybutane, meso-inositol, lactose and their mixture, especially preferred sorbyl alcohol.
Other examples comprise Mn gluconate, Mn (CF
3SO
3)
2With the complex compound of double-core Mn and four-N-dentate and two-N-dentate part formation, dentate comprises [bipy
2Mn
III(u-O)
2Mn
VIBipy
2]-(ClO
4)
3
Other bleaching catalysts are at for example EP-A-408,131 (cobalt complexs), EP-A-384,503 and EP-A-306,689 (metal-porphyrins), US-A-4,728,455 (manganese/polygamy position ylidene ligands), US-A-4,711,748 (manganese is absorbed on the aluminosilicate), US-A-4,601,845 (by manganese, zinc or magnesium salts prop up the aluminosilicate that carries), US-A-4,626,373 (manganese/parts), US-A-4,119,557 (iron complexs), US-A-4,430,243 (sequestrant and manganese positively charged ion and non--catalytic metal positively charged ion) and US-A-4 have explanation in 728,455 (managanese gluconates).
Other are suitable for containing metal-catalyzer of the present invention and comprise and contain cobalt-catalyzer as five amine Cobaltous diacetate (III) salt, with contain manganese-catalyzer such as those are at EPA 549 271, EPA 549 272, EPA 458397, US 5,246,621, EPA458 398, US 5,194,416 and US 5,114,611 in the narration.The bleaching composition of patent application 94870206.3 narrations of publishing under one's name at EP-A-718 398 contains peralcohol, contains manganese-bleaching catalyst and sequestrant.
Preferred catalyzer is the catalyzer based on cobalt, reaches at WO96/23859, WO96/23860 and WO96/23861 and US-A-5, explanation is arranged in 559,261.WO96/23860 has narrated [Co
nL
mX
p]
ZY
zThe cobalt catalyst of type, wherein L is a kind of containing more than a heteroatomic organic ligand molecule, heteroatoms is selected from N, P, O and S; X is a kind of coordination kind; N preferred 1 or 2; M preferred 1～5; P preferred 0～4; And Y is counter ion.An example of this catalyzer is N, N '-two (salicylidene) quadrol cobalt (II).In this application other cobalt catalyst of Miao Shuing based on Co (III) and ammonia and singly-, two-, three-and the complex compound of tetradentate ligand, as [Co (NH
3)
5OAc]
2+And Cl
-, OAc
-, PF
6 -, SO
4 =, BF
4 -Negatively charged ion.Preferred cobalt catalyst is at US 5,798,326 and US 5,703,030 in the catalyzer of narration.US 5,798, and 326 have described a kind of selection of cobalt (III) catalyzer, and it has chemical formula: Co[(NH
3)
nM
mB
bT
tQ
qP
p] Y
y, wherein cobalt is in+3 oxidation state; N is 0～5 integer, and is preferred 4～5, more preferably 5; M represents the monodentate part; M is 0～5 integer, and is preferred 1～2, more preferably 1; B represents the bidentate part; B is 0～2 integer; T represents the tri-dentate part; T is 0 or 1; Q is a tetradentate ligand; Q is 0 or 1; P is the pentacoordinate ylidene ligands; P is 0 or 1; And n+m+2b+3t+4q+5p=6; Y is one or more counter anion that exist with number y of suitably selecting, wherein when Y be that y is 1～3 integer when being with the negatively charged ion of a-1 electric charge, preferred 2～3, more preferably 2, to obtain the salt of charge balance.US 5,703, and 030 cobalt catalyst of describing has chemical formula [Co (NH
3) 5M] T
y, wherein cobalt is in+3 oxidation state; M is the part of carboxylate-containing, has chemical formula RC (O) O-; And T is one or more counter anion, and the number of its existence is y, and wherein y is the integer that obtains the salt of charge balance (preferred 1～3 when T is the negatively charged ion of band-1 electric charge, more preferably 2).
The bleaching catalyst that contains certain transition metal can be reflected at in-situ preparing by transition-metal-salt and suitable sequestrant, for example a kind of mixture of manganous sulfate and ethylenediamine disuccinate.The bleaching catalyst that contains dark transition metal can be processed to reduce the influence of color with zeolite is common.
For the metal catalyst of target optimum selecting of the present invention is the catalyzer of describing at WO98/39406, it contains the complex compound that transition metal and the big shape of a kind of intersection-bridge-type are encircled part more, wherein:
(1) this metal is selected from Mn (II), Mn (IV), Mn (V), Fe (II), Fe (III), Fe (IV), Co (I), Co (II), Co (III), Ni (I), Ni (II), Ni (III), Cu (I), Cu (II), Cr (III), Cr (IV), Cr (V), Cr (VI), V (III), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (Vl), Pd (II), Ru (II), Ru (III) and Ru (IV); And
(2) big shape is encircled rigid ligand more and is selected from:
(i) to have ligancy be 4 or 5 part to chemical formula (I);
(ii) to have ligancy be 5 or 6 part to chemical formula (II);
(iii) to have ligancy be 6 or 7 part to chemical formula (III); (E=(CRn) a-X-(CRn) a ' part wherein; X=O, S, NR or P, or covalent linkage (especially covalent linkage); To each E sum a+a '=1～5 (especially 2 and 3; G=(CRn) b; R=H, alkyl, alkenyl, alkynyl, aryl, alkylaryl or heteroaryl, or two or more covalent bonds form the ring of aromatic or heteroaromatic, cycloalkyl or Heterocyclylalkyl; The D=donor atom is selected from N, O, S or P, and at least two D atoms are the end of the bridge donor atoms with transition-metal coordination; B=C or D or cycloalkyl or heterocyclic ring; N=1 or 2 is to finish the R part valency of the C atom of bonding with it; N '=0 or 1 is to finish the R part valency of the D donor atom of bonding with it; N "=0,1 or 2, to finish the R part valency of the B atom of bonding with it; A, a '=0～5, preferred a+a '=2 or 3, all the summation of a+all the summation of a ' is 7～12 in chemical formula (I), the whole summation of a+a ' (especially 8)～12 that are 6 in chemical formula (II), in chemical formula (III) all the summation of a+a ' (especially 10)～15 that are 8 and in chemical formula (IV) the whole summation of a+a ' (especially 12)～18 that are 10; B=0～9 (especially 0～5), perhaps do not exist one or more from any D to B atom covalence key bonded (CRn) b part, as long as at least two (CRn) b are covalently bound to two D donor atoms on the B atom, and the summation of whole b is 1～5; And
(iv) any one or multiple non--big shape encircles part more, is preferably selected from H
2O, ROH, NR
3, RCN, OH
-, OOH
-, RS
-, RO
-, OCN
-, SCN
-, N
3 -, CN
-, F
-, Cl
-, Br
-, I
-, O
2-, NO
3 -, NO
2 -, SO
4 2-, SO
3 2-, PO
4 3-, organophosphate, organic phosphonate, organic sulfate, organic sulfonate and aromatic series N-donor such as pyridines, pyrazine class, pyrazoles, imidazoles, benzimidazoles, miazines, triazole species and R be the thiazoles of H, the alkyl or aryl that replaces arbitrarily; (b) at least 0.1% attachment component, the preferred oxygen SYNTHETIC OPTICAL WHITNER.The donor atom that preferred big shape is encircled part more is N, S, O or P, especially N or O, more specifically all is N.Part contains 4 or 5 donor atoms, all is connected with same transition metal.The many rings of the organic big shape that this part contains contain at least 12, particularly 12～20 atoms.A is 2 or 3, and all X are covalent linkage, a ' be 0 and B be 0.1 or 2.Transition metal is 1: 1 to the mol ratio of part, and transition metal is Mn or Fe.
It is preferred that to contain the catalyzer that this transition metal and the big shape of intersection-bridge-type encircle ligand complex more be [Mn (Bcyclam) Cl
2]:
" Bcyclam " (5,1 2-dimethyl-1,5,8,12-four aza-bicyclos [6.6.2] n-Hexadecane) is according to J.Amer.Chem.Soc., (1990), 112,8604 preparations.(1.00g. 3.93mmol) is dissolved in anhydrous CH with Bcyclam
3(35mL is from CaH for CN
2Last steaming slips out), this solution is found time up to CH at 15mm
3CN comes to life, and flask is charged to normal atmosphere with Ar gas then, and so the program of the degassing repeats 4 times.Under Ar gas, add according to document J.Inorg.Nucl.Chem. (1974), 36,1535 step synthetic Mn (pyridine)
2Cl
2(1.12g., 3.93mmol), and mixture is in stirred overnight at room temperature.With 0.2 μ strainer filtering reacting liquid, the filtrate evaporation is collected product 1.35g, productive rate 90%.
Bleaching catalyst is typically effectively measured with catalysis and is used in composition and the method here.
" catalysis is effectively measured " is meant under any employed comparison test condition, is enough to improve the amount of bleaching and remove deliberate stain or multiple stain from target matrix.To change the condition of test according to employed scrubber and user's custom.Some user selects to use awfully hot water in laundry operations; And other people use warm water or even cold water.Certainly, the catalytic performance of bleaching catalyst will be subjected to the influence of these factors, and can suitably adjust the level of bleaching catalyst in the washing composition of complete-preparation and the bleaching composition.With regard to actual content and unrestricted mode, can adjust here composition and method, the bleaching catalyst class at a ten million/order of magnitude is provided in water at least, and preferably in washings, provides about 1ppm～the about catalyzer class of 200ppm.For further specifying this point, under the European condition 40 ℃, when using perborate and crossing the acid blanching precursor during pH10, the order of magnitude is that 3 micromolar Mn catalysts are effective.Under U.S.'s condition, need increase by 3～5 times for reaching same concentration as a result.
Therefore, generally on the level of 1ppb～10%, preferably approximately 0.1ppm～about 1% by composition weight meter for the metal bleach catalyst that contains in the detergent composition of the present invention, most preferably about 1ppm～about 0.1%.
The preferred metal bleach catalyst of detergent composition of the present invention is at US 5,798, the cobalt catalyst Co[(NH of narration in 326 (the consulting above)
3)
nM
mB
bT
tQ
qP
p] Y
y, at US 5,703, cobalt catalyst [Co (NH3) 5M] T of narration in 030 (the consulting above)
y, contain catalyzer [Mn (Bcyclam) Cl that transition metal and the big shape of intersection-bridge-type are encircled part more
2] and/or their mixture.
The bleaching secondary accelerator
The 3rd bleach system that detergent composition of the present invention is selected is bleaching secondary accelerator binding substances, and it comprises the zwitter-ion imines, has about-1～approximately negatively charged ion imines polyion of-3 net negative charges and their mixture; And peroxygen source.
The compound structure that the imines bleaching secondary accelerator that the present invention suits comprises is:
Wherein, R
1～R
4Can be hydrogen or group unsubstituted or that replace, group be selected from phenyl, aryl, heterocyclic cyclic group, alkyl and cycloalkyl, as long as R
1～R
4In at least one is to contain the anionic charge part.
The present invention preferably bleaches secondary accelerator and comprises the anionic charge part that is attached on the imines nitrogen, with following chemical formulation:
Wherein:
R
1～R
3Be to have about 0～approximately-1 the part of total charge;
R
1～R
3Can be hydrogen or group unsubstituted or that replace, group be selected from phenyl, aryl, heterocyclic cyclic group, alkyl and cycloalkyl;
T is selected from :-(CH
2)
b-wherein b be about 1～about 8 ,-(CH (R
5))-R wherein
5Be C
1-C
8Alkyl ,-CH
2(C
6H
4)-,
With-(CH
2)
d(E) (CH
2)
f-wherein d is 2～8, f be 1～3 and E be-C (O) O-,-C (O) NR
6Or
-R wherein
6Be H or C
1-C
4Alkyl.
Z is the covalent linkage that is connected with T, is selected from-CO
2 -,-SO
3 -With-OSO
3 -And a is 1 at least.Therefore, owing to being connected to T, the Z covalent linkage (works as R
1～R
3On total charge when being zero), imines is a zwitter-ion when a is 1, perhaps when a imines greater than 1 time be polyion with net negative charge.Preferably, a or 1 or 2, and the polyion of bleaching secondary accelerator or zwitter-ion or having net charge-1.
In a more preferred embodiment, to bleach secondary accelerator be aryl imonium zwitter-ion, have approximately-1～approximately aryl imonium polyion of-3 net negative charges or their mixture in the present invention.In this preferred embodiment, R
1And R
2Form the part of common ring together.Particularly, R
1And R
2Can form one or more five-units, six-unit or seven-unit's ring together.Most preferred aryl imonium by following non--alive part forms:
Therefore, preferred aryl groups imonium zwitter-ion comprises the R that forms non--alive part (III) together
1And R
2And T, T is selected from-(CH
2)
b-wherein b be about 1～about 6 ,-(CH (R
5))-R wherein
5Be methyl and-CH
2(C
6H
4)-, and a be 1 and Z be selected from CO
2 -With-SO
3 -Aryl imonium zwitter-ion more preferably of the present invention contains the R that forms non--alive part (III) together
1And R
2And T, T is-(CH
2)
b-or-CH
2(C
6H
4)-, a is 1, and Z is-SO
3 -With b be 2～4.Most preferred aryl imonium zwitter-ion is with following chemical formulation according to the present invention: (IV) (V)
Or
Be respectively 3-(3, the 4-dihydro-isoquinoline) propane sulfonate and 4-(3, the 4-dihydro-isoquinoline) butane sulfonate.
Preferred aryl groups imonium polyion comprises the R that forms non--alive part (III) together according to the present invention
1And R
2And T, T is selected from:
With-(CH
2)
d(E) (CH2)
f-wherein d is 2～8, f be 1～3 and E be:
A be at least 2 and Z be selected from CO
2 -With-SO
3 -The present invention more preferably aryl imonium polyion has the R that forms non--alive part (III) together
1And R
2And T, T is selected from:
With-(CH
2)
d(E) (CH
2)
f-wherein d is 2～6, f be 1 and E be:
And a be 2 and Z be-SO
3 -According to the present invention most preferably polyion by following chemical formulation:
Other suitable imines bleaching secondary accelerators of the present invention contain season imines zwitter-ion, by following chemical formulation:
Wherein:
R
1～R
3Can be hydrogen or group unsubstituted or that replace, group be selected from phenyl, aryl, heterocyclic cyclic group, alkyl and cycloalkyl;
T is:
Wherein x equals 0 or 1; J if exist, then is selected from-CR
11R
12-,-CR
11R
12CR
13R
14-and-R
11R
12CR
13R
14CR
15R
16-; R
7～R
16Respectively be independently selected from the C of H, straight or branched
1～C
18That replace or unsubstituted alkyl, alkylidene group, oxyalkylene group, aryl, the aryl of replacement, the aryl carbonyl group and the amide group of replacement, just R
7～R
8In at least one must be H or methyl, and work as R
9Or R
10When being not H, R
7～R
8In one must be H.Preferred R
9And R
10Among at least one must be H.C
bAnd C
dIt is carbon atom.
When x was 1, the Z covalent linkage was connected to J
xOn, when x was 0, Z was connected to C
bOn, and Z is selected from-CO
2 -,-SO
2 -,-PO
3 -,-OPO
3 -,-SO
3 -With-OSO
3 -, wherein-OSO
3 -Be preferred, and a is 1.Therefore, because being the covalent linkage connection, Z (works as R
1～R
3On total charge when being zero), this in season imines be zwitter-ion.
In a preferred embodiment, it is aryl imonium zwitter-ion that the present invention bleaches secondary accelerator.In this preferred embodiment, R
1And R
2Form the part of common ring together.Particularly, R
1And R
2Can form one or more five-units, six-unit or seven-unit's ring together.Most preferred aryl imonium by following non--alive part forms:
Therefore, preferred aryl groups imonium zwitter-ion is included in the R that forms non--alive part (III) together
1And R
2And T, T is:
Wherein a is 1, and Z is selected from-OSO
3 -With-SO
3 -Aryl imonium zwitter-ion more preferably of the present invention has the R that together forms non--alive part (III)
1And R
2And T, T is:
Wherein a is 1, and Z is-OSO
3 -According to the present invention most preferably aryl imonium zwitter-ion by following chemical formulation:
R wherein
17Be selected from the C of H, straight or branched
1～C
18That replace or unsubstituted alkyl, preferred C
1～C
14Alkyl and even more preferably C
8～C
10Linear alkyl chain.
Such bleaching secondary accelerator can prepare according to the method for narrating among the common co-pending application WO97/10323 in the world, and this application is by Procter﹠amp; Gamble company proposed on August 30th, 1996, the method for narrating among reference example I-III and/or the international common co-pending application WO98/16614 especially, and this application is by Procter﹠amp; Gamble company proposed on August 28th, 1997, and reference example I-VIII especially.
The present invention bleaches secondary accelerator and will use with the peroxygen source associating in bleaching composition.Peroxygen source general level that exists in detergent composition of the present invention is 0.1%～60% of a composition weight, reaches 1%～40% of preferred composition weight.In detergent composition of the present invention the general level that exists of bleaching secondary accelerator be composition weight 0.01%～10% and more preferably composition weight 0.05%～5%.
Imines bleaching secondary accelerator of the present invention and peroxygen source are united the effect that increases bleaching efficiency of playing.Bleaching secondary accelerator and peroxygen source reaction form more active bleaching kind: a kind of oxaziridinium compound.Formed oxaziridinium compound is because be imines bleaching secondary accelerator, it or zwitter-ion, or the polyion of band net negative charge.Having activity with respect to peralcohol oxaziridinium compound at low temperature has increased.The oxaziridinium compound can be used following chemical formulation:
And can produce with following reaction by imines of the present invention:
Like this, the present invention preferably generates active oxaziridinium bleaching kind by following chemical formulation by the bleaching secondary accelerator of chemical formula (IV) expression:
Peroxygen source
Peroxygen source is well known in the art, and the peroxygen source that reaches the present invention's use can contain the peroxygen source that any of these is known, and comprises peralcohol reaches provides the significant quantity peroxide in position under the condition that the human consumer uses compound.Peroxygen source can comprise hydrogen peroxide cource, is reflected at original position by hydrogen peroxide cource and bleach-activating agent and forms acid anion, ready-formed peracid compound or suitable peroxygen source mixture.Such peroxygen source comprises, for example, and inorganic hydrogen peroxide compound SYNTHETIC OPTICAL WHITNER or organic peroxy acids.Bleach system contains hydrogen peroxide cource and peroxy acid bleach precursor compound in preferred an enforcement.Be reflected at the generation that peroxy acid appears in original position by precursor compound and hydrogen peroxide cource.Preferred hydrogen peroxide cource comprises that inorganic hydrogen peroxide compound SYNTHETIC OPTICAL WHITNER is certain, and this area those skilled in the art will admit that need not to leave scope of the present invention can use other peroxygen sources.
Here employed prefabricated peracid compound is the compound that condition provides the anionic any satisfaction of peracid of significant quantity under the human consumer uses.Suitable limiting examples comprises percarboxylic acids and salt, percarbonic acid and salt, crosses imido acid and salt, permonosulphuric acid and salt and their mixture.The suitable example of percarboxylic acids and salt comprises magnesium salts, the 4-nonyl amino-magnesium salts of 4-oxo Perbutyric Acid and the magnesium salts of diperoxy dodecanedioic acid of monoperphthalic acid magnesium hexahydrate, metachloroperbenzoic acid.Such SYNTHETIC OPTICAL WHITNER is disclosed in the United States Patent (USP) 4 of the announcement in 20 days November in 1984 of Hartman, 483,781, people's such as Burns United States Patent (USP) 4,634,551, the United States Patent (USP) of announcing on the people's such as Banks that announced on February 20th, 1985 european patent application 0,133,354 and November 1 nineteen eighty-three 4, in 412,934.Described in the United States Patent (USP) of announcing on January 6th, 1987 as people such as Bums 4,634,551, peroxygen source comprises that also 6-nonyl amino-6-oxo crosses oxy hexanoic acid.Persulfate compound, as for example commercial by E.I.DuPont deNemours of Wilmington, the OXONE that DE produces also can be used as the source of suitable permonosulphuric acid.
Here employed hydrogen peroxide cource is compound or the mixture that condition provides any satisfaction of significant quantity hydrogen peroxide under the human consumer uses.The general level of using is range extensively, reaches about 0.1%～about 60%, more typically about 1%～about 40% of bleaching composition weight typically.Hydrogen peroxide cource used herein can be any source easily, comprises hydrogen peroxide itself.Here spendable is perborate for example, as Sodium peroxoborate (hydrated product arbitrarily, but preferred single-or four-hydrate), yellow soda ash peroxyhydrate or suitable percarbonate, trisodium phosphate peroxyhydrate, urea peroxyhydrate or sodium peroxide.Also can use the mixture of any hydrogen peroxide cource easily.
Inorganic hydrogen peroxide compound SYNTHETIC OPTICAL WHITNER
Inorganic perhydrate salts is preferred hydrogen peroxide cource.These salt generally mix with the form of sodium salt, and the level of mixing is 1%～95% of a bleaching composition weight, and more preferably 10%～90% and most preferably 20%～80%.In the time of in mixing the bleaching composition that comprises according to detergent composition of the present invention, the level that preferred inorganic perhydrate salts exists is 1%～40% of a detergent composition weight, more preferably 2%～30% and most preferably 5%～25%.
The example of inorganic perhydrate salts comprises perborate, superphosphate, persulphate and persilicate.Preferred inorganic perhydrate salts is the percarbonate of basic metal or alkaline-earth metal.
Be the component according to bleaching composition of the present invention, preferred percarbonate is a SPC-D, and it is a kind of addition compound, and corresponding chemical formula is 2Na
2CO
33H
2O
2, be crystalline solid, can utilize commodity.Most preferably percarbonate mixes this composition with the form that is coated with one deck, provides stability to product like this.Preferred percarbonate bleach contains the exsiccant particulate, average particle size is about 500 microns～about 1,000 micron scope, less than about 200 microns by said particulate weight no more than about 10%, and greater than about 1,250 micron by said particulate weight also no more than about 10%.Percarbonate can at random be coated with last layer silicate, borate or water-soluble surfactants.Can adopt the percarbonate of various commercial source, as FMC, Solvay and TokaiDenka.
Sodium peroxoborate can be the form with monohydrate, and its nominal chemical formula is NaBO
2H
2O
2, or tetrahydrate NaBO
2H
2O
23H
2O.
Inorganic perhydrate salts is an alkali metal salt normally.Inorganic perhydrate salts is as crystalline solid, and need not other protection can directly add.Yet to some perhydrate salt, the coating form of this material is used in the making of preferred this granular composition, and this provides better stability in storage to the perhydrate salt in the granulated product.
The suitable coated material that product stability is provided contains the mixture of water-soluble alkali vitriol and carbonate.This coating and coating treatment process be together before at GB-1, narrated in 466,799, and this patent on March 9th, 1977 was issued to Interox.The mixing salt coated material to the weight ratio of percarbonate at 1: 200～1: 4, the scope of more preferably 1: 99～1: 9 and most preferably 1: 49～1: 19.Preferred mixing salt is the mixing salt of sodium sulfate and yellow soda ash, and its chemical formula is generally Na
2SO
4NNa
2CO
3, wherein n is 0.1～3, preferred n be 0.3～1.0 and most preferably n be 0.2～0.5.
It also is favourable that other coatings that contain silicate (separately or with borate or boric acid or other inorganicss), wax, grease, fatty soap are used in the present invention.
Here other inorganic perhydrate salts of using in detergent composition were a persulfuric acid sylvite (potassium peroxymonopersulfate).
The peroxyacid bleach precursor compound
Preferably with 1%～50% of bleaching composition weight, more preferably 2%～30%, most preferably 5%～20% level is mixed the peroxy acid bleach precursor.
When the peroxy acid bleach precursor is mixed the bleaching composition that comprises according to detergent composition of the present invention, the level that preferred peroxy acid bleach precursor exists is 0.5%～20% of a detergent composition weight, more preferably 1%～15%, most preferably 1.5%～10%.
Suitable peroxy acid bleach precursor typically contains a kind of and multiple N-or O-acyl group, and this precursor can be selected from the classification of wide scope.Suitable classification comprises the acyl derivative of acid anhydrides, ester, imide and imidazoles and oxime.Narrated the example of material useful in these classifications among the GB-A-1586789, GB-A-836988,864798,1147871,2143231 and EP-A-0170386 suitable ester is disclosed.
N-acylations lactan precursor compound
General lactams N-acylations precursor compound is open in GB-A-855735.Though can consider to use aspect topmost in the present invention and anyly make the useful lactan of peroxyacid precursor, and preferable material comprises hexanolactam and Valerolactim.
Suitable N-acylations lactan precursor has chemical formula:
Wherein n be 0～about 8, preferred 0～2, and R
6Be H, contain alkyl, aryl, alkoxy aryl or the alkaryl of 1～12 carbon, or contain the substituted-phenyl of 6～18 carbon atoms.
The chemical formula of suitable caprolactam bleach agent precursor is:
R wherein
1Be H, or alkyl, aryl, alkoxy aryl or alkaryl, 1～12 carbon atom contained, preferred 6～12 carbon atoms.Most preferred R
1It is phenyl.
Suitable Valerolactim has chemical formula:
R wherein
1Be H, or alkyl, aryl, alkoxy aryl or alkaryl, 1～12 carbon atom contained, preferred 6～12 carbon atoms.In highly preferred embodiment, R
1Be selected from phenyl, heptyl, octyl group, nonyl, 2,4,4-tri-methyl-amyl, decene base and their mixture.
Most preferred material is to be the solid material at＜30 ℃ usually; phenyl derivatives particularly; be the benzoyl Valerolactim, benzoyl analogue such as chloro, aminoalkyl group, alkyl, aryl and the alkoxy derivative of benzoyl caprolactam and their replacement.
Hexanolactam and Valerolactim precursor material, wherein R
1Part contains at least 6, preferred 6～12 carbon atoms, and at the supply peroxide acids in the oxygen hydrolysis of crossing of hydrophobic character, it provides protophilic and the removing health dirt.R wherein
1The precursor compound that contains 1～6 carbon atom provides hydrophilic SYNTHETIC OPTICAL WHITNER class, and they are effective especially to bleaching beverage stain.The mixture of " hydrophobic " and " hydrophilic " hexanolactam and Valerolactim, typically with weight ratio 1: 5～5: 1, preferred 1: 1, the removal benefit that can be used for mixing stain here.
Hexanolactam very preferably and Valerolactim precursor comprise benzoyl caprolactam; nonanoyl oneself-lactan; the benzoyl Valerolactim; the nonanoyl Valerolactim; 3; 5; 5-trimethyl acetyl base hexanolactam; 3; 5,5-trimethyl acetyl base Valerolactim; the capryloyl hexanolactam; the capryloyl Valerolactim; the decanoyl hexanolactam; the decanoyl Valerolactim; the undecylene acyl caprolactam; undecylene acyl group Valerolactim; (the amino caproyl of 6-decoyl) oxygen base-sulphonate; (6-nonanoyl amino-caproyl) oxygen base sulphonate; (the amino caproyl of 6-caprinoyl)-oxygen base-sulphonate and their mixture.The example of substituted benzoyl lactan very preferably comprises the methyl benzoyl hexanolactam; the methyl benzoyl Valerolactim; ethylamino benzonitrile acyl group hexanolactam; ethylamino benzonitrile acyl group Valerolactim; the propyl group benzoyl caprolactam; propylbenzene formyl radical Valerolactim; the sec.-propyl benzoyl caprolactam; isopropyl benzene formyl radical Valerolactim; the butyl benzoyl caprolactam; butylbenzene formyl radical Valerolactim; the tert-butyl benzoyl caprolactam; tert-butyl benzoyl Valerolactim; the amyl group benzoyl caprolactam; amylbenzene formyl radical Valerolactim; the hexyl benzoyl caprolactam; hexyl benzene formyl radical Valerolactim; the ethoxy benzonitrile acyl caprolactam; phenetole formyl radical Valerolactim; the propoxy-benzoyl caprolactam; propoxy-benzoyl Valerolactim; isopropoxy benzoyl hexanolactam; isopropoxy benzoyl Valerolactim; the butoxy benzoyl caprolactam; butyl phenyl ether formyl radical Valerolactim; uncle-butoxy benzoyl caprolactam; uncle-butyl phenyl ether formyl radical Valerolactim; the pentyloxy benzoyl caprolactam; amyl phenyl ether formyl radical Valerolactim; the hexyloxy benzoyl caprolactam; hexyloxy benzoyl Valerolactim; 2; 4; 6-trichloro-benzene formyl radical hexanolactam; 2; 4; 6-trichloro-benzene formyl radical Valerolactim; phenyl-pentafluoride formyl radical hexanolactam; phenyl-pentafluoride formyl radical Valerolactim; the dichloro-benzoyl caprolactam; dimethoxy benzoyl hexanolactam; 4-chloro benzoyl caprolactam; 2; 4-dichloro-r benzoyl caprolactam; the terephthaloyl dicaprolactam; phenyl-pentafluoride formyl radical hexanolactam; phenyl-pentafluoride formyl radical Valerolactim; dichlorobenzene formyl radical Valerolactim; dimethoxy benzoyl Valerolactim; 4-chlorinated benzene formyl radical Valerolactim; 2,4-dichlorobenzene formyl radical Valerolactim; terephthaloyl two Valerolactims; 4-nitro benzoyl hexanolactam; 4-nitro benzoyl Valerolactim and their mixture.
Peroxybenzoic acid precursors
Basically any peroxybenzoic acid precursors here all suits, and comprises preferred N-acylations lactams.
Suitable O-acylations peroxybenzoic acid precursors compound comprises and comprises replacement and unsubstituted benzoyloxy benzene sulfonate as the benzoyloxy benzene sulfonate:
The suitable benzoyl product that also has sorbyl alcohol, glucose and all carbohydrates and benzoyl reagent for example comprises:
Ac=COCH
3The Bz=benzoyl
Preferred imide type peroxybenzoic acid precursors compound comprises the urea that N-benzoyl succinimide, four benzoyl ethylene diamines and N-benzoyl replace.Suitable imidazole type peroxybenzoic acid precursors comprises that N-benzoyl imidazoles and N-benzoyl benzo imidazoles and other useful peroxybenzoic acid precursors that contains the N-acyl group comprise N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.
Preferred peroxybenzoic acid precursors comprises benzoyl diacyl peroxide, benzoyl four acyl peroxides and has the compound of following chemical formula:
Tetra hydro Phthalic anhydride is another kind of here suitable peroxybenzoic acid precursors compound:
Peroxybenzoic acid acid derivative precursor
Suitable peroxybenzoic acid derivative precursor comprises any peroxybenzoic acid based precursor disclosed herein, and wherein the peroxybenzoic acid group can be replaced by any functional group basically, and functional group comprises alkyl.
The positively charged ion peroxyacid precursor
Positively charged ion peroxyacid precursor compound here also suits.Typical this positively charged ion peroxyacid precursor partly forms preferred ethyl of alkyl ammonium group or ammonium methyl group by replacing peroxy acid with ammonium or alkyl ammonium group.
The positively charged ion peroxyacid precursor is at United States Patent (USP) 4,904, and 406,4,751,015,4,988,451,4,397,757,5,269,962,5,127,852,5,093,022,5,106,528, U.K.1,382,594, EP 475,512,458, in 396 and 284,292 and, 332 report is arranged at JP 87-318.
The example of the peroxyacid precursor of preferred cation has report in UK Patent Application 9407944.9 and U.S. Patent application 08/298903,08/298650,08/298904 and 08/298906.
Suitable positively charged ion peroxyacid precursor comprises alkyl or the tetra-acetylated glucose benzoyl peroxide of benzoyloxy benzene sulfonate, N-acylations hexanolactam and single benzoyl that ammonium or alkylammonium replace.
Preferred cation substituted benzoyl acyl-oxygen base benzene sulfonate is 4-(TMA (TriMethylAmine)) methyl-derivatives of benzoyloxy benzene sulfonate:
Preferred cation substituted alkyl hydroxy benzene sulfonate is 2,3, the ammonium methyl derivative of 3-three-methyl hexylyloxy benzene sulfonate.
Preferred N-acylations hexanolactam cationoid peroxyacid precursor comprises trialkyl ammonium methylene radical benzoyl caprolactam, particularly trimethyl ammonium methylene radical benzoyl caprolactam:
The preferred cation peroxyacid precursor is 2-(N, N, a N-trimethyl ammonium) ethyl 4-sulfo group phenyl-carbonic acid na chloride in addition.
The alkyl fatty peroxyacid bleach precursor
The alkyl fatty peroxyacid bleach precursor derives from the oxygen hydrolysis of crossing of alkyl fatty peroxide acids, and preferably this class precursor produces peracetic acid in crossing oxygen hydrolysis.
Preferred imide type alkyl fatty peroxyacid precursor compound comprises N, N, N
1, N
1-tetrem acidylate Alkylenediamine, wherein alkylidene group contains 1～6 carbon atom, and particularly wherein alkylidene group contains the compound of 1,2 and 6 carbon atom.Preferred especially tetra acetyl ethylene diamine (TAED).
The peroxyacid bleach precursor that acid amides replaces
A preferred in addition class peroxy acid bleach activator compound is the compound that acid amides replaces, and it has following chemical general formula:
Or
R wherein
1Be the alkyl or aryl that 1～14 carbon atom is arranged, R
2Be the alkylidene group that contains 1～14 carbon atom, arylidene, and alkyl arylene, and R
5Be that H or alkyl, aryl or the alkaryl that contains 1～10 carbon atom and L can be any leavings group basically.Preferred R
1Contain 6～12 carbon atoms, preferred R
2Contain 4～8 carbon atoms.R
1Can be straight chain or contain branch, substituting group or the branched-chain alkyl of the two, its source can be synthetic source or natural source, natural source comprises as animal tallow.To R
2Allow similar structural changes, substituting group can comprise alkyl, aryl, halogen, nitrogen, sulphur and other typical substituting group or organic compound.R
5Preferred H or methyl.R
1And R
5Should not contain sum more than 18 carbon atom.L is optional to be R certainly hereinbefore
1It is any leavings group that the analogue of aryl or alkaryl is narrated.In EP-A-0170386, narrated such acid amides substituted bleach activator compound.
The L group must have enough reactivities, makes to be reflected in the Best Times framework (as wash(ing)cycle) to take place.Yet if the excessive reactivity of L, this activator will be difficult to the stable bleaching composition that is used for.These features are generally parallel with the pKa of the conjugate acid of leavings group, though known have exception to this routine.Usually the leavings group that presents this behavior be their the pKa scope of conjugate acid 4～13, preferred 6～11 and most preferably 8～11.
Preferred bleach precursor is R wherein
1, R
2And R
5Definition compound and the L identical with the acid amides substitution compound be selected from:
With
With
And their mixture, wherein R
1Be alkyl, aryl or the alkaryl that contains 1～14 carbon atom, R
3Be the alkyl chain that contains 1～8 carbon atom, R
4Be H or R
3, and Y is H or solubilizing group.
Preferred solubilizing group is-SO
3 -M
+,-CO
2 -M
+,-SO
4 -M
+,-N
+(R
3)
4X
-And O ← N (R
3)
3, and most preferably-SO
3 -M
+With-CO
2 -M
+, R wherein
3Be the alkyl chain that contains 1～4 carbon atom, M is the positively charged ion that solubleness is provided to bleach-activating agent, and X is the negatively charged ion that solubleness is provided to bleach-activating agent.Preferred M is the ammonium cation of basic metal, ammonium or replacement, most preferably sodium and potassium; And X is halogeno-group, hydroxide radical, methylsulfate or acetic acid anion.Should indicate as bleach-activating agent with leavings group do not contain solubilizing group, then bleach-activating agent should be dispersed in the liquid lime chloride well, so as to help their the dissolving.
Organic peroxide acid
Composition can contain the organic peroxy acids as the bleach system composition, and the level that the typical case is contained is 2%～30% of a bleaching composition weight, and more preferably 5%～20%.In the time of in this bleaching composition is comprised in according to detergent composition of the present invention, preferably the level that exists of this organic peroxide acid is 1%～15% of a detergent composition weight, and more preferably 1%～10%.
A preferred class organic peroxy acid compound is the acid amides substitution compound of following chemical general formula:
Or
R wherein
1Be alkyl, aryl or the alkaryl of 1～14 carbon atom, R
2Be alkylidene group, arylidene and the alkyl arylene that contains 1～14 carbon atom, and R
5Be H or alkyl, aryl or the alkaryl that contains 1～10 carbon atom.Preferred R
1Contain 6～12 carbon atoms, preferred R
2Contain 4～8 carbon atoms.R
1Can be the aryl of straight or branched alkyl, replacement or contain branch, substituting group or both alkaryls, its source can be synthetic source or natural source, natural source comprises as animal tallow.To R
2Allow similar structural changes, substituting group can comprise alkyl, aryl, halogen, nitrogen, sulphur and other typical substituting group or organic compound.R
5Preferred H or methyl.R
1And R
5Should not contain sum more than 18 carbon atom.In EP-A-0170386, narrate such acid amides and replaced organic peracetic acid compound.
Other organic peroxy acids comprise diperoxy dodecanedioic acid, diperoxy tetradecane diacid, diperoxy Thapsic acid, list-and two cross nonane diacids, list-and two mistake undecane dicarboxylic acids.
Suitable nonanoyl-oxygen base-sulfonate (NOBS, at US 4,412,934 state) in addition.At our common co-pending application USSN 08/136,626, narrated useful SYNTHETIC OPTICAL WHITNER among PCT/US95/07823, WO95/27772, WO95/27773, WO95/27774 and the WO95/27775, comprised peroxide acids that is used for detergent composition and the bleach system that contains bleach-activating agent and peroxy bleaching compound according to the present invention.
Also can provide hydrogen peroxide by enzyme system (being enzyme and substrate) at beginning or the hydrogen peroxide that adding can produce in washing and/or rinse cycle.This kind of enzyme system is disclosed in the european patent application 91202655.6 that proposed on October 9th, 1991.Detergent ingredients
Detergent composition of the present invention preferably further contains the additional detergent composition.The clean operation characteristic that the accurate kind of these supplementary components and the level of its adding will depend on the physical form of composition and use it.
According to detergent composition of the present invention can be liquid, paste, gel, strip, tablet, sprays, foams, powder or granular.Granular composition also can be " compression " type, and liquid composition also can be " concentrating " type.Tablet composition can be unipolar type or heterogeneous type.
Be surprisingly found out that pectate lyase cleaning performance can come optimization and optimizing with the release tech of time control.Particularly, Time Control Technique be a kind of tablet, wherein other detergent ingredients of pectate lyase and can suppressing/deactivation are isolated, they are in different product phases, being in the suds has different solubleness.Be surprised to find said enzyme is mixed the optimum performance efficient that tablet can reach the pectate lyase, and such system provides the cleaning performance of tangible dirt and stain.Find also that further so the release tech of time control allows the scope of employed pectate lyase wideer, be included in the enzyme that shows high stability in the standard wash agent material.The quick dissolving part of really, can be preferably pectate lyase and buffer material being mixed tablet.Do not wish to be limited by theory, think that the release of pectate lyase is prior to other detergent ingredients of meeting inhibition/deactivation, and when the washing beginning, under buffer condition, obtained best pectate lyase activity like this, it is all available allowing the pectate lyase in the pectate lyase detergent formulation.
Suitable tablet is that a kind of not only fully firmly standing operated and transportation, and at least a portion is dissolved the detergent tablet that pectate lyase snap-out release is provided fast in washing water.At least one beginning ten minutes of preferred tablet, preferred five minutes, more preferably be dissolved in washing water within four minutes in automatic dish washer or washing machine wash(ing)cycle.Preferred washing machine or automatic dish washer, or automatic washing machine.According to the dishwasher of DIN 44990 uses available from Bosch, use normal 65 ℃ of washing procedures, water hardness is 18 ° of H, uses minimum six repetitions or multiple number of times to be enough to guarantee repeatability, has measured the time of the solubilization of active ingredient of many-phase tablet or a phase wherein or washing composition.
In first embodiment, the laundry service detergent composition that the present invention relates to contains pectate lyase and selected bleach system (embodiment 1～16).In second embodiment, the dish washing agent composition that the present invention relates to contains pectate lyase, peroxygen source and bleaching secondary accelerator (embodiment 17～27).
Bleaching composition of the present invention can be advantageously used in laundry applications, hard-surface cleaning, wash dish automatically uses, and cosmetic application such as artificial tooth, tooth, hair and skin.Yet, because the two special advantages of the increase of low temperature solution efficient and good color-safety performance, the present invention bleaches secondary accelerator and is ideally suited laundry applications, comes bleached woven fabric as the SYNTHETIC OPTICAL WHITNER that contains washing composition or laundry bleaching additive by use.In addition, the present invention bleaches secondary accelerator and can be used for granular and liquid composition among the two.
The present composition can, for example, be formulated as and wash the dish composition, hand washing and machine scouring agent composition comprise laundry additive composition and are suitable for immersion and/or the pretreated composition that pollutes fabric, and the composition that is used for the hard-surface cleaning operation of general family.When preparation is used for manually washing the composition of dish mode, the present composition preferably contains tensio-active agent and preferred other detergent compounds, and these compounds are selected from organic polymer compounds, foam dose, II family metal ion, solvent, hydrotropic agent and additional enzymes.
When preparing the composition of suitable washing mode of washing machine, the present composition preferably contain tensio-active agent and washing-aid compound the two and additional one or more detergent ingredients are preferably selected from organic polymer compounds, SYNTHETIC OPTICAL WHITNER, additional enzymes, suds suppressor, dispersion agent, lime-soap dispersion agent, dirt suspends and anti--deposition agent and corrosion inhibitor again.Laundry composition also can contain tenderizer and make the additional detergent composition.When being formulated as the scouring agent composition, the composition that so contains pectate lyase, peroxygen source and bleaching secondary accelerator can provide the outward appearance of clean fabric, stain removal and color and luster.
When preparation is suitable for machine and washes the composition of dish mode, the present composition preferably contains low-foaming honionic surfactant, builder system and one or more compositions, and preferably these compositions are selected from organic polymer compounds, SYNTHETIC OPTICAL WHITNER, additional enzymes, suds suppressor, dispersion agent, lime-soap dispersion agent, dirt suspension agent and anti--again deposition agent and corrosion inhibitor.
All right solid of the present composition or liquid form are as the detergent additives product.This additive product has a mind to replenish or advance the performance of conventional detergent composition, and can add in any stage of cleaning course.
If desired, the density range of scouring agent composition is determined as 400～1200g/ liter at 20 ℃, preferred 500～950g/ rises composition.
" compression " type composition is subjected to density most and according to the influence of the mineral filler salt amount of composition; Mineral filler salt is the conventional ingredient of powder type detergent composition; In conventional detergent composition, filling salt exists with fundamental quantity, typically is the 17-35% of total composition weight.In compressed compositions, the amount of filling salt is no more than 15% of total composition, preferably is no more than 10% of composition weight, is most preferably not exceeding 5%.Mineral filler salt is selected from the vitriol and the hydrochloride of basic metal and alkali-soil-metal in this composition.Preferred filling salt is a sodium sulfate.
According to liquid detergent composition of the present invention also " concentrated type ".In this case, compare with the conventional liq washing composition, liquid detergent composition of the present invention contains the water of lower amount.Typically, the water-content of concentrated liquid detergent preferably is lower than 40% of detergent composition weight, more preferably less than 30%, most preferably is lower than 20%.
Suitable detergent compound used herein is selected from the compound of description.Surfactant system
Preferred detergent composition of the present invention contains surfactant system, and wherein tensio-active agent can be selected from cationic, non-ionic type and/or conventional anionic and/or their mixture.Suitable amphoteric in addition and/or zwitterionic and/or half-polar tensio-active agent.
It is 0.1%～60 weight % that typically there is level in surfactant system, and more preferably the level of Jia Ruing is 1%～35 weight %, most preferably is 1%～30% of scouring agent composition weight of the present invention.
There is the enzyme component compatibility in preferred preparation tensio-active agent and the composition.In liquid or gelatinous composition, most preferably prepare the stability that tensio-active agent makes its promotion or do not reduce any enzyme in these compositions at least.
The condenses of polyethylene oxide, poly(propylene oxide) and polybutylene oxide and induced by alkyl hydroxybenzene is the nonionic surface active agent that is suitable for surfactant system of the present invention, wherein preferred polyethylene oxide condensation compound.Alkyl in the induced by alkyl hydroxybenzene condensed products that these compounds comprise contains about 6～about 14 carbon atoms, preferably approximately 8～about 14 carbon atoms, alkylene oxide can be no matter straight-chain or-chain.In preferred embodiments, the amount of oxyethane equals in every mole of alkylphenol about 2～about 25 moles, more preferably about 3～about 15 moles oxyethane.This type of commercial available nonionic surface active agent comprises Igepal
TMCO-630, GAF company produces; And Triton
TMX-45, X-114, X-100 and X-102 all are Rohm﹠amp; The product of any company of Haas Comp.These tensio-active agents refer generally to the alkoxy compound (as ethoxylated alkylphenol) of alkylphenol.
The condensed products of the oxyethane of firsts and seconds fat family's alcohols and about 1～about 25 moles is the suitable nonionic surface active agent of nonionic surface active agent system of the present invention.The Fatty Alcohol(C12-C14 and C12-C18) alkyl chain can be straight chain or side chain, one-level or secondary, and generally contain about 8～about 22 carbon atoms.The condensed products of preferred alcohols and every mol of alcohol and about 2 about 10 moles of ethylene oxide, the wherein pure alkyl that has contains about 8～about 20 carbon atoms, more preferably about 10～about 18 carbon atoms.Every relatively mol of alcohol exists about 2～about 7 moles of ethylene oxide and 2～5 moles of ethylene oxide most preferably in the said condensed products.The commercial available example of this type nonionic surface active agent 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 alcohol and 6 moles of ethylene oxide has narrow molecular weight distribution), the two is the product of Union Carbide company; Neodol
TM45-9 (C
14-C
15The condensation product of linear alcohol and 9 moles of ethylene oxide), NeodoI
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), Neodol
TM45-5 (C
14-C
15The condensation product of linear alcohol and 5 moles of ethylene oxide), Shell chemical company product; Kyro
TMEOB (C
13-C
15The condensation product of alcohol and 9 moles of ethylene oxide), The Procter﹠amp; The product of Gamble company and Genapol LA O3O or O5O (C
12-C
14The condensation product of alcohol and 3～5 moles of ethylene oxide), the product of Hoechst.The preferable range of HLB is 8～11 and most preferably 8～10 in these products.
The useful nonionic surface active agent of surfactant system of the present invention in addition is an alkyl polysaccharide, is disclosed in the United States Patent (USP) 4,565,647 of Llenado distribution on January 21st, 1986.Alkyl polysaccharide has hydrophobic grouping and polysaccharide such as polysaccharide glycosides, this hydrophobic grouping contains about 6～about 30 carbon atoms, preferably approximately 10～about 16 carbon atoms, and hydrophilic group contains about 1.3～about 10, preferably approximately 1.3～about 3, most preferably about 1.3～about 2.7 sugar units.Can use any reducing sugar that contains 5～6 carbon atoms, (hydrophobic group can be connected to 2-arbitrarily can be substituted the glucosyl part as glucose, semi-lactosi and galactosyl part, 3-, positions such as 4-provide glucose or the semi-lactosi relative with glucoside or galactoside like this).Key between the sugar can be, as the position of other sugar unit and the 2-of front sugar unit, and 3-, 4-, and/or connect between the 6-position.
Preferred APG has chemical formula:
R
2O (C
nH
2nO)
1(glycosyl)
x
R wherein
2Be selected from alkyl, alkyl phenyl, hydroxyalkyl, the mixture of hydroxyalkyl phenyl and they, wherein alkyl contain about 10～about 18, preferably approximately 12～about 14 carbon atoms; N is 2 or 3, preferred 2; T is 0～about 10, preferred 0; With x be about 1.3～about 10, preferably approximately 1.3～about 3, most preferably about 1.3～about 2.7.Preferably by glucose deutero-glycosyl.Preparing these compounds is at first to form alcohol or alkyl polyethoxye alcohol, and forms glucoside (the 1-position is connected) with glucose or source of glucose reaction then.Other then glycosyl units can be at their the 1-position and the 2-of previous glycosyl units, 3-, and 4-and/or 6-position join, preferably mainly in the 2-position.
Condensed products between the hydrophobic group that oxyethane and propylene oxide and propylene glycol condensation form is also suitable to be used as the other nonionic surface active agent system of the present invention.That the hydrophobic part of these compounds preferably has molecular weight is about 1500～and about 1800, and show water insoluble.The adduction of polyoxyethylene part and this hydrophobic part trends towards increasing the water-soluble of molecule integral body, and the characteristics of liquids of product can remain into about 50% this point that polyoxyethylated content is the condensation product gross weight, this corresponding to the oxyethane of institute's condensation up to about 40 moles.The example of this type compound comprises some commercial-available Plurafac
TMLF404 and Pluronic
TMTensio-active agent, BASF produces.
Suitable nonionic surface active agent as nonionic surface active agent system of the present invention also has the condensed products of oxyethane and propylene oxide and product that reacting ethylenediamine generates.The hydrophobic part of these products contains the reaction product of quadrol and excessive propylene oxide, and general molecular weight is about 2500～about 3000.This hydrophobic part and ethylene oxide condensation are about degree of 5,000～about 11,000 to polyoxyethylene and the molecular weight that this condensation product contains about 40%～about 80 weight %.The example of this type nonionic surface active agent comprises some commercial available Tetronic
TMCompound, BASF produces.
Preferred nonionic surface active agent as surfactant system of the present invention is the polyethylene oxide condensation compound of induced by alkyl hydroxybenzene, the aliphatics alcohols of firsts and seconds and product, alkyl polysaccharide class and their mixture of about 1～about 25 moles of ethylene oxide condensations.The C that most preferably has 3～15 oxyethyl groups
8-C
14Alkylphenol ethoxylate, has the C of 2～10 oxyethyl groups
8-C
18Alcohol ethoxylate (preferred average C
10) and their mixture.
The polyhydroxy fatty acid amide surfactant of nonionic surface active agent very preferably, its chemical formula is:
R wherein
1Be H, or R
1Be C
1～4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture, R
2Be C
5～31Alkyl and Z are polyhydroxy alkyls, and it has linear hydrocarbyl chain, and at least 3 hydroxyls are directly linked on this chain, or their alkoxy derivative.Preferred R
1Be methyl, R
2Be the C of straight chain
11～15Alkyl or C
16～18Alkyl or alkenyl chain such as cocounut oil alkyl and their mixture and Z are by reducing sugar such as glucose, fructose, maltose, lactose deutero-in reductive amination process.
The suitable anion surfactant that uses is linear alkyl benzene sulfonate, alkyl sulfonate surfactants, and the latter comprises C
8～C
20The ol ester of carboxylic acid (being fatty acid), according to " The Journalof the American Oil Chemists Society ", 52 (1975), the method for pp.323-329 is by the sulfonation of SO3 gas.Suitable raw material comprises the natural fat material that is derived from Tallow, beef, palm wet goods.
Preferably, especially laundry service is used, alkyl sulfonate surfactants contains the alkyl sulfonate surfactants of following structural chemistry formula:
R wherein
3Be C
8～C
20Alkyl, preferred alkyl, or their mixing; R
4Be C
1～C
6Alkyl, preferred alkyl, or their mixing; With M be positively charged ion, it and alkyl ester sulfonic acid form water-soluble salt.The suitable salifiable positively charged ion of shape comprises metal such as sodium, potassium and lithium and replacement or unsubstituted ammonium ion, as monoethanolamine, diethanolamine and trolamine.Preferred R
3Be C
10～C
16Alkyl; And R
4Be methyl, ethyl or sec.-propyl.Especially preferable methyl sulfonated ester, wherein R
3Be C
10～C
16Alkyl.
Other suitable anion surfactants comprise alkyl sulfate surfactant, and they are that chemical formula is ROSO
3The water-soluble salt of M or acids, the wherein preferred C of R
10～C
24Alkyl, this alkyl preferred alkyl or C is arranged
10～C
20The hydroxyalkyl of alkyl component, more preferably C
12～C
18Alkyl or hydroxyalkyl, with M be H or positively charged ion, as alkali metal cation (as sodium, potassium, lithium) or ammonium or replace ammonium (as methyl-, dimethyl-and trimethyl ammonium positively charged ion and quaternary ammonium cation such as tetramethyl-ammonium and lupetidine positively charged ion and by alkylamine such as ethamine, diethylamide, triethylamine and their deutero-quaternary ammonium cations such as mixture).Typically, to the preferred C of low wash temperature (promptly being lower than about 50 ℃)
12～C
16Alkyl chain and to the preferred C of higher wash temperature (promptly being higher than about 50 ℃)
16～18Alkyl chain.
For cleaning purpose other useful anion surfactants also can be comprised among the detergent composition of the present invention.These can comprise soap salt (ammonium salt that comprises for example sodium, potassium, ammonium and replacement as single-, two-and triethanolamine salt), C
8～C
22The alkane sulfonate of firsts and seconds, C
8～C
24Alkene sulfonate, as british patent specification number 1,082,179 described sulfonated polycarboxylic acid, C by the sulfonated preparation of alkaline earth metal citrate thermal cracking products
8～C
24Alkyl polyglycol ether sulfate (containing oxyethane), alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol vitriol, alkyl phenol epoxy ethane ether salt, paraffin sulfonate, alkylphosphonic, isethionate such as acyl isethinate, N-acyl taurine salt, amber alkyl amide salts and sulfosuccinate, sulfosuccinic acid monoesters (especially saturated and undersaturated C up to 10 moles
12～C
18Monoesters) and sulfosuccinic acid diester (especially saturated and undersaturated C
6～C
12Two i esters), the one-level alkyl-sulphate of the vitriol of the vitriol of acyl sarcosinate, alkyl polysaccharide such as alkyl dextran glycosides (non-ionic type non-sulfuric acid compound will be narrated hereinafter), side chain and be RO (CH as chemical formula
2CH
2O)
k-CH
2COO
-M
+Alkyl polyethoxye carboxylate salt wherein R be C
8～C
22Alkyl, k are that 1～10 integer and M are the positively charged ions that forms soluble salt; Resin Acid and hydrogenated resin acids also suit, as rosin, staybelite and Resin Acid and the hydrogenated resin acids that exists or derive in Yatall MA.
In " tensio-active agent and washing composition " (volume I and II, Perry Schwartz and Berch work), narrated further example.Also in the United States Patent (USP) 3,929,678 that people such as Laughlin issued on December 30th, 1,975 23 row, 58 the row～29 row, 23 the row in (being added herein by reference) various such tensio-active agents are usually disclosed.
As long as wherein comprise, scouring agent composition typically of the present invention contains about 1%～about 40 weight %, preferably approximately 3%～approximate weight 20% this anion surfactant.
The included alkyl alkoxylated sulfate surfactant of anion surfactant very preferably is that chemical formula is RO (A)
mSO
3The water-soluble salt of M or acids, wherein R is unsubstituted C
10～C
24Alkyl or C is arranged
10～C
24The hydroxyalkyl of alkyl composition, preferred C
12～C
20Alkyl or hydroxyalkyl, more preferably C
12～C
18Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3 and M be H or positively charged ion, can be as metallic cation (as sodium, potassium, lithium, calcium, magnesium etc.), ammonium or replacement-ammonium cation.Alkyl ethoxylated sulfate and alkyl propoxylated sulphates are that this paper watches attentively.Replace the special example of ammonium cation comprise methyl-, dimethyl, trimethylammonium-ammonium cation and quaternary ammonium cation such as tetramethyl--ammonium and lupetidine positively charged ion and those alkylamines such as ethamine, diethylamine, triethylamine and their mixture deutero-ammonium cation, etc.The enforcement of tensio-active agent is C
12～C
18Alkyl polyethoxylated (1.0) vitriol (C
12～C
18E (1.0) M), C
12～C
18Alkyl polyethoxylated (2.25) vitriol (C
12～C
18E (2.25) M), C
12～C
18Alkyl polyethoxylated (3.0) vitriol (C
12～C
18E (3.0) M) and C
12～C
18Alkyl polyethoxylated (4.0) vitriol (C
12～C
18E (4.0) M), wherein M generally is selected from sodium and potassium.
That detergent composition of the present invention also can contain is cationic, amphoteric, zwitterionic and half-polar tensio-active agent, and the non-ionic type and/or the anion surfactant that are different from above to be narrated.
The cationic cleansing surfactants that is suitable for detergent composition of the present invention has a long-chain alkylene.The example of this cats product comprises ammonium surfactant such as alkyl-trimethylammonium halide salt, is the tensio-active agent with following chemical formula: [R
2(OR
3)
y] [R
4(OR
3)
y]
2R
5N
+X
-R wherein
2Be alkyl or the alkyl benzyl that about 8～about 18 carbon atoms are arranged on alkyl chain; Each R
3Be selected from-CH
2CH
2-,-CH
2CH (CH
3)-,-CH
2CH (CH
2OH)-,-CH
2CH
2CH
2-and their mixture; Each R
4Be selected from C
1～C
4Alkyl, C
1～C
4Hydroxyalkyl, by connecting two R
4The benzyl rings of group formation structure ,-CH
2CHOH-CHOHCOR
6CHOHCH
2OH is R wherein
6Be any hexose or molecular weight less than about 1000 hexose polymkeric substance, and be hydrogen when y is not 0; R
5Be and R
4Identical, or alkyl chain R wherein
2Add R
5The total number of carbon atoms is not more than about 18; Each y be 0～about 10 and the y value and be 0～about 15; With X be the negatively charged ion of any compatibility.
The quaternary ammonium surfactant that the present invention suits has chemical formula (I):
Formula I is R wherein
1Be the alkyl (C of chain length
6～C
10) or the alkyl amido alkyl of chemical formula (II):
Formulae II
Y is 2～4, preferred 3.
R wherein
2Be H or C
1～C
3Alkyl;
Wherein x is 0～4, and is preferred 0～2, most preferably 0;
R wherein
3, R
4And R
5Be identical or different, and can be short alkyl chain (C
1～C
3) or the alkoxylated alkyl of Formulae II I;
X wherein
-Be counter ion, preferred halogeno-group example hydrochloric acid salt or Methylsulfate.
Formulae II I
R
6Be C
1～C
4With z be 1 or 2.
Preferred quaternary ammonium surfactant is the compound of Formula I definition, wherein R
1Be C
8, C
10Or their mixture, x=0,
R
3, R
4=CH
3And R
5=CH
2CH
2OH.
Useful cats product very preferably is water-dissolubility quaternary ammonium compound in this composition, and its chemical formula is:
R
1R
2R
3R
4N
+X
-(i)
R wherein
1Be C
8～C
18Alkyl, each R
2, R
3And R
4Be C independently
1～C
4Alkyl, C
1～C
4Hydroxyalkyl, benzyl and-(C
2H
4O)
xThe H wherein value of x is 2～5, and X is a negatively charged ion.R
2, R
3Or R
4Middle benzyl is answered no more than one.Preferred R
1Alkyl chain length be C
12～C
15, particularly wherein alkyl is the mixing of different chain length degree, is derived or is constructed or the OXO alcohols is synthetic manually derives by alkene by Oleum Cocois or palm seed oil; Preferred R
2, R
3And R
4Group is that methyl and hydroxyethyl and negatively charged ion X can be selected from halogeno-group, methylsulfate, acetate moiety and phosphate anion.
Here Shi Yi chemical formula (i) quaternary ammonium compound example has:
The muriate of cocounut oil trimethyl ammonium or bromide; The muriate or the bromide of cocounut oil methyl dihydroxy ethyl ammonium; The muriate of decyl triethyl ammonium; The muriate or the bromide of decyl dimethyl hydroxyl ethyl ammonium; C
12～15The muriate of dimethyl hydroxyl ethyl ammonium or bromide; The muriate or the bromide of coco dimethyl hydroxyethyl ammonium; The Methylsulfate of myristyl trimethyl ammonium; The muriate of lauryl dimethyl hexadecyldimethyl benzyl ammonium or bromide; The muriate or the bromide of lauryl dimethyl (oxyethylene group) 4 ammoniums; Cholinesterase (chemical formula (i) compound, wherein R
1Be:
Alkyl and R
2R
3R
4Be methyl); Two-alkyl imidazoline [chemical formula (i) compound].
The United States Patent (USP) 4,228,044 of October 14 authorizing at Cambre1980 and in European patent application EP 000,224, also narrated other useful cats products here.
Typical cationic fabric softening ingredient comprises water-insoluble season-ammonium fabric-softening activator or their corresponding amine precursors, and using the most common is two-long alkyl chain ammonium muriate or Methylsulfate.
Comprise following compounds among the preferred cation tenderizer:
1) two tallow base dimethyl ammonium chlorides (DTDMAC);
2) dihydro tallow base dimethyl ammonium chloride;
3) dihydro tallow base Dimethyl Ammonium Methylsulfate;
4) distearyl dimethyl ammonium chloride;
5) two oil base dimethyl ammonium chlorides;
6) two palmityl hydroxyethyl ammonium methyl muriates;
7) stearyl benzyl dimethyl ammonium muriate;
8) tallow base trimethyl ammonium muriate;
9) hydrogenated-tallow group trimethyl ammonium muriate;
10) C
12～14Alkyl hydroxy ethyl dimethyl ammonium chloride;
11) C
12～18Alkyl dihydroxy ethyl ammonium methyl muriate;
12) two (stearoyl-oxy ethyl) dimethyl ammonium chlorides (DSOEDMAC);
13) two (tallow-oxygen base-ethyl) dimethyl ammonium chloride;
14) two tallow tetrahydroglyoxaline Methylsulfates;
15) 1-(2-tallow l amido ethyl)-2-tallow base tetrahydroglyoxaline Methylsulfate.
Exist biodegradable quaternary ammonium compound as the muriate of two-long alkyl chain ammonium of routine use and the alternative surrogate of Methylsulfate.So quaternary ammonium compound contains long-chain alkane (alkene) base that inserts functional group such as carboxyl.Said material and the fabric softener composition that contains them is disclosed in numerous publications such as EP-A-0, in 040,562 and EP-A-0,239,910.
Here quaternary ammonium compound and amine precursor have following chemical formula (I) or (II):
Wherein Q be selected from-O-C (O)-,-C (O)-O-,-O-C (O)-O-,-NR
4-C (O)-,-C (O)-NR
4
R
1Be (CH
2)
n-Q-T
2Or T
3
R
2Be (CH
2)
m-Q-T
4Or T
5Or R
3
R
3Be C
1～C
4Alkyl or C
1～C
4Hydroxyalkyl or H;
R
4Be H or C
1～C
4Alkyl or C
1～C
4Hydroxyalkyl;
T
1, T
2, T
3, T
4, T
5Be C independently
11～C
22Alkyl or alkenyl;
N and m are 1～4 integers; And
X
-Be the negatively charged ion of tenderizer-compatibility, tenderizer-compatibility anionic non--limitative examples comprises chloro base or methylsulfate.
Alkyl or alkenyl chain T
1, T
2, T
3, T
4, T
5Must contain at least 11 carbon atoms, preferably at least 16 carbon atoms.Chain can be straight chain or side chain.Tallow is long-chain alkyl group and the convenient and cheap source of alkenyl compound.Particularly preferred compound is T wherein
1, T
2, T
3, T
4, T
5Represent typical tallow long-chain mixtures of material.
Here be suitable for the example bag of the special quaternary ammonium compound of aquosity fabric softener composition
Draw together:
1) N, N-two (tallow-oxygen base-ethyl)-N, N-dimethyl ammonium chloride;
2) N, N-two (tallow-oxygen base-ethyl)-N-methyl-N-(2-hydroxyethyl) ammonium methyl sulphate;
3) N, N-two (2-tallow-oxygen base-2-oxo-ethyl)-N, N-dimethyl ammonium chloride;
4) N, N-two (2-tallow-oxygen base-ethyl carbonyl-oxygen base-ethyl)-N, N-dimethyl ammonium chloride;
5) N-(2-tallow-oxygen base-2-ethyl)-N-(2-tallow-oxygen base-2-oxo-ethyl)-N, the N-dimethyl ammonium chloride;
6) N, N, N-three (tallow-oxygen base-ethyl)-N-ammonium methyl muriate;
7) N-(2-tallow-oxygen base-2-oxo-ethyl)-N-(tallow base-N, N-dimethyl-ammonium muriate; And
8) 1,2-two tallows-oxygen base-3-trimethylammonium ammonium propane chloride;
Mixture material with any above-claimed cpd.
If comprise, detergent composition of the present invention typically contains 0.2%～about 25 weight %, this cats product of preferably approximately 1%～about 8 weight %.
The amphoteric tensio-active agent also is suitable for detergent composition of the present invention.These tensio-active agents can be described as secondary aliphatic amine or tertiary amines derived thing widely, or aliphatics heterocyclic secondary and tertiary amines derived thing, and wherein aliphatic group can be straight chain-or side chain-chain.An aliphatics substituting group contains about at least 8 carbon atoms, and typically about 8～about 18 carbon atoms and at least one have anionic water-solubilizing group, i.e. carboxyl, sulfonate, vitriol.Consult the United States Patent (USP) 3,929 that people such as Laughlin delivered on December 30th, 1975,678 the 19th row, 18～35 row are as amphoterics.
If comprise, detergent composition of the present invention typically contains 0.2%～and about 15%, the amphoterics of preferably approximately 1%～about 10 weight %.
The zwitterionics detergent composition also suits.These tensio-active agents can be described as secondary amine and tertiary amines derived thing, heterocyclic secondary and tertiary amines derived thing or quaternary ammonium derivative ， quaternary phosphine or uncle's sulphur compound widely.19 row, 38 row～22 row, 48 row of consulting the United States Patent (USP) 3,929,678 that people such as Laughlin delivers on December 30th, 1975 are as zwitterionics.
If comprise, detergent composition of the present invention typically contains 0.2%～about 15%, the zwitterionics that preferably approximately 1%～about 35 weight 10% are such.
Half-the polarity nonionic surface active agent is a special class nonionic surface active agent, it comprises water-dissolubility amine oxide, and it contains the moieties of about 10～about 18 carbon atoms and 2 and is selected from alkyl and the hydroxyalkyl part that contains about 1～about 3 carbon atoms; The water soluble oxidized phosphine, it contain one about 10～approximately the moieties of 18 carbon atom and 2 are selected from alkyl and the hydroxyalkyl part that contains about 1～about 3 carbon atoms; With water-soluble sulfoxide, it contains moieties and an alkyl and a hydroxyalkyl part that is selected from about 1～about 3 carbon atoms of about 10～about 18 carbon atoms.
Half-polarity non-ionic detergent tensio-active agent comprises the amine oxide surfactant with following chemical formula:
R wherein
3Be to contain alkyl, hydroxyalkyl or the alkyl phenyl of about 8～about 22 carbon atoms or their mixture; R
4Be alkylidene group, hydroxy alkylidene or their mixture that contains about 2～about 3 carbon atoms; X is 0～about 3; With each R
5Be alkyl or the hydroxyalkyl that contains about 1～about 3 carbon atoms, or contain the polyethylene oxide of about 1～about 3 ethylene oxide groups.R
5Group can be as being interconnected to form ring structure by oxygen or nitrogen-atoms.
These amine oxide surfactants are particularly including C
10～C
18Alkyl dimethyl amine oxide and C
8～C
12Alkoxyethyl dihydroxy ethyl amine oxide.
If contain, cleaning compositions of the present invention typically contains 0.2%～and about 15%, the half-polarity nonionic surface active agent that preferably approximately 1%～about 10 weight % are such.
Detergent composition of the present invention can further contain tensio-active agent and be selected from primary amine or tertiary amine.
Suitable primary amine used herein comprises according to chemical formula R
1NH
2Amine, R wherein
1Be C
6～C
12, preferred C
6～C
10Alkyl chain, or R
4X (CH
2)
nWherein X be-O-,-C (O) NH-,-NH-, R
4Be C
6～C
12Alkyl chain, n are between 1～5, preferred 3.R
1Alkyl chain can be straight chain or side chain, and can insert up to 12, preferably less than 5 ethylene oxide moieties.Preferably according to the amine of formula hereinabove be just-alkylamine.Suitable amine used herein can be selected from 1-hexyl amine, 1-octyl amine, 1-decyl amine and lauryl amine.Other preferred primary amine comprise C
8～C
10Oxygen propyl group amine, octyl group oxygen propyl group amine, 2-ethylhexyl-oxygen propyl group amine, the amino propylamine of lauroyl and amido propylamine.
Suitable tertiary amine used herein comprises chemical formula R
1R
2R
3The tertiary amine of N, wherein R
1And R
2Be C
1～C
8Alkyl chain or
R
3Or 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
12N is between 1～5, preferred 2～3; R
5Be H or C
1～C
2Alkyl and x are between 1～6.
R
3And R
4Can be linearity or side chain; R
3Alkyl chain can insert up to 12, preferably less than 5 ethylene oxide moieties.
Preferred tertiary amine is R
1R
2R
3N is R wherein
1Be C
6～C
12Alkyl chain, R
2And R
3Be C
1～C
3Alkyl or
R wherein
5Be H or CH
3And x=1～2.
Amidoamines further preferably, its chemical formula is:
R wherein
1Be C
6～C
12Alkyl; N is 2～4, preferably n is 3; R
2And R
3Be C
1～C
4
The most preferred amine of the present invention comprises 1-octylame, 1-hexylamine, 1-decyl amine, 1-n-Laurylamine, C
8-10Oxygen propyl group amine, N-cocounut oil-1, two (hydroxyethyl) amine of 3-diaminopropanes, cocounut oil alkyl dimethyl amine, lauryl dimethyl amine, lauryl, two (hydroxyethyl) amine of cocounut oil, 2 moles of propoxylation lauryl amines, 2 moles of propoxylation octylames, the amino propyl-dimethyl amine of lauroyl, C
8-10Amido propyl-dimethyl amine and C
10The amido propyl-dimethyl amine.
The most preferred amine that uses at this composition is 1-hexylamine, 1-octylame, 1-decyl amine, the 1-n-Laurylamine.Especially desirable be just-dodecyl dimethyl amine and double hydroxyethyl cocounut oil alkylamine and 7 times of ethoxylation oleyl amines, the amino propylamine of lauroyl and cocounut oil amido propyl group amine.SYNTHETIC OPTICAL WHITNER
Detergent composition of the present invention except the selected bleach system of the present invention, also can further contain other SYNTHETIC OPTICAL WHITNER.
Spendable SYNTHETIC OPTICAL WHITNER comprises halogen bleaching agent.Sodium and sylvite and N-chloro and the N-bromoalkane sulphonamide of the example of inferior halite SYNTHETIC OPTICAL WHITNER as comprising three chloro isocyanuric acids and dichloro-isocyanuric acid.These materials generally add 0.5～10 weight % of final product, preferred 1～5 weight %.
This area is also understood the SYNTHETIC OPTICAL WHITNER that is different from oxygen bleaching agent and can be used at this.Non--the oxygen bleaching agent of one class particularly important comprises photoactivation SYNTHETIC OPTICAL WHITNER such as sulfonated zinc phthalocyanine and/or aluminium phthalocyanine.These materials can deposit on the substrate in washing process.By the irradiation of light, dry down as clothing being hung over outside daylight, Sulfonated zinc phthalocyanine is activated in the presence of oxygen, and substrate has just been bleached.At United States Patent (USP) 4,033, preferred zinc phthalocyanine and photoactivation bleaching method have been narrated in 718.Detergent composition typically contains the sulfonated zinc phthalocyanine of about 0.025%～about 1.25 weight %.Builder system
Detergent composition of the present invention can further contain washing assistant.Any conventional builder system all suits in this use, it comprises aluminosilicate material, silicate, polycarboxylate, alkyl-or alkenyl-succsinic acid and fatty acid material such as ethylenediamine tetraacetate, diethylenetriamine pentylidene acetic ester, metal ion chelation agent such as amino polyphosphonate, particularly ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentylidene phosphonic acids.Phosphate builders also can use at this.
Suitable washing assistant can be an inorganic ion exchange material, generally is inorganic hydrated aluminum silicate material, more particularly the synthetic zeolite of hydration such as hydrated zeolite A, X, B, HS or MAP.
Shi Yi inorganic builders material is a layered silicate in addition, i.e. SKS-6 (Hoechst).SKS-6 is by water glass (Na
2Si
2O
5) crystalline layered silicate formed.
Disclose the suitable polycarboxylate that contains a carboxyl in the belgian patent 831,368,821,369 and 821,370 and comprised lactic acid, oxyacetic acid and their ether derivant.The multi-carboxylate of containing two carboxyls comprises that the water-soluble salt and the ether carboxylate of succsinic acid, propanedioic acid, (ethylidene dioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid disclose 2 in Germany, 446,686, with 2,446,687 and United States Patent (USP) 3,935.257 in explanation is arranged; The carboxylic acyl ester has explanation in belgian patent 840,623; The carboxylate salt that contains three carboxyls comprises, particularly, water-soluble citrate, aconitate and stubborn health hydrochlorate and succinate derivative such as carboxyl methoxy succinate be in English Patent 1,379, explanation arranged in 241; The lactyl succinate has explanation in Holland's application 7205873; With oxidation multi-carboxylate material such as 2-oxygen-1,1,3-tricarballylic acid salt is in English Patent 1,387, explanation arranged in 447.
The multi-carboxylate of containing four carboxyls is included in English Patent 1,261, disclosed oxygen di-succinate, 1,1,2 in 829,2-ethane tetracarboxylic acid salt, 1,1,3,3-propane tetramethyl hydrochlorate and 1,1,2,3-propane tetramethyl hydrochlorate.Contain the substituent multi-carboxylate of sulfo group and be included in English Patent 1,398,421 and 1,398,422 and United States Patent (USP) 3,936,448 in disclosed sulfo-succinic acid salt derivative, with in English Patent 1, the sulfonated thermo-cracking Citrate trianion of 082,179 narration contains the substituent multi-carboxylate of phosphorus simultaneously in English Patent 1, open in 439,000.
Alicyclic ring and heterocycle multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetramethyl hydrochlorate, cyclopentadiene five formate, 2,3,4,5-tetrahydrochysene-furans-suitable, suitable, suitable-tetramethyl hydrochlorate, 2,5-tetrahydrochysene-furans-suitable-diformate, 2,2,5,5-tetrahydrofuran (THF)-tetramethyl hydrochlorate, 1,2,3,4,5, the carboxymethyl derivant of 6-hexane-pregnancy hydrochlorate and poly-hydroxy alcohols such as sorbyl alcohol, N.F,USP MANNITOL and Xylitol.Aromatic multi-carboxy acid's salt comprises mellitic acid, benzene tetracarboxylic acid and phthalic acid derivatives in English Patent 1,425, and is open in 343.
Preferred in sum multi-carboxylate is the hydroxycarboxylate of containing up to three carboxyls of per molecule, more particularly Citrate trianion.
Be used for the mixture that the preferred builder system of this composition comprises water-insoluble aluminosilicate washing assistant such as zeolite A or layered silicate (SKS-6) and water-soluble carboxylate sequestrant such as citric acid.Other preferred builder systems comprise the mixture of water-insoluble aluminosilicate washing assistant such as zeolite A and water-soluble carboxylate sequestrant such as citric acid.The builder system that is preferred for liquid detergent composition of the present invention is soap and multi-carboxylate.
Other washing assistant materials of part builder system be can be formed in the granular composition and inorganic materials such as alkaline carbonate, supercarbonate, silicate and organic materials such as organic phosphonate, amino poly-(alkylidene group) phosphonate and aminopolycanboxylic acid's salt comprised.Other suitable water-soluble organic salts are homopolymerization-or copolymerization-acids or their salt, and wherein poly carboxylic acid contains at least two carboxyls, and they are spaced from each other by no more than two carbon atom.The polymkeric substance of this type is at GB-A-1, and is open in 596,756.The example of such salt is the multipolymer of the polyacrylate of MW 2000～5000 and they and maleic anhydride, and this multipolymer has molecular weight 20,000～70,000, and especially be about 40,000.
Usually the detergency builder salt amount that comprises is 5%～80% of a composition weight, preferred 10%～70% and be generally 30%～60 weight % most.Conventional detergent enzyme
Detergent composition can further contain one or more enzymes except the pectate lyase, and they provide clean-up performance, fabric nursing and/or health interests.Preferred detergent composition of the present invention will further contain a kind of pectin lyase.
Said enzyme comprises that enzyme is selected from cellulase, hemicellulase, peroxidase, proteolytic enzyme, glucose-amylase, amylase, zytase, lipase, Phospholipid hydrolase, esterase, at, other polygalacturonases, keratanase, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannic acid enzyme, pentosanase, malanases, beta-glucanase, arabinofuranosidase/xylosidase, Unidasa, chondroitinase, laccase or their mixture.Preferred combination is to have the common detergent composition of using the enzyme mixed thing, these enzymes such as proteolytic enzyme, and amylase, lipase, at and/or cellulase are united one or more plant cell-wall degrading enzymes.
All types of pectin degrading enzymes, under different hardness, pH, temperature, tensio-active agent and other detergent ingredients matrix conditions, the Substratspezifitaet with unique types, active and stable.Pectin degrading enzyme certain orientation depolymerized pectin material and particularly plant cell wall.Particularly, the pectate lyase be certain orientation in the pectic acid chain of plant cell wall such as low methoxypectin, and the pectin lyase certain orientation is in esterify pectin chain such as high methoxyl pectin.And find the pectate lyase to metal and calcium sensitivity especially, but pectin lyase does not need metal for stable with best enzymic activity.Be surprisingly found out that and pectate lyase of the present invention and the further combination of pectin lyase can be reached the Substratspezifitaet of wide region and the high-adaptability of various wash conditions.This causes synergic cleaning and the especially removal of plant-Ji dirt/stain and health dirt.
Pectin lyase is classified as EC 4.2.2.10 in EC classification, preferably do not contain other polygalacturonases substantially, and act on pectic acid cause α-(1 → 4)-glycosidic link non--hydrolysis decomposes, and provides the terminal oligosaccharides of 4-deoxidation-6-α-D-gala-glycal aldehydic acid group that is.Pectin lyase of the present invention does not contain other polygalacturonases substantially." do not contain other polygalacturonases substantially " and be meant the composition that contains pectin lyase and contain that to be less than 25% be not the polygalacturonase of pectin lyase, preferably be less than 15%, more preferably less than 5%.Can be according to K.Horikoshi at Agr.Biol.Chem, Vol 36 (2), and method is measured the activity of this enzyme described in 286 " trans-elimination enzyme is to the activation of pectin and pectic acid ".
Preferred in the present invention pectin lyase is the pectin lyase of narrating in common co-pending international patent application PCT/DK98/00514, this application submission on November 24th, 1998 and open with WO99/27083, and this pectin lyase is:
I) polypeptide a kind of by Bacillus licheniformis, that ATCC14580 produces, or
An ii) peptide species, it contains among the PCT/DK98/00514 SEQ ID NO:2 at 31-494
The aminoacid sequence that the position shows, or
Iii) by i) or the ii) analogue of polypeptide of definition, wherein have at least with said polypeptide
60% homology, or
Iv) be substituted, delete, increase and spread out by one or several amino acid by said polypeptide
Give birth to, just in relevant PCT/DK98/00514 SEQ ID NO:2 377 and 283
Arginine on the position keeps, and this polypeptides derived and said polypeptide have
At least 60% homology, or
The polyclonal antibody that produces with the said polypeptide of purified form has immunological response.
Suitable proteolytic enzyme is subtilysin, and it derives from special bacterial classification B.subtilis and B.licheniformis (subtilysin BPN and BPN ').A kind of suitable proteolytic enzyme derives from the genus bacillus bacterial classification, has maximum activity in whole scopes of pH 8～12, and this enzyme is by the Denmark Novo Industries A/S exploitation that hereinafter claims " Novo ", and sells with ESPERASE .At the GB1 of Novo, 243,784 kinds of preparations of having narrated this enzyme and similar enzyme.Other suitable proteolytic enzyme comprise ALCALASE , DURAZYM and SAVINASE that derives from Novo and MAXATASE , MAXACAL , PROPERASE and the MAXAPEM that derives from Gist-Brocades (Maxacal of protein design).Proteolytic ferment also comprises modifies bacterial serine proteolytic enzyme, as explanation (particularly 17 is arranged in the european patent application series number 87 303761.8 that proposes on April 28th, 1987,24 and 98 pages), this kind of enzyme is known as " proteolytic enzyme B " at this paper, and the modification bacterial serine proteolytic ferment that relates in the european patent application 199,404 of the Venegas that delivers on October 29th, 1986 is known as " protease A " at this paper.Suitable is that this paper is called the proteolytic enzyme of " proteolytic enzyme C ", it is a kind of variant that derives from the alkaline serine protease of genus bacillus, wherein Methionin has replaced 27 arginine, tyrosine replaces 104 Xie Ansuan, Serine replaces l-asparagine and 274 Threonines of L-Ala replacement of 123.Proteolytic enzyme C has explanation in EP 90915958:4, the WO 91/06637 that this article was delivered corresponding on May 16th, 1991.The variant that has comprised genetic modification in this article, particularly proteolytic enzyme C.
The proteolytic enzyme that preferably is called " proteolytic enzyme D " is the mutant of carbonylic hydrolase, and its aminoacid sequence does not find that at nature it is by the deutero-with most amino-acid residues on some position of different aminoacid replacement by the carbonylic hydrolase precursor, the position of this replacement is equivalent in said carbonylic hydrolase+76 with the preferably combination of one or more amino acid residue positions, these positions according to the numbering of bacillus amyloliquefaciens subtilysin be equivalent to be selected from+99 ,+101, + 103 ,+104 ,+107, + 123 ,+27 ,+105, + 109 ,+126 ,+128, + 135 ,+156 ,+166, + 195, + 197 ,+204 ,+206, + 210, + 216 ,+217 ,+218, + 222, + 260 ,+265, and/or+274, in people's such as WO95/10591 and C.Ghosh patent application " bleaching composition that comprises the proteolytic enzyme enzyme ", explanation is arranged, this patent application proposed on October 13rd, 1994, and application number is 08/322,677.The carbonylic hydrolase mutant of the proteolytic enzyme that also suitable is narrates in WO95/10591, its aminoacid sequence is derived from the replacement of most amino-acid residues on some position of pre-enzyme, this position in pre-enzyme corresponding to the combination of+210 and and a plurality of following residues :+33, + 62 ,+67 ,+76, + 100 ,+101 ,+103, + 104 ,+107 ,+128, + 129 ,+130 ,+132, + 135 ,+156 ,+158, + 164 ,+166 ,+167, + 170, + 209 ,+215 ,+217, + 218, with+222, wherein numbered positions is equivalent to the subtilysin that is derived from bacillus amyloliquefaciens or other carbonylic hydrolases or the subtilysin of nature-appearance, as amino-acid residue equal in the bacillus lentus subtilysin (common unexamined patent application u.s. id 60/048, on June 04th, 550,1997 proposed).
What the present invention was also suitable is the proteolytic enzyme of narration in patent application EP 251 446 and WO 91/06637, in WO 91/02792 the proteolytic enzyme BLAP of narration with WO 95/23221 in their mutant of narration.
Also consult the high pH proteolytic enzyme of narrating among the WO93/18140 A of Novo that is derived from genus bacillus kind NCIMB40338.Narrated the enzyme-containing detergent that contains proteolytic enzyme, one or more other enzymes and reversible protease inhibitors in the WO of Novo 92/03529 A kind.When needed, can utilize as at Procter﹠amp; The proteolytic enzyme with absorption reduction and hydrolysis property increase of narration among the WO 95/07791 of Gamble.In the WO 94/25583 of Novo, narrated suitable detergent use recombination classes Regular Insulin-proteolytic enzyme here.Other suitable proteolytic enzyme in the EP 516 200 of Unilever, have been narrated.
The level of mixing of proteolytic ferment is 0.0001%～2% of a composition weight in the detergent composition of the present invention, and is preferred 0.001%～0.2%, more preferably 0.005%～0.1% pure enzyme.
The useful cellulase of the present invention comprises cellulase bacterium or fungi.Preferably they have best pH between 5～12, are higher than 50 CEVU/mg (Mierocrystalline cellulose viscosity unit) than living.Suitable cellulase is at people's such as Barbesgoard United States Patent (USP) 4,435,307, open among J61078384 and the WO96/02653, they disclose plants the fungal cellulase that mould insolens, Trichoderma, shuttle spore shell fungi and Sporotrichum are produced by corruption respectively.EP 739 982 has narrated by the isolating cellulase of new gemma bacillus specie.Suitable cellulase also is disclosed among GB-A-2.075.028, GB-A-2.095.275, DE-OS-2.247.832 and the WO 95/26398.
So the example of cellulase is to plant mould insolens (mould var.thermoidea is planted in grey corruption) by the bacterial classification corruption, particularly rotten cellulase of planting mould kind DSM1800 production.
Other suitable cellulases are to be derived from the cellulase that mould insolens is planted in corruption, and the molecular weight that it has is about 50 KDa, and iso-electric point is 5.5 and contains 415 amino acid; And be derived from corruption and plant mould insolens, DSM 1800～endoglucanase of 43kD, the activity of the plain enzyme of its display fibers, the aminoacid sequence that preferred endoglucanase component is had is disclosed among the PCT patent application WO91/17243.Suitable cellulase also has the EGIII cellulase from long beach Trichoderma, and the WO 94/21801 that September 29 delivered at Genencor1994 has explanation.Especially Shi Yi cellulase is the cellulase that color nursing advantage is arranged.So the example of cellulase is the cellulase of narration in european patent application 91202879.2, this application proposition on November 6th, 1991 (Novo).Carezyme and Celluzyme (Novo Nordisk AIS) are particularly useful.Also consult other cellulases that are suitable for fabric nursing and/or clean-up performance of WO91/17244 and WO91/21801. and in WO96/34092, WO96/1 7994 and WO95/24471, explanation is arranged.
The level of mixing said cellulase in the detergent composition usually is 0.0001%～2% a pure enzyme of detergent composition weight.
The peroxidase enzyme uses with oxygen source, and oxygen source such as percarbonate, perborate, persulphate, hydrogen peroxide etc. are done bleaching with aldehydes matter and strengthened molecule.They are used for " solution bleaching ", promptly prevent to transfer on other matrix of washing soln from dyestuff and pigment that matrix is removed in washing operation.The peroxidase enzyme that this area is understood comprises, for example horseradish peroxidase, lignoenzyme and haloperoxidase such as chloro-and bromo-peroxidase.The detergent composition that contains peroxidase is in for example PCT International Application No. WO 89/099813, and is open among the EP No.96870013.8 that the European patent application EP No.91202882.6 that WO89/09813 and on November 6th, 1991 propose and on February 20th, 1996 propose.Also suitable is laccase.
The level that general toughener contains is 0.1%～5% of a total composition weight.The thiodiphenylamine that preferred toughener is replacement is with the syringates (C of phenoxazine lysivane propionic acid (PPT), 10-ethyl thiodiphenylamine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP) and 10-Jia Ji phenoxazine (have in WO94/12621 and state) and replacement
3～C
5Substituted alkyl syringates) and phenols.Percarbonic acid or Sodium peroxoborate are preferred hydrogen peroxide cources.
The level of mixing said peroxidase in the detergent composition usually is 0.0001%～2% a pure enzyme of detergent composition weight.
Other preferred enzymes that can be included in the detergent composition of the present invention comprise lipase.In English Patent 1,372, the lipase enzyme that suitable washing composition uses is disclosed in 034, it comprises those enzymes of being produced by Pseudomonadeae microorganism such as Situ thatch aeruginosa atcc 19.154.Suitable lipase comprises that those and lipase antibody present the enzyme of positive immunology intersection-reaction, and this lipase is produced by microorganism pseudomonas fluorescence IAM 1057.This lipase can utilize the product of Japan Nagoya Amano pharmaceutical Co. Ltd, and commodity are called lipase P " Amano ", hereinafter are called " Amano-P ".Other suitable commercial lipase comprise Amano-CES, the sticking look bacillus of the lipase of the Toyo Jozo company of Japan Tagata, promptly separate the sticking look bacillus NRRLB 3673 of fat, the sticking look bacillus purport fat enzyme of the Disoynth company of U.S. Biochemics Inc. of the U.S. and Holland, with lipase ex gladiolus pseudomonas, especially Shi Yi lipase is lipase such as Ml Lipase
RAnd Lipomax
R(Gist-Brocades) and Lipolase
RWith Lipolase Ultra
R(Novo), find that they mix when using with the present composition be very effective.Suitable also have lipolytic enzyme, at EP 258 068, the WO92/05249 of Novo Nordisk and WO 95/22615 with at WO 94/03578, WO 95/35381 and the WO96/00292 of Unilever explanation arranged.
Suitable at [EC 3.1.1.50] in addition, it can be considered to a kind of special lipase, does not promptly need interface activated lipase.In as WO-A-88/09367 (Genencor), WO90/09446 (plant genetic system) and WO 94/14963 and WO 94/14964 (Unilever), narrated and in detergent composition, added at.
The level of mixing lipase and/or in the detergent composition usually is 0.0001%～2% a pure enzyme of detergent composition weight.
Can comprise amylase (α and/or β) to remove carbohydrate-Ji stain.NovoNordisk A/S on February 03rd, 1994 disclosed WO94/02597 the composition that adds mutant amylase washing composition has been described.Consult the WO95/10603 that Novo Nordisk A/S delivered in April 20 nineteen ninety-five.Other amylase that become known for detergent composition comprise α-and beta-amylase.This area has been understood α-Dian Fenmei, and it comprises and is disclosed in US Pat, no.5,003,257, EP 252,666, WO/91/00353, FR 2,676,456, EP 285,123, EP 525,610, EP 368,341 and british patent specification no.1, those enzymes among 296,839 (Novo).Other suitable amylase are stability-enhancing amylase, among the WO96/05295 that WO94/18314 that delivers on August 18th, 1994 and Genencor1996 delivered at February 22 explanation are arranged; And in the WO95/10603 that delivers in April, 95 the disclosed amylase variant of on immediate parent, being modified, parent utilizes the product of Novo Nordisk A/S.Suitable also has at EP 277 216, the amylase of narration among WO95/26397 and the WO96/23873 (all being proposed by Novo Nordisk).
The example of commercial α-Dian Fenmei product has Purafect Ox Am and Termamyl , Ban , Fungamyl and the Duramyl of Genencor production, all can utilize the product of Denmark Novo NordiskA/S.Other suitable amylase have been described: a kind of α-Dian Fenmei in WO95/26397, feature is that it is higher than 25% than the ratio work of termamyl at least than work, than work is temperature in 25 ℃～55 ℃ scopes and pH value in 8～10 scopes, chemically examines with Phadebas alpha-amylase activity and measures.In WO96/23873 (Novo Nordisk), narrated the variant of suitable above-mentioned enzyme.Relevant activity level and thermostability and other amylolytic enzymes of the bonded improvement in performance of high reactivity level more in WO95/35382, have been narrated.
The level that adds amylolytic enzyme in the detergent composition of the present invention is 0.0001%～2% of a composition weight, and is preferred 0.00018%～0.06%, more preferably 0.00024%～0.048% pure enzyme.
Above-mentioned enzyme can be derived from any suitable source, as vegetables, and animal, bacterium, fungi and yeast source.The source can further be have a liking for temperature or have a liking for extreme environment (psychrophilic, suitable cold, thermophilic, have a liking for pressure, that have a liking for alkali, have a liking for acid, happiness salt etc.).Can use form these enzyme purifications or non--purifying.Now, in order to make their effectiveness of performance optimizings in detergent composition of the present invention, convention is to modify the enzyme of wild-type by protein/gene engineering usually.For example, design variable makes enzyme and the consistency of these composition components of running into usually increases.Perhaps design variable is fit to special cleaning applications so that repair best pH, bleaching or sequestrant stability, the catalytic activity etc. of this enzyme variants.
Particularly, should concentrate on the amino acid to oxidation-sensitive, and should concentrate on the surface charge for the surfactant compatibility attention the situation attention of bleach stability.Can revise the iso-electric point of these enzymes by replacing some charged amino acid, can help to improve consistency with anion surfactant as increasing iso-electric point.Increase sequestrant stability by creating other salt bridge and strengthening the calcium binding site, further improve the stability of enzyme.Cellulase must be paid special attention to,, the performance of these enzymes can be changed by modifying these zones because most cellulase has isolating calmodulin binding domain CaM (CBD).
The level of mixing said enzyme in the detergent composition usually is 0.0001%～2% a pure enzyme of detergent composition weight.Enzyme can be used as separately single component (containing a kind of bead, saccharoid of enzyme, stable liquid etc.) or adds (as closing saccharoid altogether) as the mixture of two or more enzymes.
Other suitable detergent ingredients that add are oxydasis scavenging agents, and the common pending trial european patent application 92870018.6 that proposes on January 31st, 1992 has explanation.The example of this oxydasis scavenging agent is ethoxylation four ethylidene polyamines.
WO 9307263 A of Genencor International and WO 9307260 A, WO 8908694 A of Novo, with also disclose a series of enzyme materials and they joined the method for going in the synthetic detergent composition in U.S. 3,553,139 on January 5th, 1971 such as McCarty.These enzymes are further disclosed in the U.S. 4,507,219 in U.S. 4,101,457 on July 18th, 1978 such as Place and Hughes1985 March 26.In U.S.'s on April 14th, 1981 such as Hora 4,261,868, disclose the enzyme material that is used for liquid detergent formula and they have been joined the method for prescription like this.Can be by the various consistent enzymes that are used for washing composition.The EP199 in the U.S. 3,600,319 on August 17th, 1971 such as Gedge, Venegas1986 October 29,405 and EP 200,586 in open and the enzyme stabilization technology has been described as an example.For example in the U.S. 3,519,570, also narrated the enzyme stabilization system.In the WO of Novo 9401532 A, narrated a kind of useful genus bacillus kind AC13 that provides proteolytic enzyme, zytase and cellulase.Color nursing and fabric nursing benefit
Also can comprise the technology that a class color care benefit is provided.The example of these technology is to be used for the metal catalyst that color is safeguarded.In common pending trial european patent application No.92870181.2., narrated this metal catalyst.Dye-fixing agent, resist-wrinkle and improve absorptive polyolefine dispersion agent, be used for that color nursing is handled and the spices and the amino-functional polymer (PCT/US97/16546) of spices affinity are the further examples of color nursing/fabric nursing technology, and in the common unexamined patent application No.96870140.9 of proposition on November 07th, 1996, explanation is arranged.
According to also mixing fabric softener in the detergent composition of the present invention.These tenderizers can be inorganic type or organic type.Example as inorganic tenderizer is at GB-A-1 400 898 and USP5,019,292 disclosed be terre verte.The organic fabric tenderizer comprises as disclosed water-fast tertiary amine in GB-A1 514 276 and EP-B0011 340 and they and single C
12～C
14The mixture of quaternary ammonium salt and two-length-chain acid amides, this list C
12～C
14Quaternary ammonium salt is open in EP-B-0 026 527 and EP-B-0 026 528, and two-length-chain acid amides is open in EP-B-0 242 919.Other useful organic compositions of fabric-softening system are included in disclosed high molecular weight polyethylene oxide material in EP-A-0 299 575 and 0 313 146.
The horizontal extent that adds terre verte is usually 2%～20%, more preferably 5%～15 weight %, and this material is added in other components of prescription as the dry mixed component.The level that is mixed with woven fabrics tenderizer such as water-fast-tertiary amine or two long-chain acid amides materials is 0.5%～5 weight %, common 1%～3 weight %, and the level of high molecular weight polyethylene oxide material and water-soluble cationic material is 0.1%～2%, common 0.15%～1.5 weight %.These materials are added in the spraying drying part of composition usually, though they are added as the exsiccant hybrid fine particles or they are sprayed onto in other solids components of composition more convenient as fused liquid in some situation.Sequestrant
This detergent composition can contain one or more iron and/or manganese sequestrant arbitrarily.This sequestrant can be selected from all aminocarboxylate, amino phosphonates do, the multi-functional-aromatic chelator of replacement and their mixtures as hereinafter defining.Do not wish to be bound by theory, think these materials benefit be partly because they remove the unusual ability of iron and mn ion by forming the soluble chelating thing from washing soln.
As can selecting the useful aminocarboxylate of sequestrant to comprise edetate, N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid(EDTP) salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol Diglycocol, their basic metal, ammonium and substituted ammonium salt and their mixture.
Amino phosphonates do is used as sequestrant and also suits in the present composition, although only allow to exist the total phosphorus of minimum level in detergent composition.Amino phosphonates do and comprise that ethylenediamine tetraacetic (methylene phosphonic acid salt) is as DEQUEST.Preferred these amino phosphonates do do not contain alkyl or the kiki alkenyl group more than about 6 carbon atoms.
Here multi-functional-substituted aromatic sequestrant also is useful in composition.Consult the United States Patent (USP) 3,812,044 that people such as Connor issued on May 21st, 1974.The preferred compound of this class acid type is the dihydroxyl disulfobenzene, as 1, and 2-dihydroxyl-3,5-disulfobenzene.
Preferred as used herein biodegradable chelated dose has, as explanation in the United States Patent (USP) 4,704,233 in Hartman and Perkins1987 November 3, ethylenediamine disuccinate (" EDDS "), especially [S, S] isomer.
The composition here also can contain water-soluble methylglycine oxalic acid MGDA) salt (or acid type) as sequestrant or altogether-washing assistant, be useful with for example insoluble washing assistant as zeolite, layered silicate etc.
If use, these sequestrants generally will contain about 0.1%～about 15% of this detergent composition weight.More preferably, if use, sequestrant will contain 0.1% of about said composition weight～about 3.0%.Suds suppressor
Another selectable composition is a suds suppressor, and the example is siloxanes and silicon-dioxide-mixture of siloxanes.Siloxanes can generally exist with the alkylation silicone materials, and silicon-dioxide uses with the form of fine dispersion usually, for example aerosil and xerogel and all kinds water drain silica.Can be used as particulate and add these materials, in particulate, mix convenient releasable suds suppressor, particulate be water soluble or water-dispersible, do not have substantially-the impermeable carrier of surface-activated detergent.Perhaps, suds suppressor solubilized or be dispersed in the liquid vehicle, and use by being sprayed onto on one or more other compositions.Preferred silicone foam control agent is open in people's such as Bartollota United States Patent (USP) 3 933 672.Other useful especially suds suppressors are self-emulsifying silicone suds suppressors, in the German patent application DTOS 2 646 126 that delivered on April 28th, 1977 explanation are arranged.This examples for compounds is DC-544, is the product of the commercial Dow of utilization Corning, and it is a siloxane-glycol copolymer.Especially preferred Foam Control is the suds suppressor system that contains silicone oil and 2-alkyl-chain triacontanol mixture.Suitable 2-alkyl-alkanol is 2-butyl-octanol, is commercial available, and commodity are called Isofol 12 R.
This suds suppressor system has explanation in the common pending trial european patent application N92870174.7 that proposed November 10 in 1992.
The explanation in common pending trial european patent application N ° 92201649.8 of especially preferred silicone foam control agent.Said composition can contain and pyrolysis method atresia silicon-dioxide such as Aerosil
RBonded siloxanes/silica mixture.
Above-mentioned suds suppressor with 0.001%～2 weight % of composition weight, uses on the level of preferred 0.01%～1 weight % usually.Other
Can use other compositions that are used for detergent composition, as dirt-suspension agent, dirt-releasing agent, light brightener, abrasive material, sterilant, tarnishing inhibitor, tinting material and/or capsule is arranged or nothing-capsule spices.
It is especially suitable that to form capsular material be water-soluble capsule, it by as at GB 1,464,616 described polysaccharide and polyol matrix are formed.Other suitable capsular water-soluble materials of formation comprise the replacement dicarboxylic acid starch acid-ester deutero-dextrin by last gelation, and as at US 3,455,538 is described.Preferred these acid-ester dextrin is by as wax shape corn, wax shape Chinese sorghum, and sago, the starch of cassava and potato prepares.The example of the capsular material of said suitable formation comprises the N-Lok that is made by National Starch.This N-Lok capsule material is made up of W-Gum and the glucose modified.The modification of this starch is single function substituted radical such as an octenyl succinic acid anhydride in the addition.
Here Shi Yi antiredeposition and dirt suspension agent comprise derivatived cellulose such as methylcellulose gum, carboxy methyl cellulose and hydroxy ethyl cellulose and homopolymerization-or copolymerization-multi-carboxylic acid or their salt.This type polymer comprises polyacrylic ester and the maleic anhydride-acrylic copolymer of above mentioning as washing assistant, and the multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid, and wherein maleic anhydride constitutes 20 molecular fractions of multipolymer at least.Usually use 0.5%～10 weight % of the level of these materials as composition weight, more preferably 0.75%～8 weight %, most preferably 1%～6 weight %.
On the preferred light brightener feature is negatively charged ion, the example has 4,4 '-two-(2-diethanolamino-4-anilino-s-triazine-6-base is amino)-1,2-toluylene-2,2 '-disulfonic acid disodium salt, 4,4 '-two-(2-morpholino-4-anilino-s-triazine-6-base is amino)-1,2-toluylene-2,2 '-disulfonic acid disodium salt, 4,4 '-two-(2,4-hexichol amido-s-triazine-6-base is amino)-stilbene-2,2 '-disulfonic acid disodium salt, 4 '; 4 "-two-(2,4-hexichol amido-s-triazine-6-base is amino)-stilbene-2-sulfonic acid list sodium salt, 4,4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazine-6-base is amino)-stilbene-2,2 '-disulfonic acid disodium salt, 4,4 '-two-(4-phenyl-2,1,3-triazolyl-2-yl)-1,2-toluylene-2,2 '-disulfonic acid disodium salt, 4,4 '-two-(2-anilino-4-(1-methyl-2-hydroxyethyl amino)-s-triazine-6-base is amino)-1,2-toluylene-2,2 '-disulfonic acid disodium salt, 2 (stilbene radicals-4 "-(naphtho--1 ', 2 ': 4; 5)-1; 2,3-triazole-2 "-sodium sulfonate and 4,4 '-two (2-sulfo group styryl) biphenyl.Brightener very preferably is a disclosed brightener in EP 753 567.
Other useful polymer materialss are polyoxyethylene glycol, and particularly those molecular weight are 1000～10000, more especially 2000～8000 and most preferred about 4000 polyoxyethylene glycol.The level that they use is 0.20%～5%, more preferably 0.25%～2.5 weight %.Can adopt when having transition metal impurity that these polymkeric substance and above-mentioned homopolymerization-or copolymerization-carboxylate salt improves that whiteness is safeguarded, fabric dust precipitation and to the clean-up performance of earth, proteinic and oxidable dirt.
Normally terephthalic acid and ethylene glycol and/or the unitary multipolymer of propylene glycol or the ter-polymers of various arrangements of useful dirt releasing agent in the present composition.The example of this polymkeric substance be disclosed in common transfer United States Patent (USP) 4116885 and 4711730 and European publication patent application No.0 272 033 in.Have chemical formula according to EP-A-0 272 033 particularly preferred polymkeric substance:
(CH
3(PEG)
43)
0.75(POH)
0.25[(T-PO)
2.8(T-PEG)
0.4] T (PO-H)
0.25((PEG)
43CH
3)
0.75Wherein PEG is-(OC
2H
4) O-, PO is (OC
3H
6O) and T be (pcOC
6H
4CO).
Also very useful have dimethyl terephthalate (DMT), sulfoisophthalic acid dimethyl ester, ethylene glycol and 1, the modified poly ester of the random copolymerization of 2-propylene glycol, and this end group is made up of main sulfosalicylic acid ester and accessory ethylene glycol and/or third-diol monoester.Its target is to obtain the polymkeric substance that two ends all connect the sulfosalicylic acid ester group, and " mainly " refers to that in this paper context most end groups of said multipolymer here are by on the sulfosalicylic acid ester group cover.Therefore yet some multipolymers are by on the cover fully, and their end group may contain ethylene glycol and/or 1, the monoesters of 2-propylene glycol, and promptly wherein " inferior strategic point " contains these groups.
Here selected polyester contains 1 of the dimethyl terephthalate (DMT) of about 46 weight %, about 16 weight %, the sulfosalicylic acid dimethyl ester of the ethylene glycol of 2-propylene glycol, about 10 weight %, about 13 weight % and the sulfoisophthalic acid of about 15 weight % and to have molecular weight be about 3.000.This polyester and their preparation method have detailed description in EPA 311 342.
The very fast passivation of the enzyme that free chlorine in the tap water known in the state of the art contains detergent composition.Therefore, use chlorine scavenger such as perborate, ammonium sulfate, S-WAT or polymine in prescription, the level of use is more than 0.1% of total composition weight, will provide the wash stability of complete improved detergent enzyme.In the european patent application 92870018.6 that proposed on January 31st, 1992, narrated the composition that contains chlorine scavenger.
Be used herein to the grease that provides other as alkoxylate polycarboxylate and remove performance by the polyacrylic ester preparation.Such material is at WO 91/08281 and PCT 90/01815 page 4 and explanation is arranged later, and they add as a reference at this.Chemically the every 7-8 of the polyacrylic ester acrylic ester unit that contains of these materials has an oxyethyl group side-chain.The chemical formula of this side-chain is-(CH
2CH
2O)
m(CH
2)
nCH
3, wherein m be 2～3 and n be 6～12.This side-chain is connected to ester-key on " main chain " of polyacrylic ester " pectination " polymer type structure is provided.Its molecular weight may change, but typically in about scope of 2000～about 50,000.These alkoxylate polycarboxylates can contain about 0.05%～about 10% of this paper composition weight.Dispersion agent
Detergent composition of the present invention also can contain dispersion agent: suitable water-soluble organic salt is homopolymerization-or copolymerization-carboxylic acid or their salt, and wherein poly carboxylic acid contains at least two carboxyls, is spaced from each other by no more than two carbon atoms.This type polymer is at GB-A-1, and is open in 596,756.The example of this salt is the multipolymer of the polyacrylate of MW 2000～5000 and they and maleic anhydride, and the molecular weight of this multipolymer is 1,000～100,000.
Especially, acrylate and methacrylic acid salt copolymer such as 480N, the molecular weight that it has are 4000, are added in the detergent composition of the present invention with the level of composition weight 0.5～20%.
The present composition contains lime soap peptizing agent compound, preferably it have hereinafter definition lime soap dispersive ability (LSDP) for being not more than 8, preferably be not more than 7, most preferably be not more than 6.The level that preferred this lime soap peptizing agent compound exists is 0%～20 weight %.
Provide the efficient of the lime soap peptizing agent of digital metric by lime soap dispersion agent ability (LSDP), lime soap dispersion agent ability (LSDP) is at J.Am.Oil.Chem.Soc. according to H.C.Borghetty and C.A.Bergman, 27 volumes, 88-90 page or leaf, the method described in the article of (1950) use the test determination of lime soap dispersion agent.One of skill in the art is extensive use of this lime soap distributed test method, and it relates to as following survey article: W.N.Linfield, tensio-active agent, natural science series, 7 volumes, 3 pages; W.N.Linfield, tensio-active agent surf.det., 27 volumes, 159-163 page or leaf, (1990); And M.K.Nagarajan, W.F.Masler, makeup and toiletry, 104 volumes, 71-73 page or leaf, (1989).This LSDP is the percent by weight of the needed dispersion agent of dispersion stone ash soap throw out to sodium oleate, and lime soap throw out is that the 0.025g sodium oleate forms in 30ml water, this water hardness and 333ppm CaCO
3(Ca: Mg=3: 2) suitable.
Tensio-active agent with good lime soap peptizing agent performance will comprise some amine oxide, trimethyl-glycine, sultaine, oxyethyl group alkyl sodium sulfate ester and ethoxylation alcohols.
Used according to the invention have LSDP and be not more than 8 tensio-active agent example and comprise C
16～C
18Dimethyl oxidation amine, C
12～C
18The oxyethyl group sulfuric ester of alkyl, the average degree of ethoxylation of the latter is 1～5; C particularly
12～C
15The oxyethyl group sulfuric acid ester surfactant of alkyl, its degree of ethoxylation equal 3 (LSDP=4); And C
14-C
15The average degree of ethoxylation of ethoxylation alcohols or 12 (LSDP=6) or 30 are sold by BASFGmbH with trade(brand)name Lutensol A012 and Lutensol A030 respectively.
Suitable polymkeric substance lime soap peptizing agent used herein has explanation at M.K.Nagarajan in the article of W.F.Masler, and this article can be at makeup and toiletry, 104 volumes, and the 71-73 page or leaf finds in (1989).
The amino caproyl of hydrophobic SYNTHETIC OPTICAL WHITNER such as 4-[N-capryloyl-6-] benzene sulfonate, the amino caproyl of 4-[N-nonanoyl-6-] benzene sulfonate, the amino caproyl of 4-[N-decanoyl-6-] benzene sulfonate and their mixture; Also can be used as lime soap peptizing agent compound together with nonanoly acyloxy benzene sulfonate and hydrophilic/hydrophobic SYNTHETIC OPTICAL WHITNER prescription.Dye migration suppresses
Detergent composition of the present invention also can comprise the compound that suppresses dye migration, suppresses to include the dissolved that runs in the fabric laundering operation of yarn dyed fabric or the dyestuff of suspension and moves on another from a fabric.The polymeric dye migration inhibitor
Detergent composition contains 0.001%～10% according to the present invention, and is preferred 0.01%～2%, more preferably the polymeric dye migration inhibitor of 0.05%～1 weight %.Usually in detergent composition, mix said polymeric dye migration inhibitor, move on the fabric of therewith washing from colored fabric so that suppress dyestuff.These polymkeric substance have compound or adsorb the not ability of fast colo(u)r, and these dyestuffs come out from DYED FABRICS, and other article in this dyestuff has an opportunity to be washed are compound or adsorb them before adhering to.
Especially the suitable polymer blend dye transfer inhibitor is multipolymer, polyvinylpyrrolidonepolymers polymers, Ju Yi Xi oxazolidinone and the polyvinyl imidazol or their mixture of N-oxidation polyamines polymkeric substance, N-vinyl pyrrolidone and N-vinyl imidazole.
Add such polymkeric substance and also improve the performance of enzyme of the present invention.
A) N-oxidation polyamines polymkeric substance: suitable have following structural chemistry formula as contained unitary N-oxidation polyamines polymkeric substance:
Wherein P is the polymerisable unit that the R-N-O group can be attached thereto, or the R-N-O group forms the part polymerizable unit therein, or its two mixing.A is
-O-,-S-,-N-; X is 0 or 1;
R is the mixing of aliphatics, ethoxylated fat family, aromatic series, heterocycle or alicyclic group or any of these group, and the nitrogen in the N-O group can be connected on these groups or the nitrogen in the N-O group forms the part of these groups therein.
This N-O group can be represented with following general structural formula:
Wherein R1, R2 and R3 are the mixing of aliphatic group, aromatic series, heterocycle or alicyclic group or any of these group, x or/and y or/and z be 0 or 1 and wherein the nitrogen in the N-O group can be connected on these groups or the nitrogen in the N-O group forms the part of these groups therein.
Above-mentioned N-O group can be the part of polymerizable unit (P), maybe can be connected on the main polymer chain, or its two mixing.
The N-O group forms therein that R is selected from aliphatics, aromatic series, alicyclic ring or heterocyclic group in the N-oxidation polyamines that the suitable N-oxidation polyamines of part polymerizable unit contains.
The nitrogen of N-O group forms part R-group in the N-oxidation polyamines group that the said N-oxidation of one class polyamines contains.Preferred N-oxidation polyamines is that wherein R is a heterocyclic group, as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and their derivative.
The nitrogen of N-O group is connected with the R-group in the N-oxidation polyamines group that another kind of said N-oxidation polyamines contains.
Other suitable N-oxidation polyamines are that wherein the N-O group is connected to the oxidation polyamines of polymerizable unit.
This N-oxidation polyamines of a preferred class is the N-oxidation polyamines that chemical general formula (I) is arranged, and wherein R is aromatic series, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is the part of said R group.
The example of these oxidation polyamines classes is that wherein R is the oxidation polyamines of heterogeneous ring compound, heterogeneous ring compound such as pyridine, pyrroles, imidazoles and their derivative.
Another kind of preferred N-oxidation polyamines is the oxidation polyamines that chemical general formula (I) is arranged, and wherein R is aromatic series, heterocycle or alicyclic group, and wherein the nitrogen of N-O functional group is connected with said R group.
But the example of these oxidation polyamines classes is oxidation polyamines of R group aromatic series such as phenyl wherein.
Can use any main polymer chain, as long as formed amine oxide polymers is water miscible and has the dye migration rejection.The suitable example of main polymer chain is polyethylene, polyalkylene, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and their mixture.
It is 10: 1～1: 1000000 to the ratio of N-amine oxide that N-amine oxide polymers of the present invention typically has amine, yet the amount that the amine oxide group exists in oxidation polyamines polymkeric substance can change by suitable copolymerization or suitable N-degree of oxidation.Preferred amines is 2: 3～1: 1000000 to the ratio of N-amine oxide, more preferably 1: 4～1: 1000000, and most preferably 1: 7～1: 1000000.Polymkeric substance of the present invention in fact comprises random or segmented copolymer, and wherein a class monomer is N-amine oxide and another kind of monomer or yes or no N-amine oxide.The unitary PKa of amine oxide＜10 of N-oxidation polyamines, preferred PKa＜7, more preferably PKa＜6.
Resulting oxidation polyamines almost has any polymerization degree.The polymerization degree is not crucial, as long as material has required water-solubleness and dyestuff-suspending power.
Typically, molecular-weight average is 500～1000, and is preferred 1,000～50,000 in 000 scope, more preferably 2,000～30,000, most preferably 3,000～20,000.
B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole:
It is 5,000～1,000,000 that the N-vinyl imidazole N-vinyl pyrrolidone polymer that the present invention uses has average molecular weight range, preferred 5,000～200,000.
Be used for that detergent composition polymkeric substance very preferably contains the polymkeric substance that is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer according to the present invention, wherein to have average molecular weight range be 5 to the said polymer, 000～50,000, more preferably 8,000～30,000, most preferably 10,000～20,000.
Average molecular weight range passes through determination of light scattering according to H.G.Barth and J.W.May described in chemical analysis 113 volumes " modern polymer characterization method ".
It is 5,000～50,000 that N-vinyl imidazole N-vinylpyrrolidone copolymer very preferably has average molecular weight range, more preferably 8,000～30,000, most preferably 10,000～20,000.
Feature is that the N-vinyl imidazole N-vinylpyrrolidone copolymer with said average molecular weight range provides extraordinary dye migration rejection, and the clean-up performance of detergent composition to preparation does not with it have negative impact simultaneously.
The N-vinyl imidazole that N-vinyl imidazole N-vinylpyrrolidone copolymer of the present invention has is 1～0.2 to the mol ratio of N-vinyl pyrrolidone, more preferably 0.8～0.3, most preferably 0.6～0.4.
C) Polyvinylpyrolidone (PVP):
Detergent composition of the present invention also can use Polyvinylpyrolidone (PVP) (" PVP "), and it has molecular-weight average is about 2,500～about 400,000, preferably approximately 5,000～about 200,000, more preferably about 5,000～about 50,000 and most preferably about 5,000～about 15,000.Suitable Polyvinylpyrolidone (PVP) can utilize New York, New York and Canada to cover the commodity of Trier ISP company, commodity are called PVP K-15, and (viscosity-average molecular weight is 10,000), (molecular-weight average is 40 to PVP K-30,000), (molecular-weight average is 160 to PVP K-60,000) and PVP K-90 (molecular-weight average is 360,000).Other suitable Polyvinylpyrolidone (PVP)s can be used to the commodity from BASF AG, comprise Sokalan HP 165 and Sokalan HP 12; Polyvinylpyrolidone (PVP) is understood (consulting for example EP-A-262,897 and EP-A256,696) by the technician of detergent applications.
D) Ju Yi Xi oxazolidinone:
Detergent composition of the present invention also can use Ju Yi Xi oxazolidinone as the polymeric dye migration inhibitor.The molecular-weight average that said Ju Yi Xi oxazolidinone has be about 2,500～about 400,000, preferably approximately 5,000～about 200,000, more preferably about 5,000～about 50,000 and most preferably about 5,000～about 15,000.
E) polyvinyl imidazol:
Detergent composition of the present invention also can use polyvinyl imidazol as the polymeric dye migration inhibitor.Said polyvinyl imidazol have molecular-weight average be about 2,500～about 400,000, preferably approximately 5,000～about 200,000, more preferably about 5,000～about 50,000 and most preferably about 5,000～about 15,000.
F) cross-linked polymer:
Cross-linked polymer is the interconnective to a certain degree polymkeric substance of its main chain, and these connections can be by the active group on its main chain or the side chain, and it connects essence can be chemical or physics.Cross-linked polymer is at Journal of Polymer Science, and 22 roll up, and the 1035-1039 page or leaf has explanation.
In one embodiment, prepare cross-linked polymer, catch dyestuff by the hole that forms in three-dimensional-space structure in its mode that forms three-dimensional-space rigid structure.In another embodiment, cross-linked polymer is caught dyestuff by swelling.This cross-linked polymer has explanation in common unexamined patent application 94870213.9.Washing methods
The present composition can use in any washing or cleaning method basically, and these methods comprise infusion method, method for pretreating and have the method for rinse step, and rinse step can add separately and helps rinse composition.
Method described here comprises fabric, tableware or any other crust and cleaning soln is contacted with common mode or the mode of hereinafter making example.Conventional clothes washing method comprises that usefulness is wherein dissolved or the water liquid of the scouring agent of the significant quantity that suspended and/or Fabrid care composition is handled the fabric that pollutes.Preferred machine is washed the dish method and is comprised that usefulness is wherein dissolved or the machine of the significant quantity that suspended is washed the article of the water liquid processing pollution of dish or rinse composition.The conventional significant quantity that machine is washed the dish composition refers to dissolve or disperse 8～60g product in 3～10 liters of wash volumes.Wash the dish method according to manual, the dish composition of washing of the dish of pollution and significant quantity contacts, and this significant quantity is 0.5～20g (25 dish of every processing) typically.Preferred manual wash the dish method, be included in and use strong solution on the vessel surface or with the Macrodilution solution soaking of detergent composition.Conventional crust method comprises to be used as sponge, brush, cloth etc. and wherein dissolve or disperseed the water liquid of hard surface cleaner of significant quantity and/or the said composition of dilution to handle the hard object/surface of polluting, and also is included in the hard object of immersion in the strong solution of detergent composition or the large volume dilute solution.
The inventive method can be implemented in the cleaning course process easily.This cleaning method is especially implemented the pH value preferred 7～12 of treatment soln preferably at 5 ℃～95 ℃ between 10 ℃ and 60 ℃.Preparation embodiment 1: preparation sulfonic acid [3-(3, the 4-dihydro-isoquinoline) propane] salt (4):
Be equipped with in the 250ml circle-end flask of magnetic agitation, argon gas inlet, addition funnel and reflux condensing tube and add 3, and the 4-dihydro-isoquinoline (2,5.005g) and methyl alcohol (23ml).This mixture cools off with ice bath, and drips 1, and the 3-N-morpholinopropanesulfonic acid lactone (3, the 4.670g) solution in methyl alcohol (23ml).Dropwise and remove ice bath, and the reaction reflux is spent the night.Allow this mixture be cooled to temperature and to reduce pressure remove volatile matter.The gained solid product adds the acetone pulping and cleans three times and dry air.The following reaction of this preparation:
Preparation embodiment 2: preparation 1-(3.4-dihydro-isoquinoline)-decane-2-vitriol (5):
Step 1: preparation 3,4-dihydro-isoquinoline (2):
Be equipped with and add styroyl amine (1,0.0413 mole) and 88% formic acid (7.6g, 3.5 equivalents) in the 100mL round-bottomed flask of stirrer and water distilling apparatus, will be reflected at about 100 ℃ of distillations or backflow.After 1 hour, added 88% whole formic acid of 2mL until ruing out of with gas chromatographic detection styroyl amine every about 30 minutes.This reaction mixture is about 45 minutes of about 200 ℃ of distillations (use Dean-Stark collector), allowed cool to room temperature then.
Be equipped with that to add weight ratio in the 250mL round-bottomed flask of stirrer, reflux condensing tube and addition funnel be 10.5: 1 Vanadium Pentoxide in FLAKES (7.07g) and Tripyrophosphoric acid.Mixture is stirred and heated about 1 hour at about 180 ℃, be cooled to about 150 ℃ then.Drip the refrigerative styroyl methane amide crude product of above-mentioned preparation in this mixture.Dropwise, will be reflected at about 170 ℃ of heating and stirring and spend the night.This mixture cool to room temperature and water (300mL) dilution, (150mL) washes with ether, with saturated potassium hydroxide pH is transferred to 9 under the cooling in acetone/the dry ice bath.(3 * 150mL) extractions and the organic phase dried over mgso, filtration and the concentrating under reduced pressure that merge, the oily matter that obtains provide the compound of Chemical formula 2 further by Kugelrohr distillation (70 ℃, 1mm Hg) purifying to this aqueous solution with ether.
Step 2: preparation 1,2-decane glycol cyclic sulfates (4):
Three mouthfuls of round-bottomed flasks of 500mL of mechanical stirring, pressure balanced addition funnel and reflux condensing tube are housed, have the drying tube that anhydrous calciumsulphate is filled on the reflux condensing tube, add 1 in the bottle, (3,8.72g is 50.0mmol) with the 50mL tetracol phenixin for 2-decane glycol.When 1, after the dissolving of 2-decane glycol, (5.5mL 75mmol), is heated to about 60 ℃ with reaction in the room temperature thionyl chloride.After two hours, allow sluggish be cooled to about 0 ℃.Add deionized water (50mL) and acetonitrile (75mL).Add ruthenium chloride hydrate (0.13g, 0.50mmol) and sodium periodate (21.4g, 100mmol) and reaction mixture stirring at room 1 hour.Mixture with extracted with diethyl ether (4 * 175mL), organic phase with deionized water (5 * 100mL), saturated sodium hydrogen carbonate solution (3 * 100mL) and salt solution (2 * 100mL) wash, and pass through diatomite/silica dioxide gel filtration then.Filtrate concentrates with magnesium sulfate salt drying, filtration with by rotary evaporation and provides limpid oily matter.
Step 3: preparation 1-(3 4-dihydro-isoquinoline)-decane-2-vitriol (5)
Be equipped with in the 100mL round-bottomed flask of magnetic stir bar and add 3, and the 4-dihydro-isoquinoline (2.02g, 15.4mmol) and acetonitrile (15.2mL) whole 1 toward once adding here, 2-decane glycol cyclic sulfates (3.78g, 16.0mmole).Along with the reaction mixture retrogradation, add acetonitrile (60mL) again and will react to stir and spend the night.Its dry air is washed 5 times and allowed to the collecting precipitation thing with acetone.
The following example will illustrate the present composition, but needn't mean it is to limit or limit in addition scope of the present invention.In detergent composition, unless otherwise indicated, the level of enzyme is to represent with the pure enzyme in the total composition weight, and detergent ingredients is to represent with total composition weight.The abbreviation sign of component has following meanings in the literary composition:
LAS: linear C
11～13Sodium alkyl benzene sulfonate.
TAS: tallow alkyl sodium sulfate.
CxyAS:C
1x～C
1ySodium alkyl sulfate.
CxySAS:C
1x～C
1ySecondary amine (2,3) sodium alkyl sulfate.
MBASx, y: in the middle of the chain-and the sodium alkyl sulfate of side chain, x carbon atom on average arranged, wherein
On a chain unit, on average contain y carbon atom.
CxyEz: be mainly linear primary alcohol with the ethylene oxide condensation of average z mole
CxyEzS: with the C of the ethylene oxide condensation of average z mole
1x～C
1ySodium alkyl sulfate
CxEOy: the Cy alcohol of average y ethoxylation
Non-ionic type: mixed ethoxylated/propoxylated fatty alcohol as Plurafac EF404 is
Average degree of ethoxylation be 3.8 and average degree of propoxylation be 4.5
Alcohol
QAS:R
2N+ (CH
3)
2(C
2H
4OH), R wherein
2=C
12-C
14
SADS C
14～22Alkyl two sodium sulfate, chemical formula are 2-RC4H7-1,4-(SO
4 -)
2,
R=C wherein
10～18
MES:C
18The x-sulfo group methyl ester of lipid acid
Soap: tallow by 80/20 and coconut oil fat acid mixture deutero-linear alkyl
Carboxylic acid sodium
Silicate amorphous sodium silicate (SiO
2: Na
2O ratio=1.6～3.2: 1).
Metasilicate water glass (SiO
2: Na
2O ratio=1.0)
Zeolite A hydrated aluminum silicate, chemical formula are Na
12(AlO
2SiO
2)
1227H
2O,
(weight is done with anhydrous at 0.1～10 micrometer range to have main particle size
Heavily be basic representation).
(Na-) the SKS-6 chemical formula is -Na
2Si
2O
5Crystalline layered silicate
Citrate trianion trisodium citrate monocalcium salt compound.
The Citric Citric Acid, usp, Anhydrous Powder
The random copolymers of 4: 1 acrylate/maleic acid esters of carbonate anhydrous sodium carbonate supercarbonate sodium bicarbonate vitriol anhydrous sodium sulphate STPP tripolyphosphate sodium salt TSPP tetrasodium pyrophosphate salt MA/AA, molecular-weight average
Be about 70,000～80,000.6: 4 acrylate/maleic acid ester random copolymerss of MA/AA1, molecular-weight average is
About 10,000.AA polyacrylic acid sodium polymer, molecular-weight average are 4,500.Polycarboxylate contains carboxylic acid ester monomer such as acrylate, maleic acid ester and methacrylic
The multipolymer of acid esters mixture, MW scope be 2,000～80,000 it
Between, be propylene as the commodity Sokolan of commercial available BASF
Acid copolymer, MW4,500.BB1 prepares the sulfonic acid [3-(3, the 4-dihydro-isoquinoline) propane] of embodiment 1 preparation
Salt BB2 prepares 1-(3, the 4-dihydro-isoquinoline)-decane-2-sulphur of embodiment 2 preparations
Hydrochlorate PB1 exsiccant peroxyboric acid sodium salt monohydrate PB4 sodium perborate tetrahydrate, nominal formula is NaBO
34H
2The anhydrous SPC-D of O percarbonate, nominal formula are 2.74Na
2CO
33H
2O
2DAP1 diacyl peroxide particulate, contain 30% dibenzoyl superoxide,
40% sodium sulfate, 5% Acusol 480N polymkeric substance, 2% Fructus Hordei Germinatus magma
The water of essence, 12% ethoxylated octadecanol and remaining sum.DAP 2 two bay acyl peroxides can utilize the commodity NaDCC dichloro-isocyanuric acid sodium of Akzo.The TAED tetra acetyl ethylene diamine.The nonanoly acyloxy benzene sulfonate of NOBS sodium-salt form.NACA-OBS (the amino caproyl of 6-nonanoyl) oxygen base sulfonate.The acyloxy benzene sulfonate DTPA diethylene triaminepentaacetic acid(DTPA) in the last of the ten Heavenly stems of DOBS sodium-salt form.HEDP 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid.DETPMP diethyl triamine five (methylene radical) hydrochlorate of seeing, the product of Monsanto,
Trade name is Dequest 2060.EDDS quadrol-N, N '-disuccinic acid, (S, S)-isomer, sodium-salt form.The sequestrant sequestrant, be selected from EEDS, HEDP, DTPA, DETPMP and/
Or their mixture.Catalyzer Mn (bcyclam) Cl
2The sulfonated zinc phthalocyanine capsule of MnTACN manganese (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) photoactivation SYNTHETIC OPTICAL WHITNER in the dextrin soluble polymer.The sulfonated aluminium phthalocyanine capsule of photoactivation SYNTHETIC OPTICAL WHITNER in the dextrin soluble polymer.1PAAC five amine cobaltous acetate (III) salt.Paraffinic hydrocarbon paraffin hydrocarbon ils, Wintershall sells, and commodity are called Winog 70.NaBz Sodium Benzoate pectate cracking pectate lyase, be derived from sticking agar genus bacillus, NCIMB enzyme 40482 or DSM 8721 protease protein lytic enzymes, commodity are called Savinase, Alcalase, Durazym
Novo Nordisk A/S product, commodity are called Maxacal, Maxapem
The Gist-Brocades product and patent WO91/06637 and/or
Proteolytic enzyme described in WO95/10591 and/or the EP 251 446.Amylase amylolytic enzyme: described in WO 94/18314, WO96/05295
The commodity Purafact Ox Am by name that sells of Genencor
RNovo
The termamyl of Nordisk A/S
, Fungamyl
And Duramyl
All be
Available and those in WO 95/26397 (Novo Nordisk with
Trade(brand)name Natalase sells) illustrated.The lipase lipolytic enzyme: the commodity that Novo Nordisk A/S sells are by name
The commodity that Lipolase Lipolase Ultra and GistBrocades sell
Lipomax by name.The cellulase cellulolytic enzyme: the commodity that Novo Nordisk A/S sells are by name
Carezyme, Celluzyme and/or Endolase.Pectin lyase is by Bacillus licheniformis, the pectin lyase that ATCC14580 produces.CMC sodium carboxy methyl cellulose PVNO polyvinylpyridine-N-oxide compound, molecular-weight average is 50,000.PVPVl vinyl imidazole and vinylpyrrolidone copolymers, molecular-weight average
Be 20,000.Brightener 14,4 '-two (2-sulfo group styryl) biphenyl disodium.Brightener 24,4 '-two (4-anilinos-6-morpholino-1,3,5-triazines-2-yl)-1,2-hexichol
Ethene-2:2 '-disulfonic acid disodium salt.Silicone antifoam agent polydimethylsiloxane foam control agent has siloxanes-oxyalkylene copolymers
Make dispersion agent, said foam control agent to the ratio of said dispersion agent be 10: 1～
100∶1。Suds suppressor 12% siloxanes/silicon-dioxide, 18% Stearyl alcohol, 70% starch,
Granular form.The high molecular weight crosslinked polyacrylic ester of thickening material, public as the B.F.Goodrich chemistry
Anionic polyester on Carbopol that department provides and the PolygelSRP1 distal hood.QEA: two ((C
2H
5O) (C
2H
4O)
n)) (CH
3)-N
+-C
6H
12-N
+-(CH
3)
Two ((C
2H
5O)-(C
2H
4O))
n, n=20～30 wherein.PEGX polyoxyethylene glycol, molecular weight are the xPEO polyethylene oxide, and molecular-weight average is 5,000TEPAE ethoxylation tetren BTA benzotriazole.PH measures in 1% distilled water solution at 20 ℃
Embodiment 1
Following high-density produced according to the present invention and contain SYNTHETIC OPTICAL WHITNER-the scouring agent composition:
I II III IV V VI brown ceramic powder: zeolite A 12.0-15.0 12.0-15.0 vitriol-5.0--5.0-
LAS 3.0 - 3.0 3.0 - 3.0
C45AS 3.0 2.0 4.0 3.0 2.0 4.0
QAS - - 1.5 - - 1.5
DETPMP 0.4 0.4 0.4 0.4 0.4 0.4
CMC 0.4 0.4 0.4 0.4 0.4 0.4
MA/AA 1.0 2.0 2.0 1.0 2.0 2.0 makes following compounds become block:
QAS 1.0 - - 1.0 - -
LAS - 11.0 7.0 - 11.0 7.0
TAS 2.0 2.0 1.0 2.0 2.0 1.0
Silicate 3.0-4.0 3.0-4.0
Zeolite A 8.0 8.0 8.0 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0 8.0 8.0 4.0
Agglomerate is
NaSKS-6 15.0 12.0 5.0 15.0 12.0 5.0
LAS 8.0 7.0 4.0 8.0 7.0 4.0 sprays:
Spices 0.3 0.3 0.3 0.3 0.3 0.3
C25E3 2.0-2.0 2.0-2.0 adds dried additive:
QEA 1.0 0.5 0.5 1.0 0.5 0.5
Citric/ citric acid 5.0-2.0 5.0-2.0
Salt
Supercarbonate-3.0--3.0-
Carbonate 8.0 15.0 10.0 8.0 15.0 10.0
TAED and/or 6.0-5.0 6.0-5.0
NACA-OBS
NOBS - 2.0 - - 2.0 -
DAP1 - - - 6.7 4.8 5.2
Catalyzer 0.002-0.02-0.02-
Percarbonate or 14.0 7.0 10.0 4.15 7.0 10.0
PB1
BB1 0.40 - 0.20 - - -
BB2- 0.14 - - - - -
MW is--0.2--0.2
5,000,000
Polyethylene oxide
Wilkinite--10.0--10.0
Citric acid 4.0-1.5 4.0-1.5
Pectate splits 0.001 0.02 0.01 0.001 0.02 0.01
Separate enzyme
Proteinase-10 .033 0.033 0.033 0.033 0.033 0.033
Lipase 0.008 0.008 0.008 0.008 0.008 0.008
Amylase 0.001 0.001 0.001 0.001 0.001 0.001
Cellulase 0.0014 0.0014 0.0014 0.0014 0.0014 0.0014
Siloxanes froth breaking 5.0 5.0 5.0 5.0 5.0 5.0
Agent
Vitriol-3.0--3.0-
Density (g/ liter) 850 850 850 850 850 850
Moisture and other add to 100%
Embodiment 2
Following high-density produced according to the present invention and contain SYNTHETIC OPTICAL WHITNER-scouring agent composition:
I II III
Brown ceramic powder:
Zeolite A 12.0-15.0
Vitriol-5.0-
LAS 3.0 - 3.0
C45AS 3.0 2.0 4.0
QAS - - 1.5
DETPMP 0.4 0.4 0.4
CMC 0.4 0.4 0.4
MA/AA 1.0 2.0 2.0
Make block:
QAS 1.0 - -
LAS - 11.0 7.0
TAS 2.0 2.0 1.0
Silicate 3.0-4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Agglomerate:
NaSKS-6 15.0 12.0 5.0
LAS 8.0 7.0 4.0
Spray:
Spices 0.3 0.3 0.3
C25E3 2.0 - 2.0
Dried additive:
QEA 1.0 0.5 0.5
Citric/ Citrate trianion 5.0-2.0
Supercarbonate-3.0-
Carbonate 8.0 15.0 10.0
Catalyzer 0.002 0.02 0.02
TAED and/or 6.0-5.0
NACA-OBS
NOBS - 2.0 -
Percarbonate/PB1 14.0 7.0 10.0
Polyethylene oxide ,--0.2
MW is
5,000,000
Wilkinite--10.0
Citric acid 4.0-1.5
Pectate cracking 0.001 0.02 0.01
Enzyme
Proteinase-10 .033 0.033 0.033
Lipase 0.008 0.008 0.008
Amylase 0.001 0.001 0.001
Cellulase 0.0014 0.0014 0.0014
Silicone antifoam agent 5.0 5.0 5.0
Vitriol-3.0-
Density (g/ liter) 850 850 850
Moisture and other add to 100%
Embodiment 3
Following tablet laundry composition produced according to the present invention:
I II III IV V base product:
C45?AS/TAS 8.0 5.0 3.0 3.0 3.0
LAS 8.0 - 8.0 - 7.0
C25AE3S 0.5 2.0 1.0 - -
C25AE5/AE3 2.0 - 5.0 2.0 2.0
QAS - - - 1.0 1.0
Zeolite A 20.0 18.0 11.0-10.0
SKS-6 (1) (do--9.0--
Add)
MA/AA 2.0 2.0 2.0 - -
AA - - - - 4.0
Citrate trianion-2.0---
Citric 2.0 - 1.5 2.0 -
DTPA 0.2 0.2 - - -
EDDS - - 0.5 0.1 -
HEDP - - 0.2 0.1 -
PB1 3.0 5.0 10.0 - 4.0
Percarbonate---18.0-
NOBS 3.0 4.0 - - 4.0
NACA?OBS - - 2.0 - -
TAED - - 2.0 5.0 -
DAP1 4.8 3.6 6.9 - 5.2
DAP2 - - - 4.9 -
Catalyzer-0.02---
Carbonate 15.0 18.0 8.0 15.0 15.0
Vitriol 5.0 12.0 2.0 17.0 3.0
Silicate-1.0--8.0
Proteinase-10 .033 0.033 0.033 0.046 0.033
Lipase 0.008 0.008 0.008 0.008 0.006
Amylase 0.001 0.001 0.001 0.0014 0.001
Cellulase 0.001 0.0014 0.001 0.01-
4 4
Pectin lyase 0.001---
Pectate splits 0.001 0.002 0.02 0.05 0.005
Separate enzyme
Assistant agent 0.5 0.5 0.5 0.5 0.5
Spices 0.2 0.3 0.5 0.2 0.1
Moisture and other add to 100%
Assistant agent comprises brightener/SRP1/CMC/ optical white/MgSO4/PVPVI/ suds suppressor/PEG.
Embodiment 4
Following laundry composition produced according to the present invention, it can be granular or tablet:
I II III IV V base product:
C45?AS/TAS 8.0 5.0 3.0 3.0 3.0
LAS 8.0 - 8.0 - 7.0
C25AE3S 0.5 2.0 1.0 - -
C25AE5/AE 2.0 - 5.0 2.0 2.0
3
QAS - - - 1.0 1.0
Zeolite A 20.0 18.0 11.0-10.0
SKS-6 (1) (do--9.0--
Add)
MA/AA 2.0 2.0 2.0 - -
AA - - - - 4.0
Citrate trianion-2.0---
Citric 2.0 - 1.5 2.0 -
DTPA 0.2 0.2 - - -
EDDS - - 0.5 0.1 -
HEDP - - 0.2 0.1 -
PB1 3.0 5.0 10.0 - 4.0
Percarbonate---18.0-
NOBS 3.0 4.0 - - 4.0
NACA?OBS - - 2.0 - -
TAED - - 2.0 5.0 -
BB1 0.06 - 0.34 - 0.14
BB2 - 0.14- - 0.20 -
Catalyzer-0.001--0.002
Carbonate 15.0 18.0 8.0 15.0 15.0
Vitriol 5.0 12.0 2.0 17.0 3.0
Silicate-1.0--8.0
Proteinase-10 .033 0.033 0.033 0.046 0.033
Lipase 0.008 0.008 0.008 0.008 0.006
Amylase 0.001 0.001 0.001 0.0014 0.001
Cellulase 0.0014 0.0014 0.0014 0.01-
Pectin lyase 0.001---
Pectate splits 0.001 0.002 0.02 0.05 0.005
Separate enzyme
Assistant agent 0.5 0.5 0.5 0.5 0.5
Spices 0.2 0.3 0.5 0.2 0.1 moisture and other add to 100% assistant agent and comprise brightener/SRP1/CMC/ optical white/MgSO4/PVPVI/ suds suppressor/PEG.
Embodiment 5
Following high-density scouring agent composition produced according to the present invention:
I II III IV V VI makes block:
QAS 2.0 - 2.0 2.0 - 2.0
MES - 2.0 - - 2.0 -
LAS 6.0 - - 6.0 - -
TAS - 2.0 - - 2.0 -
C45AS 6.0 4.0 2.0 6.0 4.0 2.0
MBAS16.5，1. 4.0 - - 4.0 - -
9
Zeolite A 15.0 6.0-15.0 6.0-
Carbonate 4.0 8.0 4.0 4.0 8.0 4.0
MA/AA 4.0 2.0 - 4.0 2.0 -
CMC 0.5 0.5 - 0.5 0.5 -
DETPMP 0.4 0.4-0.4 0.4-spray
C25E3 1.0 1.0 - 1.0 1.0 -
Spices 0.5 0.5 0.5 0.5 0.5 0.5 agglomerates:
SKS-6 7.0 15.0 20.0 7.0 15.0 20.0
LAS 5.8 9.0 15.0 5.8 9.0 15.0
Zeolite-0.9--0.9-
Water 0.08 0.1-0.08 0.1-dried additive:
EDDS/HEDP 0.5 0.3 0.5 0.5 0.3 0.5
NaSKS?6(I) 5.0 6.0 4.0 5.0 6.0 4.0
Citrate trianion-1.0--1.0-
Citric 2.0 - 2.0 2.0 - 2.0
NACA-OBS 4.1 - 5.0 4.1 - 5.0
TAED 0.8 2.0 - 0.8 2.0 -
Percarbonate 20.0 20.0 15.0 20.0 20.0 15.0
DAP1 - - - 3.2 2.6 3.2
Catalyzer-0.002--0.002-
BB1 0.45 - 0.30 - - -
BB2 - 0.25 - - - -
SRP1 0.3 0.3 - 0.3 0.3 -
Pectate splits 0.002 0.01 0.03 0.002 0.01 0.03
Separate enzyme
Pectin lyase 0.001--0.001--
Proteinase-10 .046 0.046 0.033 0.046 0.046 0.033
Lipase 0.008 0.008 0.006 0.008 0.008 0.006
Cellulase 0.001 0.001 0.001 0.001 0.001 0.001
4 4 4 4
Amylase 0.001 0.001-0.001 0.001-
QEA 1.0 - 1.0 1.0 - 1.0
Siloxanes froth breaking 1.0 0.5 0.5 1.0 0.5 0.5
Agent
Brightener 1 0.2 0.2-0.2 0.2-
Brightener 2 0.2-0.2 0.2-0.2
Density (g/ liter) 850 850 800 850 850 800
Moisture and other add to 100%
Embodiment 6
Following granulated detergent produced according to the present invention:
I II III IV V VI VII VIII ： STPP-22.0-15.0-22.0-15.0 A 30.0-24.0 5.0 30.0-24.0 5.0 5.5 5.0 7.0 7.0 5.5 5.0 7.0 7.0 MA/AM 3.0---3.0---AA-1.6 2.0--1.6 2.0-MA/AA ( 1 ) -12.0-6.0-12.0-6.0 LAS 14.0 10.0 9.0 20.0 14.0 10.0 9.0 20.0 C45AS 8.0 7.0 9.0 7.0 8.0 7.0 9.0 7.0 C45AE11S-1.0-1.0-1.0-1.0 MES 0.5 4.0 6.0-0.5 4.0 6.0-SADS 2.5--1.0 2.5--1.0 -1.0 0.5 10.0-1.0 0.5 10.0 -2.0---2.0--1 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 6.0 9.0 8.0 10.0 6.0 9.0 8.0 10.0 PEG 4000-1.0 1.5--1.0 1.5-DTPA-0.4---0.4--： C25E9---5.0---5.0 C45E7 1.0 1.0--1.0 1.0--C23E9-1.0 2.5--1.0 2.5- 0.2 0.3 0.3-0.2 0.3 0.3- 5.0 10.0 13.0 8.0 5.0 10.0 13.0 8.0PVPVI/PVNO 0.5-0.3-0.5-0.3- 0.03 0.03 0.03 .001 0.03 0.03 0.03 .001
33363336 lipase 0.00--0.00 0.00--0.00
8888 amylase .001--.001 .001--.001
6666 cellulase .000 .000 .000 .000 .000 .000 .000 .000
25522552 pectate cracking, 0.00 0.02 0.03 0.01 0.00 0.02 0.03 0.01 enzyme, 151 5DTPA, 0.5 0.3 0.5 1.0 0.5 0.3 0.5 1.0PB1,5 3.0 10 4.0 5 3.0 10 4.0DAP1----3.8 6.7 4.3 3.2 catalyst 0.00--0.00-0.00--
---NOBS/TAED 0.5 0.3 0.5 0.6 0.5 0.3 0.5 0.6 sulfate 4.0 5.0-5.0 4.0 5.0-5.0SRP1-0.4---0.4--foam inhibitor-0.5---0.5--bespeckle agent 0.9-2.7 1.2 0.9-2.7 1.2 moisture and other add to 100% embodiment 7 to 12 1BB1 0.2--0.5----BB2-0.3 0.4
Following scouring agent composition produced according to the present invention:
I II III IV V VI VII
LAS 12.0 16.0 23.0 19 18.0 20.0 16.0
C45AS 4.5 - - - 4.0
C45?E3S - - 2.0 - 1.0 1.0 1.0
C45E6.5S 2.0 2.0 - 1.3 - - 0.6
C
9-C
14Alkyl-dimethyl--1.0 0.5 2.0
Base hydroxyethyl season NH
4
Salt
Beef fat acid------1.0
STPP 23.0 25.0 24.0 22.0 20.0 15.0 20.0
Carbonate 15.0 12.0 15.0 10.0 13.0 11.0 10.0
Sodium polyacrylate 0.5 0.5 0.5 0.5---
(45％)
MA/AA - - 1.0 1.0 1.0 2.0 0.5
Silicate (ratio 1: 6 3.0 6.0 9.0 8.0 9.0 6.0 8.0
Vitriol 25.0 18.0 20.0 18.0 20.0 22.0 13.0
PB1 5.0 5.0 10.0 8.0 3.0 1.0 2.0
PEG MW4000 1.5 1.5 1.0 1.0 - - 0.5
(50％)
CMC 1.0 1.0 1.0 - 0.5 0.5 0.5
NOBS/DOBS 0.5 1.0 0.5 0.5 1.0 0.7 0.3
TAED 1.5 1.0 2.5 3.0 0.3 0.2 0.5
BB1 - 0.3 - 0.5 0.3 - 0.25
BB2 0.4 - 0.4 - 0.3 0.4 -
SRP1 1.5 1.5 1.0 1.0 - 1.0 -
SRP2 - - - - 1.0 - 1.0
Moisture 7.5 7.5 6.0 7.0 5.0 3.0 5.0
Sal epsom----1.0 0.5 1.5
Sequestrant----0.8 0.6 1.0
Proteinase-10 .033 0.033 0.033 0.046 0.033 0.033 0.033
Lipase 0.008 0.008 0.008 0.008 0.006--
Amylase 0.001 0.001 0.001 .0014 0.001--
Cellulase .0014 .0014 .0014 0.01-.0005 .0005
Pectate lyase 0.001 0.02 0.01 0.001 0.002 0.015 0.03
Pectin lyase 0.001--0.001 0.001--
Bespeckle agent 2.5 4.1 4.2 4.4 5.6 5.0 5.2
Assistant agent 1.0 1.0 1.0 1.0 0.5 1.5 1.0
Embodiment 8
Following scouring agent composition produced according to the present invention:
I II III IV V VI VII
LAS 12.0 16.0 23.0 19 18.0 20.0 16.0
C
45AS 4.5 - - - 4.0
C
45E0.5S - - - - - - -
C45E3S - - 2.0 - 1.0 1.0 1.0
C
9-C
14Alkyl-dimethyl--1.0 0.5 2.0
Base hydroxyethyl season NH
4
Salt
Beef fat acid------1.0
Ethoxylation (50) ox-------
Fatty Alcohol(C12-C14 and C12-C18)
STPP 23.0 25.0 24.0 22.0 20.0 15.0 20.0
Carbonate 15.0 12.0 15.0 10.0 13.0 11.0 10.0
Sodium polyacrylate 0.5 0.5 0.5 0.5---
(45％)
MA/AA - - 1.0 1.0 1.0 2.0 0.5
Silicate 3.0 6.0 9.0 8.0 9.0 6.0 8.0
( 1∶6 ) 25.0 18.0 20.0 18.0 20.0 22.0 13.0 PB1 5.0 5.0 10.0 8.0 3.0 1.0 2.0 PEG MW～1.5 1.5 1.0 1.0--0.5 4000 ( 50％ ) CMC 1.0 1.0 1.0-0.5 0.5 0.5 Citric------- 0.05 0.005 0.1 0.002 0.02 0.05 0.005 NOBS/DOBS 0.5 1.0 0.5 0.5 1.0 0.7 0.3 TAED 1.5 1.0 2.5 3.0 0.3 0.2 0.5 SRP1 1.5 1.5 1.0 1.0-1.0-SRP2----1.0-1.0 7.5 7.5 6.0 7.0 5.0 3.0 5.0 ----1.0 0.5 1.5 ----0.8 0.6 1.0 0.033 0.033 0.033 .0016 0.033 0.016 0.033 0.008--0.008 0.006-0.008 .0016--.0016 0.001 0.001 .0016 .0002 .0005 .0005 .0002-.0015 .0002 0.001 0.02 0.01 0.001 0.002 0.015 0.03 0.001--0.001 0.001-- 2.5 4.1 4.2 4.4 5.6 5.0 5.2 1.0 1.0 1.0 1.0 0.5 1.5 1.0
Embodiment 9
Following scouring agent composition produced according to the present invention:
I II III IV V VI VII VIII LAS 13.3 13.7 10.4 8.0 13.3 13.7 10.4 8.0 C
45AS 3.9 4.0 4.5-3.9 4.0 4.5-C
45E0.5S 2.0 2.0--2.0 2.0--C45E3S--------C45E6.5S 0.5 0.5 0.5 5.0 0.5 0.5 0.5 5.0C
9-C
14NH of basic hydroxyethyl season of alkyl-dimethyl 1.0--0.5 1.0--0.5
4 0.5---0.5--- ( 50 ) --1.0 0.3--1.0 0.3STPP-41.0-20.0-41.0-20.0A 26.3-21.3 1.0 26.3-21.3 1.0 23.9 12.4 25.2 17.0 23.9 12.4 25.2 17.0 3.4 0.0 2.7-3.4 0.0 2.7- ( 45％ ) MA/AA--1.0 1.5--1.0 1.5 2.4 6.4 2.1 6.0 2.4 6.4 2.1 6.0 ( 1∶6 ) 10.5 10.9 8.2 15.0 10.5 10.9 8.2 15.0PB1 1.0 1.0 1.0 2.0 1.0 1.0 1.0 2.0PEG MW 4000 1.7 0.4 1.0-1.7 0.4 1.0- ( 50％ ) CMC 1.0--0.3 1.0--0.3Citric--3.0---3.0-BB1 1.0 0.5 0.6-----BB2-0.2-1.0----DAP1----2.0 2.1 3.4 2.1NOBS/DOBS 0.2 0.5 0.5 0.1----TAED 0.6 0.5 0.4 0.3----SRP1 1.5---1.5---SRP2-1.5 1.0 1.0-1.5 1.0 1.0 7.5 3.1 6.1 7.3 7.5 3.1 6.1 7.3---1.0---1.0 ---0.5---0.5 0.5 1.0 3.0 0.5 0.5 1.0 3.0 0.5 0.03 0.03 0.03 0.04 0.03 0.03 0.03 0.04
33363336 lipase 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
88888888 amylase, 0.00 0.00 0.00 .001,0.00 0.00 0.00 .001
11141114 cellulase .001 .001 .001,0.01 .001 .001 .001 0.01
444444 pectates, 0.00 0.01 0.00 0.00 0.00 0.01 0.00 0.00 lyase, 152152 assistant agents 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
The embodiment 10 following laundry compositions that can be tablet form produced according to the present invention:
I II III IV V base product:
C45?AS/TAS 8.0 5.0 3.0 3.0 3.0
LAS 8.0 - 8.0 - 7.0
C25AE3S 0.5 2.0 1.0 - -
C25AE5/AE3 2.0 - 5.0 2.0 2.0
QAS - - - 1.0 1.0
Zeolite A 20.0 18.0 11.0-10.0
SKS-6 (1) (do--9.0--
Add)
MA/AA 2.0 2.0 2.0 - -
AA - - - - 4.0
Citrate trianion-2.0---
Citric 2.0 - 1.5 2.0 -
DTPA 0.2 0.2 - - -
EDDS - - 0.5 0.1 -
HEDP - - 0.2 0.1 -
Catalyzer 0.05 0.005 0.01 0.002 0.02
PB1 3.0 5.0 10.0 - 4.0
Percarbonate---18.0-
NOBS 3.0 4.0 - - 4.0
NACA?OBS - - 2.0 - -
TAED - - 2.0 5.0 -
Carbonate 15.0 18.0 8.0 15.0 15.0
Vitriol 5.0 12.0 2.0 17.0 3.0
Silicate-1.0--8.0
Proteinase-10 .033 0.033 0.033 0.046 0.046
Lipase 0.008 0.008 0.008 0.008 0.008
Amylase 0.001 0.001 0.001 0.0014 0.0014
Cellulase 0.001 0.0014 0.001 0.01 0.01
4 4
Pectate splits 0.001 0.002 0.02 0.05 0.005
Separate enzyme
Assistant agent 0.5 0.5 0.5 0.5 0.5
Spices 0.2 0.3 0.5 0.2 0.1
Moisture and other: add to 100%
Assistant agent comprises brightener/SRP1/CMC/ optical white/MgSO4/PVPVI/ suds suppressor/PEG.
Embodiment 11
Following high-density scouring agent composition produced according to the present invention:
I II III IV makes block:
QAS 2.0 - 2.0 -
MES - 2.0 - -
LAS 6.0 - - -
TAS - 2.0 - -
C45AS 6.0 4.0 2.0 -
MBAS16.5.1.9 4.0 - - -
Zeolite A 15.0 6.0--
Carbonate 4.0 8.0 4.0 8.0
MA/AA 4.0 2.0 - 2.0
CMC 0.5 0.5 - 0.5
DETPMP 0.4 0.4-0.5 sprays:
C25E3 1.0 1.0 - -
Spices 0.5 0.5 0.5 0.5 agglomerates:
SKS-6 7.0 15.0 20.0 10.0
LAS 5.8 9.0 15.0 10.0
Zeolite-0.9--
C45?AS - 3.0 - -
Water 0.08 0.1-0.02 dried additive:
EDDS/HEDP 0.5 0.3 0.5 0.8
NaSKS?6) 5.0 6.0 4.0 11.0
Citrate trianion-1.0--
Citric 2.0 - 2.0 4.0
Catalyzer 0.005 0.1 0.02 0.02
NACA-OBS 4.1 - 5.0 4.0
TAED 0.8 2.0 - 2.0
Percarbonate 20.0 20.0 15.0 17.0
SRP1 0.3 0.3 - 0.3
Pectate lyase 0.01 0.02 0.001 0.002
Pectin lyase--0.001 0.001
Proteinase-10 .046 0.046 0.033 0.016
Lipase 0.008 0.008 0.006-
Cellulase 0.0014 0.0014 0.001 0.001
Amylase 0.003 0.003-0.0015
QEA 1.0 - 1.0 1.0
Silicone antifoam agent 1.0 0.5 0.5 1.5
Brightener 1 0.2 0.2-6.2
Brightener 2 0.2-0.2-density (g/ liter): 850 850 800 775 moisture and other: add to 100%
Embodiment 12
Following granular fabric detergent composition produced according to the present invention, it provides " soft by washing
Change " performance:
I II III IV
C45?AS - 10.0 - 10.0
LAS 7.6 - 7.6 -
C68AS 1.3 - 1.3 -
C45E7 4.0 - 4.0 -
C25E3 - 5.0 - 5.0
Chlorination (cocounut oil-alkyl 2 1.4 1.0 1.4 1.0
Methyl hydroxyl-ethyl) ammonium
Citrate trianion 5.0 3.0 5.0 3.0
Na-SKS-6 - 11.0 - 11.0
Zeolite A 15.0 15.0 15.0 15.0
MA/AA 4.0 4.0 4.0 4.0
DETPMP 0.4 0.4 0.4 0.4
DAP1 4.8 6.7 - -
Catalyzer--0.001 0.001
Percarbonate---15.0
PB1 - - 15.0 -
TAED - - 5.0 5.0
Terre verte potter's clay 10.0 10.0 10.0 10.0
HMWPEO - 0.1 - 0.1
Pectate lyase 0.001 0.01 0.001 0.01
Proteinase-10 .02 0.01 0.02 0.01
Lipase 0.02 0.01 0.02 0.01
Amylase 0.03 0.005 0.03 0.005
Cellulase 0.001-0.001-
Silicate 3.0 5.0 3.0 5.0
Carbonate 10.0 10.0 10.0 10.0
Suds suppressor 1.0 4.0 1.0 4.0
CMC 0.2 0.1 0.2 0.1
Other and assistant agent add to 100%
Embodiment 13
Following liquid detergent preparation produced according to the present invention (given level is calculated with the umber in the unit weight, and enzyme is represented with pure enzyme):
I II III IV V LAS 11.5 9.0 - 4.0 - C25E2.5S - 3.0 18.0 - 16.0 C45E2.25S 11.5 3.0 - 16.0 - C23E9 - 3.0 2.0 2.0 1.0 C23E7 3.2 - - - - CFAA - - 5.0 - 3.0 TPKFA 2.0 2.0 0.5 2.0 Citric(50％) 6.5 1.0 2.5 4.0 2.5
Calcium formiate 0.1 0.06 0.1--
Sodium formiate 0.5 0.06 0.1 0.05 0.05
SCS 4.0 1.0 3.0 1.2 -
Borate 0.6-3.0 2.0 3.0
Sodium hydroxide 6.0 2.0 3.5 4.0 3.0
Ethanol 2.0 1.0 4.0 4.0 3.0
1,2 propylene glycol 3.0 2.0 8.0 8.0 5.0
Monoethanolamine 3.0 1.5 1.0 2.5 1.0
TEPAE 2.0 - 1.0 1.0 1.0
Catalyzer 0.01 0.01 0.005 0.005 0.1
Pectate lyase 0.001 0.002 0.01 0.01 0.005
Proteinase-10 .03 0.01 0.03 0.02 0.02
Lipase--0.002--
Amylase---0.002-
Cellulase--0.0002 0.0005 0.0001
SRP1 0.2 - 0.1 - -
DTPA - - 0.3 - -
PVNO - - 0.3 - 0.2
Brightener 1 0.2 0.07 0.1--
Silicone antifoam agent 0.04 0.02 0.1 0.1 0.1
Other and water add to 100%
Embodiment 14
Following scouring agent composition produced according to the present invention (given level is calculated with the umber in the unit weight, and enzyme is represented with pure enzyme):
I II III IV V VI VII VIII
LAS - - 19.0 15.0 21.0 6.75 8.8 -
C28AS 30.0 13.5 - - - 15.7 11.2 22.5
Sodium laurate 2.5 9.0------
Wessalith CS 2.0 1.25---1.25 1.25 1.25 carbonate 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0 calcium carbonate 27.5 39.0 35.0--40.0-40.0 sulfate 5.0 5.0 3.0 5.0 3.0--5.0TSPP 5.0----5.0 2.5-STPP 5.0 15.0 10.0--7.0 8.0 10.0 bentonites-10.0--5.0---DETPMP-0.7 0.6-0.6 0.7 0.7 0.7CMC-1.0 1.0 1.0 1.0--1.0 talcum powder--10.0 15.0 10.0---silicate--4.0 5.0 3.0---PVNO, 0.02 0.03-0.01-0.02--MA/AA, 0.4 1.0--0.2,0.4 0.5 0.4SRP, 1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 pectate cracking, 0.01 0.00 0.00 0.02 0.02 0.00 0.01 0.01 enzymes, 151 amylase--0.01---0.00-
2 proteolytic enzyme-0.00-0.00 0.00--0.00
4333 lipase-0.00-0.00----
22 cellulases-.000--.000 .000--
332 catalyst, 1.0 5.0 0.1 3.0 10.0 1.0 0.3 1.0PEO-0.2-0.2 0.3--0.3 spices 1.0 0.5 0.3 0.2 0.4--0.4 magnesium sulfate--3.0 3.0 3.0---brighteners, 0.15 0.1 0.15----, 0.1 photoactivation bleaching agent-15.0 15.0 15.0 15.0--15.0 (ppm) embodiment 15
Following scouring agent composition produced according to the present invention (given level is calculated with the umber in the unit weight, and enzyme is represented with pure enzyme):
I II III IV V VI VII VIII
LAS - - 19.0 15.0 21.0 6.75 8.8 -
C28AS 30.0 13.5 - - - 15.7 11.2 22.5
Sodium laurate 2.5 9.0------
Zeolite A 2.0 1.25---1.25 1.25 1.25
Carbonate 20.0 3.0 13.0 8.0 10.0 15.0 15.0 10.0
Lime carbonate 27.5 39.0 35.0--40.0-40.0
Vitriol 5.0 5.0 3.0 5.0 3.0--5.0
TSPP 5.0 - - - - 5.0 2.5 -
STPP 5.0 15.0 10.0 - - 7.0 8.0 10.0
Wilkinite-10.0--5.0---
DETPMP - 0.7 0.6 - 0.6 0.7 0.7 0.7
CMC - 1.0 1.0 1.0 1.0 - - 1.0
Talcum powder--10.0 15.0 10.0---
Silicate--4.0 5.0 3.0---
PVNO 0.02 0.03 - 0.01 - 0.02 - -
MA/AA 0.4 1.0 - - 0.2 0.4 0.5 0.4
SRP?1 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
Pectate cracking 0.01 0.00 0.00 0.02 0.02 0.1 0.01 0.01
Enzyme 15
Amylase--0.01---0.00-
2
Proteolytic enzyme-0.00-0.00 0.00--0.00
4 3 3 3
Lipase-0.00-0.00----
2 2
Cellulase-.000--.000 .000--
3 3 2
PEO - 0.2 - 0.2 0.3 - - 0.3
Spices 1.0 0.5 0.3 0.2 0.4--0.4
Sal epsom--3.0 3.0 3.0---
Brightener 0.15 0.1 0.15----0.1
DAP1 0.4 0.6 0.8 1.0 - - 0.2 0.1
DAP2 - - - 1.0 1.0 0.8 -
Photoactivation SYNTHETIC OPTICAL WHITNER-15.0 15.0 15.0 15.0--15.0
(ppm)
Embodiment 16
Following scouring agent composition produced according to the present invention (given level is calculated with the umber in the unit weight, and enzyme is represented with pure enzyme):
I II III IV V VI VII VIII
LAS - - 19.0 15.0 21.0 6.75 8.8 -
C28AS 30.0 13.5 - - - 15.7 11.2 22.5
5
Sodium laurate 2.5 9.0------
Zeolite A 2.0 1.25---1.25 1.25 1.25
Carbonate 8.0 3.0 1.0 8.0 10.0 15.0 3.0 10.0
Lime carbonate 27.5 27.0 35.0--28.0-28.0
Vitriol 5.0 5.0 3.0 5.0 3.0--5.0
TSPP 5.0 - - - - 5.0 2.5 -
STPP 5.0 15.0 10.0 - - 7.0 8.0 10.0
Wilkinite-10.0--5.0---
DETPMP - 0.7 0.6 - 0.6 0.7 0.7 0.7
CMC - 1.0 1.0 1.0 1.0 - - 1.0
Talcum powder--10.0 15.0 10.0---
Silicate--4.0 5.0 3.0---PVNO, 0.02 0.03-0.01-0.02--MA/AA 0.4 1.0--0.2 0.4 0.5 0.4SRP1,0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 pectate cracking 0.01 0.00 0.00 0.02 0.02 0.1 0.01 0.01 enzyme 15 pectin lyases-0.00------
1 amylase--0.01---0.00-
2 proteolytic enzyme-0.00-0.00 0.00--0.00
4333 lipase-0.00-0.00----
22 cellulases-.000--.000 .000--
33 2PEO-0.2-0.2 0.3--0.3 spices, 1.0 0.5 0.3 0.2 0.4--0.4 magnesium sulfate--3.0 3.0 3.0---brightener 0.15 0.1 0.15----0.1 catalyst 0.00--0.00----
1 1BB1,0.2 0.2 0.3--0.4--BB2---0.4 0.5-, 0.45 0.3TAED, 1.7 1.7 1.7 1.7 1.7 1.7 1.7 1.7PB4,12.0 12.0 12.0 12.0 12.0 12.0 12.0 12.0NOBS, 0.2 0.2 0.2 0.20 0.2 0.2 0.2 0.2 photoactivation bleaching agent-15.0 15.0 15.0 15.0--15.0 (ppm) embodiment 17
Following compression high-density produced according to the present invention (0.96Kg/l) is washed the dish detergent composition:
I II III IV V VI STPP-51.0 51.0--44.3 17.0--50.0 40.2- 17.5 14.0 20.0-80.0 33.6 ---26.0-- 15.0 15.0 8.0-25.0 3.6 2.5 4.5 4.5---PB1 10.0 8.0 8.0---PB4---10.0------11.8 4.8 BB1-0.1 0.1-0.5-BB2 0.2 0.05-0.1-0.6 2.0 1.5 1.5 3.0 1.9 5.9 TAED 2.0--4.0-1.4 HEDP 1.0-----DETPMP 0.6-----MnTACN----0.01-PAAC-0.01 0.01--- 0.5 0.4 0.4 0.6-- 0.04 0.1 0.03 0.5 0.005 0.005 0.072 0.053 0.053 0.026 0.059 0.01 0.012 0.012 0.012 0.021 0.021 0.006 -0.001-0.005--BTA 0.3 0.2 0.2 0.3 0.3 0.3 6.0---4.0 0.9 0.2 0.1 0.1 0.2 0.2 0.2 pH 11.0 11.0 11.3 9.6 10.8 10.9
Other, vitriol and add to 100%
Water
Embodiment 18
Following tap density produced according to the present invention is the granular dish detergent composition of washing of 1.02Kg/L:
I II III IV V VI
STPP 30.0 33.5 27.9 29.6 33.8 22.0
Carbonate 30.5 30.5 30.5 23.0 34.5 45.0
Silicate 7.0 7.5 12.6 13.3 3.2 6.2
Metasilicate-4.5----
Percarbonate----4.0-
PB1 4.4 4.5 4.3 - - -
BB1 - 0.3 - 0.2 - -
BB2 0.4 - 0.2 - 0.6 0.4
Non-ionic type 1.0 0.7 1.0 1.9 0.7 0.5
TAED 1.0 - - - 0.9 -
PAAC - 0.004 - - - -
Paraffinic hydrocarbon 0.25 0.25----
Pectate lyase 0.4 0.005 0.001 0.02 0.02 0.1
Proteinase-10 .036 0.021 0.03-0.006-
Amylase 0.03 0.05 0.004-0.005-
Lipase 0.005-0.001---
BTA 0.15 0.15 - - 0.2 -
Spices 0.2 0.2 0.05 0.1 0.2-
pH 10.8 11.3 11.0 10.7 11.5 10.9
Other, vitriol and add to 100%
Water
Embodiment 19
According to the present invention, 12 rotary press of use standard are at l3KN/cm
2Pressure under, wash the following tablet detergent compositions agent of dish washing composition preparation of compositions by compression granulated:
I II III IV V VI VII VIII STPP-48.8 54.7 38.2-52.4 56.1 36.0 citrate 20.0---35.9---carbonate 20.0 5.0 14.0 15.4 8.0 23.0 20.0 28.0 silicate 15.0 14.8 15.0 12.6 23.4 2.9 4.3 4.2 pectate cracking 0.00 0.00 0.01 0.00 0.02 0.02 0.00 0.00 enzyme 11415 proteinase-10 .04 0.07 0.04 0.03 0.05 0.02 0.02 0.02
22212339 amylase 0.01 0.01 0.01 0.00 0.01 0.00 0.01 0.00
22275372 lipase 0.00-------
5 PB1,14.3 7.8 11.7 12.2--, 6.7 6.5 PB4---22.8-3.4-percarbonate-----10.4--BB1 0.2-0.5-0.3 0.2--BB2-0.2-0.5--0.1 0.2 nonionics, 1.5 2.0 2.0 2.2 1.0 4.2 4.0 6.5 PAAC--0.02 0.00----
9 MnTACN - - - - 0.00 - - -
7 TAED, 2.7 2.4---, 2.1 0.7 1.6 HEDP 1.0--0.9-0.4 0.2-DETPMP 0.7-------paraffin hydrocarbon 0.4 0.5 0.5 0.5--0.5-BTA, 0.2 0.3 0.3 0.3 0.3 0.3 0.3-polycarboxylate 4.0---4.9 0.6 0.8-
PEG - - - - - 2.0 - 2.0
Glycerine-----0.4-0.5
Spices---0.05 0.2 0.2 0.2 0.2
Tablet weight 20g 25g 20g 30g 18g 20g 25g 24g
pH 10.7 10.6 10.7 10.7 10.9 11.2 11.0 10.8
Other, vitriol adds to 100%
And water
Embodiment 20
Following compression high-density produced according to the present invention (0.96kg/l) dish washing agent composition:
I II III IV V VI
STPP - 51.0 51.0 - - 44.3
Citrate trianion 17.0--50.0 40.2-
Carbonate 17.5 14.0 20.0-8.0 33.6
Supercarbonate---26.0--
Silicate 15.0 15.0 8.0-25.0 3.6
Metasilicate 2.5 4.5 4.5---
PB1 10.0 8.0 8.0 - - -
PB4 - - - 10.0 - -
Percarbonate----11.8 4.8
Non-ionic type 2.0 1.5 1.5 3.0 1.9 5.9
DAP1 0.2 1.0 4.3 6.7 1.7 0.3
TAED 2.0 - - 4.0 - 1.4
HEDP 1.0 - - - - -
DETPMP 0.6 - - - - -
MnTACN - - - - 0.01 -
PAAC - 0.01 0.01 - - -
Paraffinic hydrocarbon 0.5 0.4 0.4 0.6--
Pectate lyase 0.04 0.001 0.03 0.005 0.005 0.005
Proteinase-10 .072 0.053 0.053 0.026 0.059 0.01 amylase 0.012 0.012 0.012 0.021 0.021 0.006 lipase-0.001-0.005--BTA 0.3 0.2 0.2 0.3 0.3 0.3 polycarboxylates 6.0---4.0 0.9 spices, 0.2 0.1 0.1 0.2 0.2 0.2 pH 11.0 11.0 11.3 9.6 10.8 10.9 other, sulfate and add to 100% water
Embodiment 21
Following tap density produced according to the present invention is the granular dish washing agent composition of 1.02Kg/L:
I II III IV V VI STPP 30.0 33.5 27.9 29.6 33.8 22.0 carbonate 30.5 30.5 30.5 23.0 34.5 45.0 silicate 7.0 7.5 12.6 13.3 3.2 6.2 metasilicates-4.5----percarbonate----4.0-DAP1 3.3 6.7 0.03 0.5 10.0 0.03 PB1 4.4 4.5 4.3---NADCC---2.0-0.9 nonionics 1.0 0.7 1.0 1.9 0.7 0.5 TAED 1.0---0.9-PAAC-0.004----paraffin hydrocarbons 0.25 0.25----pectate lyases 0.4 0.005 0.001 0.02 0.02 0.1 proteinase-10 .036 0.021 0.03-0.006-amylase 0.03 0.005 0.004-0.005-lipase 0.005-0.001---BTA 0.15 0.15--0.2-spices 0.2 0.2 0.05 0.1 0.2-
pH 10.8 11.3 11.0 10.7 11.5 10.9
Other, vitriol and add to 100%
Water
Embodiment 22
According to the present invention, 12 rotary press of use standard are at l3KN/cm
2Pressure under, by the following tablet detergent composition of compression granulated dish washing agent preparation of compositions:
I II III IV V VI VII VIII
STPP - 48.8 54.7 38.2 - 52.4 56.1 36.0
Citrate trianion 20.0---35.9---
Carbonate 20.0 5.0 14.0 15.4 8.0 23.0 20.0 28.0
Silicate 15.0 14.8 15.0 12.6 23.4 2.9 4.3 4.2
Pectate cracking 0.1 0.00 0.01 0.4 0.02 0.02 0.1 0.00
Enzyme 15
Proteinase-10 .04 0.07 0.04 0.03 0.05 0.02 0.02 0.02
2 2 2 1 2 3 3 9
Amylase 0.01 0.01 0.01 0.00 0.01 0.00 0.01 0.00
2 2 2 7 5 3 7 2
Lipase 0.00-------
5
PB1 14.3 7.8 11.7 12.2 - - 6.7 8.5
PB4 - - - - 22.8 - 3.4 -
Percarbonate-----10.4--
DAP1 0.6 0.8 1.0 1.2 1.1 0.8 0.5 1.4
Non-ionic type 1.5 2.0 2.0 2.2 1.0 4.2 4.0 6.5
PAAC - - 0.02 0.009 - - - -
MnTACN - - - - 0.00 - - -
7
TAED 2.7 2.4 - - - 2.1 0.7 1.6
HEDP 1.0--0.9-0.4 0.2-DETPMP 0.7-------paraffin hydrocarbon 0.4 0.5 0.5 0.5--0.5-BTA 0.2 0.3 0.3 0.3 0.3 0.3 0.3-polycarboxylate 4.0---4.9 0.6 0.8-PEG-----2.0-2.0 glycerine-----0.4-0.5 spices---0.05 0.2 0.2 0.2 0.2 tablet weight 20g 25g 20g 30g 18g 20g 25g 24g pH 10.7 10.6 10.7 10.7 10.9 11.2 11.0 10.8 other, sulfate adds to 100% and water
Embodiment 23
Following compression high-density produced according to the present invention (0.96kg/l) dish washing agent composition:
I II III IV V VI STPP-51.0 51.0--44.3 citrate 17.0--50.0 40.2-carbonate 17.5 14.0 20.0-8.0 33.6 bicarbonates---26.0--silicate 15.0 15.0 8.0-25.0 3.6 metasilicates 2.5 4.5 4.5---catalyst 0.01 0.005 0.1 2.0 0.01 0.005 PB1 10.0 8.0 8.0---PB4---10.0--percarbonate----11.8 4.8 nonionics 2.0 1.5 1.5 3.0 1.9 5.9 TAED 2.0--4.0-1.4 HEDP 1.0-----DETPMP 0.6-----PAAC-0.01 0.01---
Paraffinic hydrocarbon 0.5 0.4 0.4 0.6--
Pectate lyase 0.04 0.001 0.03 0.005 0.005 0.005
Proteinase-10 .072 0.053 0.053 0.026 0.059 0.01
Amylase 0.012 0.012 0.012 0.021 0.021 0.006
Lipase-0.001-0.005--
BTA 0.3 0.2 0.2 0.3 0.3 0.3
Polycarboxylate 6.0---4.0 0.9
Spices 0.2 0.1 0.1 0.2 0.2 0.2
pH 11.0 11.0 11.3 9.6 10.8 10.9
Other, vitriol and add to 100%
Water
Embodiment 24
Following tap density produced according to the present invention is the granular dish washing agent composition of 1.02Kg/L:
I II III IV V VI
STPP 30.0 33.5 27.9 29.6 33.8 22.0
Carbonate 30.5 30.5 30.5 23.0 34.5 45.0
Silicate 7.0 7.5 12.6 13.3 3.2 6.2
Metasilicate-4.5----
Catalyzer 0.01 0.2 0.005 0.1 1.00 0.5
Percarbonate----4.0-
PB1 4.4 4.5 4.3 - - -
NADCC - - - 2.0 - 0.9
Non-ionic type 1.0 0.7 1.0 1.9 0.7 0.5
TAED 1.0 - - - 0.9 -
PAAC - 0.004 - - - -
Paraffinic hydrocarbon 0.25 0.25----
Pectate lyase 0.004 0.005 0.001 0.02 0.02 0.001
Proteinase-10 .036 0.021 0.03-0.006-
Amylase 0.03 0.005 0.004-0.005-
Lipase 0.005-0.001---
BTA 0.15 0.15 - - 0.2 -
Spices 0.2 0.2 0.05 0.1 0.2-
pH 10.8 11.3 11.0 10.7 11.5 10.9
Other, vitriol and add to 100%
Water
Embodiment 25
According to the present invention, 12 rotary press of use standard are at l3KN/cm
2Pressure under, by the following tablet detergent composition of compression granulated dish washing agent preparation of compositions:
I II III IV V VI VII VIII
STPP - 48.8 54.7 38.2 - 52.4 56.1 36.0
Citrate trianion 20.0---35.9---
Carbonate 20.0 5.0 14.0 15.4 8.0 23.0 20.0 28.0
Silicate 15.0 14.8 15.0 12.6 23.4 2.9 4.3 4.2
Pectate cracking 0.00 0.00 0.01 0.00 0.02 0.02 0.00 0.00
Enzyme 11415
Proteinase-10 .04 0.07 0.04 0.03 0.05 0.02 0.02 0.02
2 2 2 1 2 3 3 9
Amylase 0.01 0.01 0.01 0.00 0.01 0.00 0.01 0.00
2 2 2 7 5 3 7 2
Lipase 0.00-------
5
Catalyzer 0.00 0.00 0.05 0.00 0.00 0.00 0.01 0.00
1 3 1 1 3 1
PB1 14.3 7.8 11.7 12.2 - - 6.7 8.5
PB4 - - - - 22.8 - 3.4 -
Percarbonate-----10.4--
Non-ionic type 1.5 2.0 2.0 2.2 1.0 4.2 4.0 6.5
PAAC - - 0.02 0.00 - -
9 TAED, 2.7 2.4---2.1,0.7 1.6 HEDP 1.0--0.9-0.4 0.2-DETPMP 0.7-------paraffin hydrocarbons, 0.4 0.5 0.5 0.5--0.5-BTA, 0.2 0.3 0.3 0.3 0.3 0.3 0.3-polycarboxylate 4.0---4.9,0.6 0.8-PEG-----2.0-2.0 glycerine-----0.4-0.5 spices---0.05 0.2 0.2 0.2 0.2 tablet weight 20g 25g 20g 30g 18g 20g 25g 24g pH 10.7 10.6 10.7 10.7 10.9 11.2 11.0 10.8 other, sulfate adds to 100% and water
Embodiment 26
Following liquid produced according to the present invention helps detergent composition:
I II III IV
Pectate lyase 0.001 0.0005 0.01 0.001
Pectin lyase 0.001 0.001-0.001
Catalyzer 0.1 0.01 0.008 0.001
Non-ionic type 10.0 13.6 62.3 60.0
Propylene glycol--5.0 5.5
Citric 3.5 4.6 - -
SCS 10.0 7.7 - -
Liquid pH 3.0 2.5 7.2 7.2
Other, solvent and water adds to 100%
Embodiment 27
The following video disc agent (starting material are in g, and enzyme is represented with pure enzyme) of washing automatically constructed in accordance:
I II III IV V VI phase 1
STPP 9.6 9.6 10.6 9.6 9.6 10.6
Silicate 0.5 0.7 2.9 0.5 0.7 2.9
SKS-6 1.5 1.5 - 1.5 1.5 -
Carbonate 2.3 2.7 2.8 2.3 2.7 2.8
HEDP 0.2 0.2 0.2 0.2 0.2 0.2
PB1 2.4 2.4 2.8 2.4 2.4 2.8
PAAC 0.002 0.002 - - - -
Catalyzer---0.002 0.002-
BB1 0.2 0.5 - - - -
DAP1 - - 0.5 - - 0.2
Amylase 0.1 0.1 0.001 0.1 0.1 0.001
Proteinase-10 .06 0.06 0.002 0.06 0.06 0.002
Non-ionic type 0.4 0.8 0.4 0.4 0.8 0.4
PEG?6000 0.4 0.26 - 0.4 0.26 -
BTA 0.4 0.4 0.6 0.4 0.4 0.6
Paraffinic hydrocarbon 0.1 0.10 0.1 0.1 0.10 0.1
Spices 0.02 0.02 0.02 0.02 0.02 0.02 amounts to 17.7g 18.5g 20.1g 17.7g 18.5g 20.1g phase 2
Pectate splits 0.005 0.5 0.2 0.005 0.5 0.2
Separate enzyme
Pectin lyase 0.001--0.001--
Amylase 0.003 0.003 0.004 0.003 0.003 0.004
Proteinase-10 .01 0.009 0.01 0.01 0.009 0.01
Citric acid 0.3-0.6 0.3-0.6
Thionamic acid-0.3--0.3-
Supercarbonate 1.1 0.4 0.6 1.1 0.4 0.6
Carbonate-0.5--0.5-
Triactin--1.2--1.2
CaCl2 - 0.07 0.1 - 0.07 0.1
PEG?6000 - - 1.2 - - 1.2
PEG 3,000 0.06 0.06-0.06 0.06-total 2.05g 2.50g 23.6g 2.05g 2.50g 23.6g
Tablet composition I and II are prepared as follows: the preparation of 1 washing composition active composition is that granular and liquid component are mixed mutually, sends into then in the punch die of conventional rotary press.Press comprises a drift suitable with forming model, and the cross section of punch die is about 30 * 38mm.Said composition is subjected to 940kg/cm
2Pressure, and lift first phase that drift exposes tablet then, there is mould appearance on the surface thereon.2 washing composition active composition prepares with the same manner mutually, and sends in the punch die.This particulate state active composition is subjected to 170kg/cm then
2Pressure, lift drift, this many-phase tablet ejects from tabletting machine.As mentioned above, the tablet that is generated is dissolving or decompose within 12 minutes in washing machine, and the phase 2 of tablet dissolve within 5 minutes, and the intensity that tablet presented has been improved, and especially in long-time storage, and demonstrates extraordinary dissolution characteristics simultaneously.
Tablet composition III is prepared as follows: compression section is that the composition of activated detergent composition is sent in the punching press chamber of improved rotary tablet machine, at 940kg/cm
2Pressure lower compression said composition prepare.Compression section has a kind of model in the tablet that this improved tabletting machine provides.Be the purpose of EXAMPLE III, non--compression section is a particle form.Use the nozzle feed appliance that this non--compression section is accurately sent in the model of compression section, the non--compression section of coating coating with the contact compression section adheres on the compression section non--compression section.
Claims (30)
1. detergent composition; it contains detergent ingredients, pectate lyase and bleach system; bleach system is selected from composition, diacyl peroxide and/or their mixture of metal bleach catalyst, peroxygen source and bleaching secondary accelerator, and this bleaching secondary accelerator is selected from the zwitter-ion imines, has the negatively charged ion imines polyion of-1～-3 net negative charge and/or their mixture.
2. according to the detergent composition of claim 1, wherein metal bleach catalyst is selected from:
(a) catalyzer [Mn (Bcyclam) Cl
2];
(b) has chemical formula Co[(NH
3)
nM
mB
bT
tQ
qP
p] Y
yCobalt catalyst, wherein cobalt is
In+3 oxidation state, n is 0～5 integer, and is preferred 4～5, more preferably 5; M represents
The monodentate part; M is 0～5 integer, and is preferred 1～2, more preferably 1; The B table
Show the bidentate part; B is 0～2 integer; T represents the tri-dentate part; t
Be 0 or 1; Q is a tetradentate ligand; Q is 0 or 1; P is the pentacoordinate ylidene ligands; p
Be 0 or 1, and n+m+2b+3t+4q+5p=6; Y is one or more suitable selections
The number that exists be the counter anion of y, wherein y is 1～3 integer, preferred 2～
3, when Y is the negatively charged ion of band-1 valence charge more preferably 2, to obtain electric charge-balance
Salt;
(c) having chemical formula is [Co (NH
3) 5M] T
yCobalt catalyst, wherein cobalt is at+3 oxygen
Change attitude; M contains the carboxylate radical part that chemical formula is RC (O) O-; And T is a kind of
Or the multiple number that exists is the counter anion of y, and wherein y can obtain electric charge-balance
The integer (preferred 1～3, when T is band-1 valence charge negatively charged ion more preferably 2) of salt;
And/or their mixture.
3. according to the detergent composition of claim 1 or 2, it contains said metal bleach catalyst and further contains peroxygen source, preferably is selected from hydrogen peroxide cource, peroxy acid bleach precursor compound and/or their mixture.
4. according to the composition of claim 2 or 3, wherein the amount of metal bleach catalyst is 1ppb～10% of total composition weight, preferred 0.1ppm～1%, more preferably 1ppm～0.1%.
5. according to the detergent composition of above-mentioned arbitrary claim; wherein said diacyl peroxide is selected from dibenzoyl superoxide, benzoyl glutaryl-superoxide, benzoyl succinyl superoxide, two (2-methyl benzoyl) superoxide and/or their mixture.
6. according to the detergent composition of claim 5, wherein said diacyl peroxide is the dibenzoyl superoxide.
7. according to the detergent composition of above-mentioned arbitrary claim; wherein said diacyl peroxide is comprised among the particulate, and said particulate contains the water-soluble stabilization additives of the 0.01-95% of 1～80% diacyl peroxide of said particulate weight, said particulate weight.
8. according to the detergent composition of claim 7, wherein said stabilization additives is selected from alkali metal sulfates and Citrate trianion, ethoxylation C
16-20Alcohols, at polyacrylate polymers and multipolymer, ethylenediamine tetraacetic-acetate, ethylenediamine disuccinate and/or their mixture between 1.000 and 80.000 of fused polyoxyethylene glycol, Star Dri 5, molecular weight more than 100.
9. according to the detergent composition of claim 1～4, wherein said diacyl peroxide is two bay acyl peroxides.
10. according to the detergent composition of above-mentioned arbitrary claim, the level that wherein contains said diacyl peroxide is 0.01%～20% of a composition weight, and is preferred 0.5%～10%, more preferably 0.2%～3%.
11. according to the detergent composition of claim 7～10, wherein diacyl peroxide is impregnated in the particulate, and the level that said composition contains said particulate is 0.1%～30% of composition total weight, and is preferred 1%～15%, and more preferably 1.5%～10%.
12. according to the detergent composition of above-mentioned arbitrary claim, wherein said bleaching secondary accelerator is selected from aryl imonium zwitter-ion, has the aryl imonium polyion of-1～-3 net negative charge and/or their mixture.
13. according to the detergent composition of claim 12, wherein said bleaching secondary accelerator has chemical formula:
R wherein
1～R
3Be to have about 0～approximately-1 the part of total charge; R
1And R
2It is common to form part
Ring; T is selected from :-(CH
2)
b-wherein b be about 1～about 8 ,-(CH (R
5))-R wherein
5Be C
1～C
8Alkyl ,-CH
2(C
6H
4)-,
With-(CH
2)
d(E) (CH
2)
f-wherein d be 2～8, f be 1～3 and E be-C (O) O-,-C (O) NR
6Or:
R wherein
6Be H or C
1～C
4Alkyl; The Z covalent linkage is connected on the T, and Z is selected from-CO
2 -,-SO
3 -
With-OSO
3 -And a or 1 or 2.
14. according to the detergent composition of claim 12～13, wherein R
1And R
2Form not together-alive part:
15. according to the detergent composition of claim 12～14, wherein said bleaching secondary accelerator is an aryl imonium zwitter-ion, and R
3Be H, T is-(CH
2)
b-or-CH
2(C
6H
4)-, Z is-SO
3 -, a be 1 and b be 2～4.
16. according to the detergent composition of claim 12～15, wherein said bleaching secondary accelerator is the aryl imonium zwitter-ion with following chemical formula:
Or
17. according to the detergent composition of claim 12, wherein said bleaching secondary accelerator has following chemical formula:
R wherein
1～R
3Be hydrogen or group unsubstituted or that replace, these groups are selected from phenyl, aryl, heterocyclic cyclic group, alkyl and cycloalkyl; R
1And R
2Form part common ring; T has following chemical formula:
Wherein x equals 0 or 1; J if exist, is selected from-CR
11R
12-,-CR
11R
12CR
13R
14-and
-CR
11R
12CR
13R
14CR
15R
16-; R
7～R
16Be selected from H, C linear or side chain
1～C
18Replace
Or unsubstituted alkyl, alkylidene group, oxyalkylene group, aryl, substituted aryl, substituted aryl
Carbonyl group and amide group; Be R
7～R
8In at least one group must be H or methyl,
Reach and work as R
9Or R
10When neither being H, R
7～R
8In one must be H; When x is 1, Z
Covalent linkage is connected to J
xOn, and when x was 0, the Z covalent linkage was connected to C
bOn; And Z is selected from-CO
2 -,
-SO
3 -With-OSO
3 -With a be 1.
18. according to the detergent composition of claim 17, R in the wherein said bleaching secondary accelerator
1And R
2In its chemical formula, be defined as R
1And R
2Form not charged-part together:
19. according to the detergent composition of claim 17～18, wherein said bleaching secondary accelerator is aryl imonium zwitter-ion and R
3Be H, Z is-OSO
3 -, a is 1.
20. according to the detergent composition of claim 17～19, wherein said bleaching secondary accelerator is the aryl imonium zwitter-ion with following chemical formula:
R wherein
17Be selected from the C of H and linearity or side chain
1～C
18Replace or unsubstituted alkyl.
21. according to the detergent composition of above-mentioned arbitrary claim, the content of wherein said bleaching secondary accelerator is 0.01%～10% of total composition weight.
22. according to the detergent composition of claim 12～21, wherein the content of said peroxygen source is 0.01%～60% of total composition weight.
23. detergent composition according to claim 12～22, wherein said peroxygen source contains ready-formed peracid compound, hydrogen peroxide cource, bleach-activating agent and/or their mixture, and described peracid compound is selected from percarboxylic acids and salt, percarbonic acid and salt, crosses imido acid and salt, permonosulphuric acid and salt and/or their mixture.
24. according to the detergent composition of claim 23, wherein said hydrogen peroxide cource is selected from perborate compound, percarbonate compound, superphosphate compound and/or their mixture.
25. according to the detergent composition of claim 23, wherein said bleach-activating agent is selected from tetra acetyl ethylene diamine, last of the ten Heavenly stems acyloxy benzene sulfonic acid sodium salt, ninth of the ten Heavenly Stems acyloxy benzene sulfonic acid sodium salt, hot acyloxy benzene sulfonic acid sodium salt, (6-decoyl amino-hexanoyl) oxygen base benzene sulfonate, (6-nonanoyl amino-hexanoyl) oxygen base benzene sulfonate, (6-caprinoyl amino-hexanoyl) oxygen base benzene sulfonate and/or their mixture.
26. according to the detergent composition of above-mentioned arbitrary claim, the level that wherein said pectate lyase exists is 0.0001%～2% of a total composition weight, and is preferred 0.0005%～1.0%, more preferably 0.001%～0.5% pure enzyme.
27., further contain pectin lyase according to the detergent composition of above-mentioned arbitrary claim.
28. according to the composition of above-mentioned arbitrary claim remove plant-, dirt-Ji stain, dark food dirt/stain and the application in the health dirt.
29. the application of composition in good fabric whiteness is safeguarded according to above-mentioned arbitrary claim.
30. removing stain and dirt dark on the plastic ware effectively according to the composition of claim 5～11, and/or preventing that tableware from being caught application in stain and/or the variable color by dark composition.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| WOPCT/US99/00790 | 1999-01-14 | ||
| PCT/US1999/000806 WO2000042154A1 (en) | 1999-01-14 | 1999-01-14 | Detergent compositions comprising a pectate lyase and a mid-branched anionic surfactant |
| PCT/US1999/000797 WO2000042147A1 (en) | 1999-01-14 | 1999-01-14 | Detergent compositions comprising a pectate lyase and a semi-polar nonionic surfactant |
| WOPCT/US99/00800 | 1999-01-14 | ||
| PCT/US1999/000803 WO2000042151A1 (en) | 1999-01-14 | 1999-01-14 | Detergent compositions comprising a pectate lyase and a bleach booster |
| WOPCT/US99/00801 | 1999-01-14 | ||
| PCT/US1999/000800 WO2000042148A1 (en) | 1999-01-14 | 1999-01-14 | Detergent tablets comprising a pectate lyase |
| WOPCT/US99/00803 | 1999-01-14 | ||
| PCT/US1999/000802 WO2000042150A1 (en) | 1999-01-14 | 1999-01-14 | Detergent compositions comprising a pectate lyase and a metal bleach catalyst |
| WOPCT/US99/00802 | 1999-01-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1336952A true CN1336952A (en) | 2002-02-20 |
Family
ID=34199307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00802789 Pending CN1336952A (en) | 1999-01-14 | 2000-01-13 | Detergent compositions comprising pectate lyase and a blench system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1336952A (en) |
-
2000
- 2000-01-13 CN CN 00802789 patent/CN1336952A/en active Pending
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