CN1871336A - Stable compositions of spores, bacteria, and/or fungi - Google Patents

Stable compositions of spores, bacteria, and/or fungi Download PDF

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CN1871336A
CN1871336A CN 200480031302 CN200480031302A CN1871336A CN 1871336 A CN1871336 A CN 1871336A CN 200480031302 CN200480031302 CN 200480031302 CN 200480031302 A CN200480031302 A CN 200480031302A CN 1871336 A CN1871336 A CN 1871336A
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composition
borate
surfactant
present
alkyl
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V·F·曼
J·P·马格努森
L·M·桑德斯
S·E·伦特施
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Ecolab Inc
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Ecolab Inc
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Abstract

The present invention relates to a stable cleaning composition including a borate salt and spores (bacterial or fungal), vegetative bacteria, or fungi. The composition can also include a polyol.

Description

The stable composition of spore, bacterium and/or fungi
Technical field
The present invention relates to stable cleaning composition, the method that it comprises borate and spore (bacterium or fungi), nutrition (vegetative) bacterium or fungi and uses said composition.Said composition also comprises polyvalent alcohol.
Background technology
Spore, bacterium and fungi especially play important effect in those cleaning compositions that use in cleaning water shoot and grease trap in cleaning compositions.The existing composition that contains spore, bacterium or fungi typically provides with " two parts " product form, and one of them container is that biological components and second container are chemical cleaners.Mixed chemical sanitising agent and biological components, it is impossible storing this mixture then, this is because chemical has negative impact to spore, bacterium or fungi.Still need to comprise simultaneously the stable cleaning composition (for example, " single part " composition) of chemical cleaner and spore, bacterium or fungi.
Summary of the invention
The present invention relates to stable cleaning composition, the method that it comprises borate and spore (bacterium or fungi), bacterial nutrition or fungi and uses said composition.Said composition also comprises polyvalent alcohol.
In one embodiment, composition of the present invention comprises spore, bacterium or the fungi of borate and effective cleaning amount.Borate can comprise the alkanolamine borate.Borate and/or composition can be substantially free of sodium ion.In one embodiment, composition of the present invention can provide the preparation that contains spore (bacterium or fungi), bacterial nutrition or fungi, and said preparation has suitable stability under more than or equal to 9 pH.In one embodiment, composition of the present invention can provide the preparation that contains spore (bacterium or fungi), bacterial nutrition or fungi, and said preparation has suitable stability under water maximum about 65wt%'s.
Cleaning compositions of the present invention also can comprise non-ionic tensio-active agent, silicone surfactant, one or more in anion surfactant and the hydrotropic agent.This cleaning compositions can comprise one or more about nonionogenic tensides of 0.003 to about 35wt%, about silicone surfactant of 0.0005 to about 35wt%, about anion surfactant of 0.003 to about 35wt% and about hydrotropic agent of 0.001 to about 20wt%.This cleaning compositions can comprise nonionogenic tenside and silicone surfactant.This cleaning compositions can comprise about nonionogenic tenside of 0.5 to about 35wt% and about silicone surfactant of 0.1 to about 35wt%.
Method of the present invention can comprise and applies composition of the present invention on surface or object to be cleaned.The composition that is applied can be stable microbial composite or cleaning compositions.Surface to be cleaned or object can comprise one or more in ground, water shoot or the floor drain.In one embodiment, method of the present invention can comprise the frictional coefficient that increases the surface.In one embodiment, the present invention can comprise cleaning mortar (grout).In one embodiment, surface or mortar are ground (floor) or earth material (flooring).
The accompanying drawing summary
Fig. 1 shows weekly and carries out the result that frictional coefficient (sliding resistance) is measured gained for the ceramic tile in the kitchen, restaurant.
Fig. 2 A and 2B show the present composition and clean the ground mortar of clinker tile in the kitchen at the restaurant.Fig. 2 A has illustrated the ground before applying the present composition.Fig. 2 B has illustrated the ground after applying the present invention.
Fig. 3 shows a part of ground (left side) of adopting conventional cleaning compositions cleaning and a part of ground of cleaning with composition of the present invention.
Detailed Description Of The Invention
Definition
" microorganism formulation " as used herein refers to contain one or more the composition in spore (bacterium or fungi), bacterial nutrition or the fungi, and it can provide in anticorrisive agent. " bacteria preparation " as used herein refers to contain the composition of bacterial spore and/or bacterial nutrition, and it can provide in anticorrisive agent. Anticorrisive agent for example can comprise employed any or various antiseptic compositions in the preparation of spore (bacterium or fungi), bacterial nutrition or the fungi of commercial offers. This anticorrisive agent can comprise for example chelating agent, surfactant, buffer, water or analog. Microorganism formulation can for example digest or the dirt of degrading, for example fat, oil, lubricating grease, sugar, protein, carbohydrate or analog.
The representations such as percetage by weight as used herein (wt%), % by weight, % weight are synonyms, they refer to when the weight of this material divided by the weight of composition and the material concentration when multiply by 100.
Salt and the borate of boric acid as used herein are used interchangeably, and they refer to the salt such as potassium borate, MEA borate, maybe can obtain or imaginabale another salt another salt that obtains with boric acid in for example passing through. Salt or boratory percetage by weight at present composition mesoboric acid can be expressed as the ion that contains electronegative boron, for example borate and/or boric acid the part percetage by weight, perhaps whole borates, for example these two percetage by weight of the part of electronegative part and positively charged. Preferably, percetage by weight refers to the salt of whole boric acid. The percetage by weight of the salt of citric acid or other sour salt also can these modes be expressed, and preferably refers to the salt of all acid. Term as used herein " all boron compounds " refers to borate and boric acid part sum.
Alkali as used herein or alkaline pH are meant pH greater than 7, and more than or equal to 8, about 8 to about 9.5, about 8 to about 11, greater than about 9, or about 9 to about 10.5.
" being substantially free of sodium ion " as used herein is meant the composition that contains less than about 1wt% sodium ion.The embodiment of the present composition can comprise the sodium ion less than 1wt%, sodium ion less than 0.75wt%, sodium ion less than 0.5wt%, sodium ion less than 0.25wt%, sodium ion less than 0.2wt%, less than the sodium ion of 0.15wt%, less than the sodium ion of 0.1wt%, less than the sodium ion of 0.05wt%.Can change in these consumptions each by term " about ".
Term as used herein " earth material " or " ground " are meant any horizontal surface that people can walk thereon.Earth material or ground can be by inorganic materials for example ceramic tile or natural stones (for example, clinker tile), or organic materials for example Resins, epoxy, polymkeric substance, rubber or resilient material are made.Earth material or ground can be in any or various environment, for example restaurant (for example snack bar), food-processing and/or preparation enterprise, slaughterhouse, packing shop, shortening (shortening) production plant, kitchen or like environment.
Wording as used herein " frictional coefficient " and " sliding resistance " can be according to any definition the in the various Open Standards, ASTM standard D-2047 for example, " Static Coefficientof Friction of Polish Coated Floor Surfaces as Measured by theJames Machine ", with the report of ASTM Committee D-21, this report shows that the static friction coefficient according to this experimental measurement is not less than 0.5 ground and is considered to provide non-hazardous walking surface.This numerical value proves qualified in the NBS of Robert J.Brungraber Technical Note895 " An Overview of Floor Slip-Resistance; With AnnotatedBibliography ", wherein it shows that 0.5 numerical value provides safe coefficient, and the most of people that normally take a step can not slip on the surface of this numerical value greater than 0.3-0.35.Other relevant and similar standard comprises ANSI 1264.2-2001, ASTMC1028-89, ASTM D2047-93, ASTM F1679-00 (it relates to Britain XL frictional force meter), ASTM methods of test F1677-96 and UL410 (1992).Each standard in this paragraph is introduced by reference at this.
The term " about " of employed component content is the change of index amount in the change present composition as used herein or the inventive method, this Change Example as by preparation enriched material in real world or use the employed typical measurement of solution and the material processing operation, by in these operations, making unintentionally mistake, cause and may take place by difference and the analogue for preparing the present composition or carry out preparation, source or the purity of employed each composition of method of the present invention.Whether no matter change by term " about ", claim comprises the Equivalent of these content.
Stable microbial preparation
The present invention relates to the stable microbial preparation of boracic hydrochlorate and microorganism.This microorganism can be spore (bacterium or fungi), bacterial nutrition or fungi form.Microbial preparation can comprise the dirt that for example can digest or degrade, for example the spore or the spore blend of lubricating grease, oil (for example vegetables oil or animal tallow), protein, carbohydrate or analogue.Microbial preparation also can produce the enzyme of assistant degradation dirt such as lubricating grease, oil, fat, protein, carbohydrate or analogue.Borate can comprise any in the various salt of boric acid, for example some an alkali metal salts or alkanol amine salt.The salt of boric acid provides alkali source can for the cleaning compositions that contains stable microbial preparation.
Compare with the microbial preparation of the routine of for example using in cleaning compositions, the salt of boric acid can provide microbial preparation favourable stability.For example begin to have 10 4The microbial preparation of the routine of individual viable bacteria or spore only contained 10 after 4 months 3Or even only 10 2The organism of individual work.That is to say that they lose 1 or 2 logarithmic active organism, this can reduce the amount of contaminants removing, digest or degrade.In one embodiment, stable microbial preparation of the present invention internal loss in 4 months less than 1 or 2 logarithm, perhaps less than 1 logarithmic activity.This provides long shelf-life for the product that contains microbial preparation.
In one embodiment, stable microbial preparation of the present invention is a component in the cleaning compositions.Although do not limit the present invention, this microbial preparation can be regarded as the source of the detergency enzymes in cleaning compositions.This cleaning compositions also can comprise the extra enzyme that is not by the microbial preparation produce in situ.Microbial preparation can produce for example enzyme, for example proteolytic enzyme, lipase and/or amylase.Said composition also can comprise the enzyme that other adds, for example proteolytic enzyme, lipase and/or amylase.Although do not limit the present invention, provide in case the enzyme that adds can be regarded as using cleaning compositions immediately that cleaning and microbial preparation are regarded as when microorganism is retained on the goods to be cleaned, even persistent cleaning is provided after rinsing.
Most of sanitising agents only can provide scrubbing, this scrubbing only actually be make dirt from a surface or position (for example ground) move in another (for example water shoot).In some embodiments, the permanent enzyme of the cleaning compositions that contains the stable microbial preparation of the present invention by dirt decomposes can provide scrubbing and persistent dirt to descend simultaneously.The cleaning compositions that contains stable microbial preparation of the present invention can be used for various purposes, comprising be used as the lubricating grease digestive pharmaceutical as ground cleaner, as the mortar sanitising agent, as the combination of ground and waterways sanitising agent and grease-removing agent/lubricating grease digestive pharmaceutical, in grease trap, (for example in handling, municipal wastewater is used for effluent liquid and/or wastewater treatment, reduce fat, oil and grease), in refinery,, perhaps on the steamer that cruises, be used for black and grey water treatment as the lubricating grease digestive pharmaceutical.
Although do not limit the present invention, think that stable microbial composite of the present invention can make lip-deep lubricating grease or oil decomposition.Decompose lubricating grease or oil can discharge other dirt that adheres in lubricating grease or the oil.Therefore, but composition of the present invention clean surface.In one embodiment, the present invention relates to comprise the method that applies stable microbial composite of the present invention repeatedly.For example, method of the present invention can comprise and applying every day.Apply the surface that to clean light contamination in 5-14 days.Apply the surface that to clean severe contamination 3-6 week.
The salt of boric acid
The present invention relates to stable microorganism cleaning composition, its salt that adopts one or more boric acid is to provide microbial preparation even the improved stability under alkaline pH.The salt of suitable boric acid provides basicity can for stable microorganism cleaning solution.This salt comprises alkali metal borate; The amine borate, preference chain alkanolamine borate; And analogue; Or its combination.In some embodiments, the salt of boric acid comprises potassium borate, monoethanolamine ammonium borate, di-alcohol ammonium borate, three ethanol ammonium borates and analogue or its combination.In one embodiment, the salt of boric acid comprises the monoethanolamine borate.
Can obtain the salt of boric acid by any various routes, for example potassium borate or monoethanolamine borate.For example, can be with commercially available borate, for example potassium borate joins in the composition.Perhaps, can be by use alkali, for example contain the alkali of potassium such as potassium hydroxide or such as the alkali of monoethanolamine, in and boric acid, thereby acquisition borate, for example potassium borate or monoethanolamine borate.
In some embodiments, borate surpasses 5 or 10wt% in concentration in composition of the present invention, for example surpass 11,12,13,14,15,16,17,18,19 or 20wt% under be soluble.Can use employed borate in the present composition with the peak concentration that mostly is most the borate solubility limit.In some embodiments, borate is at maximum 35wt%, for example maximum 25,30 or the concentration of 35wt% under dissolve in the composition of the present invention.In some embodiments, borate is soluble at 12-35wt%, 15-30wt% or 20-25wt% under the preferred 20-25wt%.Composition of the present invention also can comprise by any consumption of term " about " change or the borate of scope.
In one embodiment, the alkanolamine borate, for example the monoethanolamine borate is soluble under the concentration of Sodium Tetraborate especially greater than other borate.Can in cleaning compositions of the present invention, use the alkanolamine borate, monoethanolamine borate for example, and under the above concentration of enumerating, preferred about 30wt% at most are soluble under about concentration of 20 to about 25wt% preferably.In one embodiment, can be at alkaline pH, for example pH about 9 obtains this high-dissolvability to about 10.5 times.
In one embodiment, potassium borate is soluble under the concentration of alkali metal borate, particularly Sodium Tetraborate especially greater than other metal borate.Can in enzymatic cleaning compositions of the present invention, use potassium borate, and under the above concentration of enumerating, preferred about 25wt% at most is soluble under preferred about concentration of 15 to about 25wt%.In one embodiment, can be at alkaline pH, for example pH about 9 obtains this high-dissolvability to about 10.5 times.
Be suitable for keeping pH and be higher than approximately 7, be higher than other buffer system of about 8, about 8 to about 11 or about 9 to about 10.5 and compare, borate can be provided at the required increase of microbial preparation stability under the alkaline pH.Keep alkaline pH bigger cleaning capacity can be provided.
Stable bacteria composition of the present invention can be substantially free of sodium ion.Advantageously, in being substantially free of the composition of sodium ion, borate is solvable under the big concentration of the concentration when having sodium ion.Regrettably, sodium ion is a kind of counter ion of common salt.Therefore, must carefully provide the composition of the present invention that is substantially free of sodium ion.For example, can be substantially free of the composition of sodium ion, wherein optionally pass through in alkanolamine or the potassium hydroxide and the reagent of described sour form by reagent preparation the present invention of sour form.For example, can be by the salt except sodium salt, for example potassium or alkanol amine salt prepare the composition that the present invention is substantially free of sodium ion.In one embodiment, composition of the present invention comprises sodium ion, and its content makes Sodium Tetraborate not be precipitated out from said composition.A kind of mode that realizes the sodium of this low levels is not comprise sodium salt in the composition or do not comprise sodium salt except amphoterics.Preferably, even under situation about adopting from the sodium in the amphoterics, composition of the present invention also is substantially free of sodium ion.The cleaning compositions that the present invention is substantially free of sodium ion can comprise for example about 15 to about 30wt% the borate of the about at most 35wt% of concentration.In one embodiment, at alkaline pH, for example pH about 9 obtains this high-dissolvability to about 10.5 times.
Be suitable for keeping pH and be higher than approximately 7, be higher than other buffer system of about 8, about 8 to about 11 or about 9 to about 10.5 and compare, the composition that comprises borate and be substantially free of sodium ion can be provided at the required increase of microbial preparation stability under the alkaline pH.Keep alkaline pH bigger cleaning capacity can be provided.
In some embodiments, the alkanolamine borate is with about 5 to about 35wt%, and about 10wt% is to about 30wt%, and about 10wt% is to about 20wt%, and about 5wt% is about 15wt% extremely, or the extremely concentration existence of about 25wt% of about 15wt%.In some embodiments, the alkanolamine borate is with about 5wt% of composition, about 10wt%, and about 15wt%, about 20wt%, the concentration of about 25wt% or about 30wt% exists.This prescription can be substantially free of sodium ion.Composition of the present invention also can comprise the alkanolamine borate that the term " about " of no use of any consumption or scope changes.
In some embodiments, to about 30wt%, perhaps about 10wt% is to about 20wt% with about 10wt% of composition for the monoethanolamine borate, and about 5wt% is about 15wt% extremely, and perhaps about 15wt% is the concentration existence of about 25wt% extremely.In some embodiments, the monoethanolamine borate is with about 5wt% of composition, about 10wt%, and about 15wt%, about 20wt%, the concentration of about 25wt% or about 30wt% exists.This prescription can be substantially free of sodium ion.Composition of the present invention also can comprise the monoethanolamine borate that the term " about " of no use of any consumption or scope changes.
In some embodiments, borate is with about 5 to about 35wt%, and about 10wt% is to about 30wt%, and about 10wt% is to about 20wt%, and about 5wt% is about 15wt% extremely, or the extremely concentration existence of about 25wt% of about 15wt%.In some embodiments, borate is with about 5wt% of composition, about 10wt%, and about 15wt%, about 20wt%, the concentration of about 25wt% or about 30wt% exists.This prescription can be substantially free of sodium ion.Composition of the present invention also can comprise the borate that the term " about " of no use of any consumption or scope changes.
Microbial preparation
Can in stable bacteria composition of the present invention, use any various spores (bacterium or fungi), bacterial nutrition or fungi.For example, composition of the present invention can comprise microorganism or its mixture of any work, the environment for use that described microorganism or its mixture can hold out against this prescription and be planned perhaps can digest, degrades or promote common analogue in degraded lipid, protein, carbohydrate, other organism or family, mechanism and industrial dirt or the effluent liquid.Many suitable bacterial strains and species are known.
Suitable spore (bacterium or fungi), bacterial nutrition or fungi comprise genus bacillus (Bacillus), pseudomonas (Pseudomonas), Arthrobacter (Arthrobacter), enterobacteria (Enterobacter), citric acid bacillus (Citrobacter), excellent bacillus (Corynebacter), its mixture of bacterium nitrobacter (Nitrobacter) or analogue; Acinetobacter calcoaceticus (Acinetobacter), aspergillus tubigensis (Aspergillus), vinelandii (Azospirillum), bulkholderia cepasea (Burkholderia), Ceriporiopsis, Escherichia (Escherichia), Bacterium lacticum (Lactobacillus), series bacillus (Paenebacillus), secondary coccus (Paracoccus), rhodococcus (Rhodococcus), Syphingomonas, suis (Streptococcus), thiobacillus (Thiobacillus), Trichoderma (Trichoderma), Xanthomonas campestris (Xanthomonas), Bacterium lacticum (Lactobacillus), Nitrosomonas (Nitrosomonas), Alcaliaens, klebsiella (Klebsiella), its mixture or analogue; And composition thereof or analogue.
Suitable genus bacillus comprises Bacillus licheniformis (Bacillus licheniformis), subtilis (Bacillus subtilis), bacillus polymyxa (Bacilluspolymyxa) or analogue; Methyl alcohol genus bacillus (Bacillus methanolicus), bacillus amyloliquefaciens (Bacillus amyloliquefaciens), Pasteur genus bacillus (Bacilluspasteurii), D-lactic acid genus bacillus (Bacillus laevolacticus), bacillus megaterium (Bacillus megaterium), its mixture or analogue; And composition thereof or analogue.Suitable pseudomonas comprises pseudomonas aeruginosa (Pseudomonas aeruginosa), separates alkali pseudomonas (Pseudomonas alkanolytica), denitrogenation pseudomonas (Pseudomonas dentrificans) or its mixture or analogue.Suitable Arthrobacter comprises arthrobacter paraffineus (Arthrobacter paraffineus), bites oil Arthrobacter (Arthrobacter petroleophagus), slightly red Arthrobacter (Arthrobacterrubellus), Arthrobacter sp., or its mixture or analogue.Suitable enterobacteria comprises enterobacter cloacae (Enterobacter cloacae), Enterobacter sp., or its mixture or analogue.Suitable citric acid bacillus comprises no propanedioic acid citric acid bacillus (Citrobacteramalonaticus), citrobacter freundii (Citrobacter freundi), or its mixture or analogue.Suitable excellent bacillus comprises Corynebacterium alkanum, Corynebacterium fujiokense, Corynebacterium hydrocarboxydano, excellent bacillus sp., its mixture or analogue.
Suitable spore (bacterium or fungi), bacterial nutrition or fungi comprise those with ATCC numbering: 21417,21424,27811,39326,6051a, 21228,21331,35854,10401,12060,21551,21993,21036,29260,21034,13867,15590,21494,21495,21908,962,15337,27613,33241,25405,25406,25407,29935,21194,21496,21767,53586,55406,55405,55407,23842,23843,23844,23845,6452,6453,11859,23492, its mixture or analogue.
The suitable microorganism that can use in the present invention is included in United States Patent(USP) Nos. 4655794,5449619 and 5863882; With described in the U.S. Patent Publication Nos.20020182184,2003012688 and 20030049832 those, its disclosure at this by with reference to introducing.
Suitable spore (bacterium or fungi), bacterial nutrition or fungi are commercially available in various sources (for example, Sybron Chemicals, Inc., Semco Laboratories, Inc., or Novozymes).The trade(brand)name of this product comprises SPORZYME  1B, SPORZYME  UltraBase 2, SPORZYME  EB, SPORZYME  BCC, SPORZYME  WC Wash, SPORZYME  FE, BI-CHEM  MSB, BI-CHEM  Purta Treat, BI-CHEM  BDO, BI-CHEM  SANI-BAC , BI-CHEM  BIO-SCRUB , BI-CHEM  GC600L , BI-CHEM  Bioclean, GREASE GUARD  or analogue.
In one embodiment, spore (bacterium or fungi), bacterial nutrition or fungi comprise the Bacillus strain that is particularly suitable for high yield extracellular enzyme, especially proteolytic enzyme, amylase and cellulase.This bacterial strain is common in the waste treatment product.This mixture can comprise Bacillus licheniformis, subtilis and bacillus polymyxa.As further example, the Pasteur genus bacillus can demonstrate high-caliber lipase production; The D-lactic acid genus bacillus can demonstrate germination circulation faster; Bacillus amyloliquefaciens can demonstrate high-caliber proteolytic enzyme production.
Suitable concentration this prescription Endospore (bacterium or fungi), bacterial nutrition or fungi comprises about 1 * 10 3To about 1 * 10 9CFU/ml, about 1 * 10 4To about 1 * 10 8CFU/ml, about 1 * 10 5To about 1 * 10 7CFU/ml, or analogue.Can in composition of the present invention, use effective cleaning amount, for example about 0.5 to about 10wt%, about 1 to about 5 (for example 4) wt%, and about 2 to about 10wt%, the commercially available composition of about 1 spore to about 3wt% or about 2wt% (bacterium or fungi), bacterial nutrition or fungi.The present composition can comprise these consumptions or the scope that changes approximately of no use.
The embodiment of stable microbial preparation
In one embodiment, stable microbial preparation of the present invention comprises microbial preparation (for example, bacteria preparation, spore blend for example), borate (for example, alkanolamine borate, for example monoethanolamine borate) and optional polyvalent alcohol (for example, propylene glycol).In some embodiments, stable microbial preparation of the present invention comprises about 2 to about 40wt% borate, about 3 to about 15wt% borate, about borate of 5 to about 30wt%, about borate of 5 to about 25wt%, about 5 to about 10wt% borate, and about 10 to about 15wt% borate or about borate of 25 to about 30wt%.In some embodiments, composition of the present invention comprises about polyvalent alcohol of 2 to about 30wt%, about polyvalent alcohol of 2 to about 10wt%, about polyvalent alcohol of 5 to about 20wt%, about polyvalent alcohol of 5 to about 10wt%, or about polyvalent alcohol of 10 to about 20wt%.In some embodiments, stable microbial preparation of the present invention comprises about polyvalent alcohol of 2 to about 40wt%, about polyvalent alcohol of 2 to about 20wt%, about polyvalent alcohol of 2 to about 15wt%, about polyvalent alcohol of 2 to about 10wt%, or about polyvalent alcohol of 3 to about 10wt%, about polyvalent alcohol of 4 to about 15wt% or about polyvalent alcohol of 4 to about 8wt%, the polyvalent alcohol of about 4wt%, the polyvalent alcohol of about 8wt%, or the polyvalent alcohol of about 12wt%.In some embodiments, stable microbial preparation of the present invention comprises about water of 10 to about 95wt%, about water of 15 to about 75wt%, about water of 15 to about 35wt%, about water of 25 to about 75wt%, about water of 40 to about 70wt%, about water of 45 to about 65wt%, or maximum about 50, about 55, about 60, about 65, or the water of about 70wt%.
In one embodiment, cleaning compositions of the present invention comprises spore, bacterium or fungi and alkanolamine borate.In one embodiment, composition can have the pH more than or equal to 9, and for example about 9 to about 10.5.In one embodiment, composition can have the pH more than or equal to 8, and for example about 8 to about 9.5.Said composition also can comprise polyvalent alcohol.In one embodiment, polyvalent alcohol can comprise propylene glycol.Said composition also can comprise the water of maximum about 65wt%.
In one embodiment, the alkanolamine borate can comprise monoethanolamine ammonium borate, di-alcohol ammonium borate, trolamine ammonium borate or its combination.Composition can comprise about 5 to about 35wt% alkanolamine borate, about 10 to about 30wt% alkanolamine borate, or about 15 to about 25wt% alkanolamine borate.
In one embodiment, cleaning compositions of the present invention comprises spore, bacterium or fungi, and borate and can be substantially free of sodium ion.Composition can have the pH more than or equal to 9, and for example about 9 to about 10.5.Composition also can comprise polyvalent alcohol.In one embodiment, polyvalent alcohol can comprise propylene glycol.Composition also can comprise the water of maximum about 65wt%.
Borate can comprise potassium borate.Potassium borate can comprise the combination of potassium hydroxide and boric acid.Composition can comprise about borate of 5 to about 35wt%, about borate of 10 to about 30wt%, or about borate of 15 to about 25wt%.
In one embodiment, spore or bacterium can comprise microbial spores.
The cleaning compositions that contains stable microbial preparation
The invention still further relates to the cleaning compositions that contains stable microbial preparation of the present invention.In one embodiment, the aqueous cleaning composition of enriched material of the present invention and dilution can comprise the blend tensio-active agent that contains nonionogenic tenside and silicone surfactant of effective concentration, and stable microbial preparation of the present invention.These compositions also can comprise anion surfactant and hydrotropic agent or solubilizing agent, and it can keep the single-phase non-isolating aqueous solution or suspension.In United States Patent(USP) Nos. 6425959 and 6506261, disclose stable microbial preparation of the present invention and can comprise within it suitable cleaning compositions, its disclosure at this by with reference to introducing.
In one embodiment, composition and method can comprise nonionogenic tenside and nonionic siloxane tensio-active agent.Said composition also can comprise anion surfactant and hydrotropic agent (it can be to have the seldom anionic compound of surfactant character), for example amine oxide material.Can use pure this composition, so that from typically hard metal or other hard surface are removed complicated oily or lubricated smectic organic dirt and mineral contaminants with thinner.Said composition can contain the blend of alkali source and capacity to obtain good clean-up performance.
In one embodiment, cleaning compositions of the present invention (enriched material or dilutable liquid) can comprise that about 0.003 to about 70wt% contains the blend surfactant composition of nonionogenic tenside and nonionic siloxane tensio-active agent.Nonionogenic tenside can not contain oxyalkylene segment, can be (PO) multipolymer of block (EO), pure alkoxide, and alkylphenol alkoxide, or amine alkoxide, wherein alkoxide is (EO) or (PO) part.The weight ratio of nonionogenic tenside and nonionic siloxane tensio-active agent can be, per 1 weight part silicone surfactant or its blend are about 1 to about 10 weight parts, preferred 3-7 part nonionogenic tenside or its blend.This composition also can comprise one or more anion surfactants of about 0.003 to about 35wt%, one or more effective hydrotropic agents of about 0.001 to about 20wt%, or its mixture.Hydrotropic agent can be an alkyl dimethyl amine oxide.Hydrotropic agent can keep sequestrant and surfactant blend is in the homogeneous single phase aqueous composition.
In one embodiment, concentrate composition of the present invention can comprise one or more nonionic siloxane tensio-active agents of about 1 to about 15wt%, one or more nonionogenic tensides of about 5 to about 75wt%, one or more anion surfactants of about 5-75wt%, one or more hydrotropic agent solubilizing agent (for example, amine oxide material) with about 2-20wt%.In this embodiment, the ratio of nonionogenic tenside and nonionic siloxane tensio-active agent can be, per 1 weight part nonionic siloxane tensio-active agent is about 3 to about 7 weight part nonionogenic tensides.
In the embodiment of the moisture compositions formulated of diluting, this aqueous solution can comprise about 0.0005 to about 35wt% or about silicone surfactant of 0.1 to about 10wt%, the nonionogenic tenside of about 0.0003-35wt% or about 0.3-30wt%, the anion surfactant of about 0.003-35wt% or about 0.3-30wt%, with the hydrotropic agent solubilizing agent of about 0.001-20wt% or 0.2 to about 30wt%, keep the ratio of nonionic listed above and silicone surfactant simultaneously.
In one embodiment, wiping concentrate can comprise sequestrant or the sequestering agent of about 0.003-35wt% or about 0.1-25wt% in aqueous base; The nonionogenic tenside of about 0.003-35wt% or about 0.3-30wt%; The nonionic siloxane tensio-active agent of about 0.0005-35wt% or about 0.01-10wt%; The anion surfactant of about 0.003-30wt%; Hydrotropic agent or surface active agent solubilization agent (for example, amine oxide) with about 0.001-20wt% or about 0.2-30wt%.
Can use pure wiping concentrate, perhaps available used water is with this wiping concentrate of dilution proportion of the active aqueous cleaning agent that is enough to obtain dilution listed above.In the context of the present invention, term " pure " is meant and does not have thinner, for example water-bearing media basically.The sanitising agent of gained dilution can be applied in the substrate of pollution for scrubbing.
For the purpose of present patent application, this cleaning compositions can comprise sequestrant, nonionic/nonionic siloxane surfactant blend, anion surfactant and hydrotropic agent (for example amine oxide).This embodiment can be used for scrubbing from the corrosion resistant surface.Sequestrant can be a sylvite.Similarly, hydrotropic agent can be a sylvite.
The embodiment of cleaning compositions
In some embodiments, can cleaning compositions of the present invention be described by composition and the consumption listed in the following table.In following table, do not list the composition in the stable microbial composite, but exist as described above.Also available these consumptions or the scope that changes approximately in the table.
Concentrate composition
Chemical wt% wt% wt%
Sequestrant 0-30 0.5-15 0.5-15
Silicone surfactant 0.1-35 0.1-10 1-7
Nonionogenic tenside 0.5-35 1-20 1-15
Anion surfactant 0.5-35 1-20 1-15
Hydrotropic agent 0.1-20 0.5-15 0.5-10
Chemical wt% wt%
Sequestrant 0.1-30 0.5-15
Surfactant blend 0.5-70 1-30
Anion surfactant 0.1-70 0.5-35
The amine oxide hydrotropic agent 0.1-20 0.5-15
Optional acid To 〉=pH9 To 〉=pH10
Chemical wt% wt% wt% wt% wt%
Nonionogenic tenside 2-16 4-16 2-8 8 4
Silicone surfactant 0.5-6 1-6 0.5-2 3 1
Amphoterics 1-10 2-10 1-6 5 3
Anion surfactant 2-16 4-16 2-8 8 4
Hydrotropic agent 1-20 5-20 1-6 11 3
The aqueous composition (former state use or as formulation additives) of dilution
Chemical ppm ppm ppm
Sequestrant 0-150,000 60-20,000 1200-10,000
Surfactant blend 30-175,000 3000-100,000 6000-50,000
Anion surfactant 30-175,000 3000-100,000 6000-50,000
Hydrotropic agent 10-100,000 1000-60,000 2000-20,000
Aqueous diluent and stable microbial composite Surplus Surplus Surplus
Chemical ppm ppm
Sequestrant 6-70,000 600-20,000
Surfactant blend 30-350,000 3000-100,000
Anion surfactant 30-350,000 3000-100,000
The amine oxide hydrotropic agent 7-80,000 700-25,000
Optional acid To 〉=pH9 To 〉=pH10
Aqueous diluent and stable microbial composite Surplus Surplus
The last useful composition that is used for cleaning compositions of the present invention that shown.This tabular has gone out the consumption of some compositions, and stable microbial composite of the present invention also comprises spore, bacterium or fungi and borate.This composition can be used as organic dirt or lubricating grease remover.Surfactant blend listed above is meant the combination of the nonionic and the siloxanes nonionogenic tenside of the above ratio.In addition, sequestrant is useful, but unessential.Sequestrant provides chelating and scrubbing, but can help corrosion or other chemical damage to some surfaces.
In one embodiment, cleaning compositions of the present invention comprises spore, bacterium or fungi, and borate, for example the alkanolamine borate.In some embodiments, said composition also can comprise about nonionogenic tenside of 0.003 to about 35wt%, for example about nonionogenic tenside of 0.5 to about 35wt%.Nonionogenic tenside can comprise and contains at least (EO) y(PO) zNon-ionic block copolymer, wherein y and z are 2 to 100 independently; C with 2-15mol oxyethane 6-24The alkylphenol alkoxide; C with 2-15mol oxyethane 6-24The alcohol alkoxide; Alkoxylated amines with 2-20mol oxyethane; Or its mixture.
In some embodiments, said composition also can comprise about silicone surfactant of 0.0005 to about 35wt%, for example about silicone surfactant of 0.1 to about 35wt%.This silicone surfactant can comprise siloxane main chain and have the epoxy alkyl of at least 1 side extension of about 2-100mol oxirane.The epoxy alkyl that side is hung can comprise (EO) n, wherein n is 3-75.
In some embodiments, said composition also can comprise about anion surfactant of 0.003 to about 35wt%, for example about anion surfactant of 0.5 to about 35wt%.Anion surfactant can comprise linear alkylbenzene sulfonate; Alhpa olefin sulfonate; Sulfuric acid alkane ester; Secondary paraffin sulfonate; Sulfosuccinate; Or its mixture.Anion surfactant can comprise the alkanol ammonium alkylbenzene sulfonate.Anion surfactant can comprise monoethanolamine ammonium alkylbenzene sulfonate.
In some embodiments, said composition also can comprise about hydrotropic agent of 0.001 to about 20wt%, for example about hydrotropic agent of 0.1 to about 20wt%.Hydrotropic agent can comprise C 6-24Alkyl dimethyl amine oxide; Alkylation phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate; Or its mixture.Hydrotropic agent can comprise iso-alkyl dimethyl oxidation amine tensio-active agent.Hydrotropic agent can comprise different C 10-14Alkyl dimethyl amine oxide.Hydrotropic agent can comprise alkylation phenyl ether disulfonic acid or its salt.
In one embodiment, said composition also can comprise about nonionogenic tenside of 0.5 to about 35wt% and about silicone surfactant of 0.1 to about 35wt%.In this embodiment, nonionogenic tenside can comprise and contains at least (EO) y(PO) zNon-ionic block copolymer; C with 2-15mol oxyethane 6-24The alkylphenol alkoxide; C with 2-15mol oxyethane 6-24The alcohol alkoxide; Alkoxylated amines with 2-20mol oxyethane; Or its mixture.In this embodiment, silicone surfactant can comprise siloxane main chain and have the epoxy alkyl of at least 1 side extension of about 2-100mol oxirane.
In this embodiment, the weight ratio of nonionogenic tenside and nonionic siloxane tensio-active agent can be that per 1 part of silicone surfactant is about 0.1 nonionogenic tenside to about 10 weight parts.In one embodiment, the weight ratio of nonionogenic tenside and nonionic siloxane tensio-active agent can be that per 1 part of silicone surfactant is about 3 nonionogenic tensides to about 7 weight parts.
In some embodiments, composition also can comprise about nonionogenic tenside of 0.5 to about 35wt%, about silicone surfactant of 0.1 to about 35wt%, about anion surfactant of 0.5 to about 35wt% and about hydrotropic agent of 0.1 to about 20wt%.
Composition in the stable microbial preparation
Stable microbial preparation of the present invention and/or cleaning compositions can comprise can be used for cleaning or the various compositions of other purposes in any.This composition can comprise enzyme, tensio-active agent, hydrotropic agent, sequestrant, divalent cation, polyvalent alcohol, aesthstic stiffeners, solvent, sanitas or analogue.
In some embodiments, said composition also can comprise one or more solvents of significant quantity; One or more enzymes of significant quantity; One or more antiseptic-germicides of significant quantity; One or more sequestrants of significant quantity; Or its mixture.Said composition can comprise the sequestrant of about 0.1-30wt%.This sequestrant can comprise small molecules or the polymerizable compound with carboxyl, or its mixture.
Enzyme can comprise detergency enzymes.Detergency enzymes can comprise proteolytic enzyme, amylase, lipase, cellulase, peroxidase, glucose enzyme (gluconase) or its mixture.Detergency enzymes can comprise Sumizyme MP, lipase, amylase or its mixture.
In some embodiments, said composition also can comprise calcium ion source, polyvalent alcohol, washing assistant, dyestuff or its binding substances or mixture.
Tensio-active agent
Tensio-active agent of the present invention or surfactant mixtures can be selected from water-soluble or the dispersible nonionic of water, semi-polarity nonionic, negatively charged ion, positively charged ion, both sexes or amphiphilic surfactant; Or its any combination.For in method of the present invention and product, using specific surfactant or the surfactant mixtures selected to can be depending on final working conditions, comprising preparation method, physical product form, use pH, use temperature, foam control and dirt type.The tensio-active agent that is incorporated in the cleaning compositions of the present invention is preferably compatible with enzyme, is not the substrate of enzyme in the composition, is not the inhibitor or the deactivator of enzyme.For example, when using proteolytic enzyme and amylase in composition of the present invention, tensio-active agent does not preferably contain peptide and glycosidic link.In addition, more known cats products reduce the effect of enzyme.
In general, the concentration that can be used on interior tensio-active agent of stable composition of the present invention or surfactant mixture is about 0.5% to about 40%, preferred about 2% to about 10%, preferred about 5% to about 8% of composition weight.These percentage ratios can refer to the percentage ratio of commercially available surfactant composition, and described surfactant composition also can contain solvent, dyestuff, odorant and analogue except containing actual tensio-active agent.In this case, the percentage ratio of real surface promoting agent chemical can be less than listed percentage ratio.These percentage ratios can refer to the percentage ratio of real surface promoting agent chemical.
Nonionogenic tenside
The feature that can be used for nonionogenic tenside of the present invention is to exist organic hydrophobic group and organic hydrophilic base usually and typically produces by the organic aliphatic series of condensation, alkyl aromatic or polyoxy alkylidene hydrophobic compound and hydrophilic basic oxide part (in common practice, these hydrophilic basic oxide partly are oxyethane or its polyhydrate product, polyoxyethylene glycol).In practice, have contain hydrogen atoms hydroxyl, carboxyl, amino or amide group any hydrophobic compound can with oxyethane or its many hydration adducts, or the mixture condensation of itself and oxirane such as propylene oxide forms nonionogenic tenside.Can easily regulate can with the length of the hydrophilic poly (oxyalkylene) base section of any specific hydrophobic compound condensation, obtain having the required hydrophilic and water hydrophobic performance balanced degree and can disperse or water-soluble cpds.
The EOPO nonionogenic tenside
The homopolymer of grafting part embedding is disconnected or assorted multipolymer in, the example of the useful nonionogenic tenside that uses with silicone surfactant is the polyether compound by oxyethane, propylene oxide production.This polyether compound is called as polyalkylene oxide polymer, polyoxyalkylene polymers or polyalkylene glycol polymers.The molecular weight ranges of this nonionogenic tenside is about 500 to about 15,000.Polyoxy propylidene-polyoxyethylene diol polymer nonionogenic tenside of finding some types is particularly useful.Can use that to contain at least one polyoxy propylidene embedding disconnected and have a disconnected tensio-active agent of other embedding that at least one is connected to the polyoxyethylene of this polyoxy propylidene embedding on disconnected.Extra polyoxyethylene or the embedding of polyoxy propylidene are disconnected can be present in an intramolecularly.Average molecular weight range is that these materials of about 500 to about 15,000 are purchased with PLURONIC  (by BASF Corporation preparation) form, and obtains with their various other trade(brand)name forms of chemical supplier.In addition, PLURONIC  R (the PLURONIC structure of counter-rotating) also can be used in the composition of the present invention.In addition, can use epoxy alkyl, lipid acid or other this group that uses with pure and mild alkylphenol.Useful tensio-active agent can comprise end capped poly-alkoxylation C 6-24Straight chain alcohol.Can adopt polyoxyethylene or polyoxy propylidene unit to prepare tensio-active agent and can adopt the common reagent that forms the ether end group to make it end-blocking.Useful this surfactant materials is (PO) xCompound or benzylic ether compound gather ethoxyquin C 12-14Straight chain alcohol; Referring to U.S. Patent No. 3444247.The polyoxy propylidene polyoxyethylene block polymer that is particularly useful is to contain those that the unitary center embedding of polyoxy propylidene is broken and the unitary embedding of polyoxyethylene on disconnected each side of this center embedding is disconnected.
These multipolymers have chemical formula shown below:
(EO) n-(PO) m-(EO) n
Wherein m is integer 21-54; N is integer 7-128.Extra useful segmented copolymer is to have the disconnected and disconnected block polymer of the unitary embedding of polyoxy propylidene on disconnected each side of this center embedding of polyoxyethylene unitary center embedding.This multipolymer has chemical formula shown below:
(PO) n-(EO) m-(PO) n
Wherein m is that integer 14-164 and n are integer 9-22.
A kind of suitable ionic surfactant pack of using in the present composition is drawn together the alkylphenol alkoxide of following formula:
Wherein R ' comprises C 2-24On behalf of the EOPO base of Oxyranyle, propylene oxide base, hybridization or embedding disconnected EO-PO, PO-EO, EOPOEO or POEOPO base and Z, aliphatic group and AO represent H or (AO), benzyl or other end group.Suitable ionic surfactant pack is drawn together the alkylphenol b-oxide of following formula:
R wherein 1Comprise C 6-18Aliphatic group, preferred C 6-12Aliphatic group and n are integers about 2 to about 24.The main example of this tensio-active agent is the nonylphenol ethoxylate that has 2.5-14.5molEO in the b-oxide base.Available (PO) xBase (x is 2.5-12.5) makes b-oxide base end-blocking, or makes it end-blocking with benzyl moiety.
Alkoxylated amines
Composition of the present invention can comprise any in the various alkoxylated amines.In one embodiment, alkoxylated amines has general formula I: N (R 1) (R 2) (R 3) (R 4), R wherein 1, R 2Or R 3In at least one comprise alkoxide or ether moiety.R 4Can be hydrogen, straight or branched alkyl, or the straight or branched alkaryl.Alkoxylated amines can be primary, the second month in a season or tertiary amine.In one embodiment, alkoxylated amines is a tertiary amine.In some embodiments, R 2And R 3In each comprise the alkoxide part, for example one or more b-oxides part, one or more propoxide part, or its combination, and R 4Be hydrogen.For example, R 1, R 2Or R 3One of can comprise that ether moiety and other two can comprise one or more b-oxide parts, one or more propoxides parts or its combination.
As further example, alkoxylated amines can be represented with general formula I Ia, IIb or IIc respectively:
IIa R 5-(PO) sN-(EO) tH
IIb R 5-(PO) sN-(EO) tH (EO) uH and
IIc R 5-N(EO) tH;
R wherein 5Can be alkyl, alkenyl or other aliphatic group of a 8-20 or 12-14 carbon atom, or alkaryl, EO is the oxygen ethylidene, PO is the oxygen propylidene.S is 1-20,2-12 or 2-5; T is 1-20,1-10,2-12 or 2-5; With u be 1-20,1-10,2-12 or 2-5.Other variant in these compound scopes can be represented with Formula Il d:
R 5-(PO) v-N[(EO) wH][(EO) zH]
R wherein 5As defined above, v is 1-20 (for example, 1,2,3 or 4, or be 2 in one embodiment), and w and z are 1-20,1-10,2-12 or 2-5 independently.
In one embodiment, alkoxylated amines is an ether amine alkoxide.Ether amine alkoxide can have Formula Il I:
Figure A20048003130200271
In formula III, R 1Can be straight or branched alkyl or alkaryl; R 2Under each situation, can be the alkyl of a hydrogen or 1-6 carbon independently; R 3Under each situation, can be the alkyl of a hydrogen or 1-6 carbon independently; M on average can be about 1 to about 20; X and y separately independently average out to 1 to about 20; X+y on average can be about 2 to about 40.
In one embodiment, in formula III, R 1Can be: the alkyl of 8-24 carbon atom, alkaryl, and contain and have an appointment 7, or alkaryl (for example, two alkaryls that are substituted with alkyl) to about 30 carbon atoms; R 2Can contain 1 or 2 carbon atom, perhaps can be hydrogen; R 3Can be hydrogen, contain the alkyl of 1 or 2 carbon; The scope of x+y can be about 1 to about 3.
This ether amine alkoxide is disclosed in United States Patent(USP) Nos. 6060625 and 6063145.
In one embodiment, in formula III, R 1Can be: the alkyl of 6-24 carbon atom, alkaryl and contain and have an appointment 7, or alkaryl (for example, two alkaryls that are substituted with alkyl) to about 30 carbon atoms; R 2Can contain 1 or 2 carbon atom, perhaps can be hydrogen; R 3Can be hydrogen, contain the alkyl of 1 or 2 carbon; The scope of x+y can be about 1 to about 20.
In one embodiment, in formula III, m can be 0 to about 20, and x and y on average can be 0 to about 20 independently of one another.In some embodiments, alkoxyl group part epoxy available ethane, propylene oxide or epoxybutane unit end-blocking or sealing.
In one embodiment, in formula III, R 1Can be C 6-C 20Alkyl or C 9-C 13Alkyl, for example straight chained alkyl; R 2Can be CH 3M can be about 1 to about 10; R 3Can be hydrogen, the scope of x+y can be about 5 to about 12.
In one embodiment, in formula III, R 1Can be C 6-C 14Alkyl or C 7-C 14Alkyl, for example straight chained alkyl; R 2Can be CH 3M can be about 1 to about 10; R 3Can be hydrogen, the scope of x+y can be about 2 to about 12.In one embodiment, this ether amine alkoxide can comprise that with propylene oxide or the end capped alkoxide part of epoxybutane unit this alkoxide part can provide low foam composition.
In one embodiment, in formula III, R 1Can be C 6-C 14Alkyl, for example straight chained alkyl; R 2Can be CH 3M can be about 1 to about 10; R 3Can be hydrogen, the scope of x+y can be about 2 to about 20.
In one embodiment, alkoxylated amines can be C 12-C 14Propoxy-amine b-oxide, wherein in formula III, R 1Can be C 12-C 14Alkyl, for example straight chained alkyl; R 2Can be CH 3M can be about 10; R 3Can be hydrogen; X can be about 2.5, and y can be about 2.5.
In one embodiment, alkoxylated amines can be C 12-C 14Propoxy-amine b-oxide, wherein in formula III, R 1Can be C 12-C 14Alkyl, for example straight chained alkyl; R 2Can be CH 3M can be about 5; R 3Can be hydrogen; X can be about 2.5, and y can be about 2.5.
In one embodiment, alkoxylated amines can be C 12-C 14Propoxy-amine b-oxide, wherein in formula III, R 1Can be C 12-C 14Alkyl, for example straight chained alkyl; R 2Can be CH 3M can be about 2; R 3Can be hydrogen; X can be about 2.5, and y can be about 2.5.
In one embodiment, in formula III, R 1Can be side chain C 10Alkyl; R 2Can be CH 2M can be 1; R 3Can be hydrogen; X+y can be about 5.This alkoxylated amines can be the uncle's ethoxylated amine that is called poly-(5) oxygen ethylidene isodecyl oxygen base propylamine.
In one embodiment, alkoxylated amines can be secondary ethoxylated amine, its available following chemical formulation: R-(PO)-N-(EO) x, x=1-7mol oxyethane wherein.
In one embodiment, alkoxylated amines can be a diamines, its available following chemical formulation: R-O-CH 2CH 2CH 2N (H) (CH 2CH 2CH 2NH 2), wherein R for example is side chain C 10Alkyl.
In one embodiment, the ether amine alkoxide of formula III is the ether amine ethoxy-c oxide compound of following formula I V:
Figure A20048003130200291
In formula IV, R 6Can be straight or branched alkyl or alkaryl; A on average can be about 1 to about 20; X and y on average can be about 0 to about 10 independently of one another; X+y on average can be about 1 to about 20.This ether amine alkoxide can be described as ether amine ethoxy-c oxide compound.In some embodiments, the alkoxyl group part can be used oxyethane, propylene oxide or epoxybutane unit end-blocking or sealing.
In one embodiment, alkoxylated amines can be C 12-C 14Propoxy-amine b-oxide, its available following chemical formulation: R-(PO) 2N[EO] 2.5-H[EO] 2.5-H.In one embodiment, alkoxylated amines can be C 12-C 14Propoxy-amine b-oxide, its available following chemical formulation: R-(PO) 10N[EO] 2.5-H[EO] 2.5-H.In one embodiment, alkoxylated amines can be C 12-C 14Propoxy-amine b-oxide, its available following chemical formulation: R-(PO) 5N[EO] 2.5-H[EO] 2.5-H.In one embodiment, alkoxylated amines can be the uncle's ethoxylated amine that is called as poly-(5) oxygen ethylidene isodecyl oxygen propylamine, and it has the side chain C away from ether oxygen 10H 21Alkyl.In one embodiment, alkoxylated amines can be a diamines, its available following chemical formulation: R-O-CH 2CH 2CH 2N (H) (CH 2CH 2CH 2NH 2), wherein R is side chain C 10Alkyl.In one embodiment, alkoxylated amines can be the uncle's ethoxylated amine that is called as different-(2-hydroxyethyl) isodecyl oxygen propylamine, and it has the side chain C away from ether oxygen 10H 21Alkyl.
Ether amine alkoxide for example is commercially available with trade(brand)name Surfonic (Huntsman Chemical) or Tomah Ether or Ethoxylated Amines.
In one embodiment, alkoxylated amines is the alkylamine alkoxide.Suitable alkylamine alkoxide can have following formula V:
Figure A20048003130200301
In formula V, R 1Can be straight or branched alkyl or alkaryl; R 3Under each situation, can be the alkyl of a hydrogen or 1-6 carbon independently; X and y separately independently average out to 0 to about 25; X+y on average can be about 1 to about 50.In one embodiment, in formula V, x and y separately independently average out to 0 to about 10; X+y on average can be about 1 to about 20.In one embodiment, the alkoxyl group part can be used oxyethane, propylene oxide or epoxybutane unit end-blocking or sealing.
In one embodiment, the alkylamine alkoxide of formula V is the alkylamine ethoxy-c oxide compound of following formula VI:
In formula VI, R 6Can be straight or branched alkyl or alkaryl (for example, C18 alkyl); X and y separately independently average out to 0 to about 25; X+y on average can be about 1 to about 50.In one embodiment, in formula VI, x and y separately independently average out to 0 to about 10 or 20; X+y on average can be about 1 to about 20 or 40.This ether amine alkoxide can be called as amine ethoxy-c oxide compound.
A kind of such alkylamine ethoxy-c oxide compound can be with following chemical name N, two-2 (Ω-hydroxyl polyoxyethylene/polyoxy propylidene) ethyl alkanamine or the N of N-, two (polyoxyethylene/propylidene) butter alkanamines (its CAS number is 68213-26-3) of N-, and/or chemical formula C 64H 130O 18Expression.
The alkylamine alkoxide for example is commercially available with trade(brand)name Armoblen (Akzo Nobel).Armoblen 600 is called as alkylamine ethoxy-c oxide compound.
In one embodiment, alkoxylated amines is an ether amine.Suitable ether amine can have general formula VII:N (R 1) (R 2) (R 3), R wherein 1, R 2Or R 3In at least one comprise ether moiety.In one embodiment, R 1Comprise ether moiety and R 2, R 3Be hydrogen.This ether amine can have chemical formula VIII:
R 4O(R 5)NH 2
In chemical formula VIII, R 4Can be C 1-C 13Aralkyl or alkyl, straight or branched, R 5Can be C 1-C 6Alkyl, straight or branched.
Ether amine can for example be available commercially from Tomah 3Products.
Suitable alkoxylated amines can comprise the amine that is called ethoxylated amine, third amine oxide, ethoxy-c amine oxide, alkoxide alkylamine, ethoxyquin alkylamine, the third oxidation of alkyl amine, ethoxy-c oxidation of alkyl amine, ethoxy-c oxidation quaternary ammonium compound, ether amine (primary, secondary or uncle), ether amine alkoxide, ether amine b-oxide, ether amine propoxide, alkoxide ether amine, alkyl ether amine alkoxide, alkyl propoxy-amine alkoxide, alkyl alkoxy ether amine alkoxide etc.
Extra nonionogenic tenside
Extra useful ionic surfactant pack is drawn together among the present invention:
1mol has about 8 saturated or unsaturated, straight or branched carboxylic acid and about 6 condensation products to about 50mol oxyethane to about 18 carbon atoms.Acid moieties can be made up of the mixture of the acid in the carbon atom scope of above definition, and perhaps it can be made up of the acid with the particular carbon atomicity in this scope.The example of the commercial compound that this is chemical obtains on market with trade(brand)name Nopalcol  (by Henkel Corporation preparation) and Lipopeg  (by LipoChemicals, the Inc. preparation).
Except the ethoxyquin carboxylic acid, common alleged macrogol ester, can be applicable in the present invention in the special embodiment by other alkanoates, during especially indirect foodstuff additive are used with glyceryl ester, glycerine and polyvalent alcohol (sugar or anhydro sorbitol/sorbyl alcohol) reaction formation.All these ester moieties have one or more reactive hydrogen site on its molecule, this site can experience further acidylate or oxyethane (alkoxide) addition, to control the water-wetness of these materials.When adding these fatty esters or acidylate carbohydrate in the present composition that contains amylase and/or lipase the time, must carefully carry out, this is because they are incompatible potentially.
The example of the tensio-active agent of the low foaming of nonionic comprises above-described nonionogenic tenside, the modification by making (multifunctional part) terminal hydroxy group " end-blocking " or " end-block " of described tensio-active agent is so that by reducing foaming with little hydrophobic molecule such as propylene oxide, butylene oxide ring, benzyl chloride reaction; And comprise and contain 1 short chain fatty acid, alcohol or alkylogen to about 5 carbon atoms; And composition thereof.Comprise reactant equally, thionyl chloride for example, it changes into the muriate group with terminal hydroxy group.This modification to terminal hydroxy group can cause that full embedding is disconnected, embedding mixes, mix embedding copolymerization or full miscellaneous nonionogenic tenside.
The polyhydroxy fatty acid amide that is suitable for using in composition of the present invention comprises having formula R 2CONR 1Those of Z, wherein R 1Be H, C 1-C 4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-or its mixture; R 2Be C 5-C 31Alkyl (it can be a straight chain); With Z be polyhydroxy alkyl (it has at least 3 hydroxyls and is directly connected to straight-chain alkyl on this chain), or its oxidation alkyl derivative (the preferred ethoxyquin or third oxidized derivatives).Z can be derived from the reducing sugar in the reductive amination process; Glycidyl (glycityl) part for example.
Especially the suitable nonionic alkyl polysaccharide surfactant that can be used for the present composition is included in those disclosed in the U.S. Patent No. 4565647 of authorizing Llenado on January 21st, 1986.These tensio-active agents comprise and contain about 6 hydrophobic groupings to about 30 carbon atoms, and polysaccharide, and for example the glycan glycosides contains 1.3 hydrophilic radicals to about 10 sugar units of having an appointment.Can use any reducing sugar that contains 5 or 6 carbon atoms, for example glucose, semi-lactosi, and the available glucosyl of galactosyl part partly replaces.(randomly, hydrophobic grouping connects in positions such as 2-, 3-, 4-, thereby obtains glucose or the semi-lactosi relative with glucoside or galactoside).In sugared key can be for example between 2-, 3-, 4-and/or the 6-position of position of extra sugar unit and sugar unit in front.
The fatty acid amide surfactant that is suitable for the present composition comprises having chemical formula R 6CON (R 7) 2Those, R wherein 6Be alkyl and each R that contains 7-21 carbon atom 7Be hydrogen, C independently 1-C 4Alkyl, C 1-C 4Hydroxyalkyl or-(C 2H 4O) xH, wherein the scope of x is 1-3.
By Marcel Dekker, Inc., New York, 1983 publication, Schick, the paper of the 1st volume of the Surfactant Science Series that M.J. edits Nonionic SurfactantsIt is a good book of reference about the various non-ionic compounds aspect of normally used wide region in the present invention's practice.The typical case who has provided nonionic group and these surfactant materials in authorizing the U.S. Patent No. 392678 of Laughlin and Heuring on December 30th, 1975 enumerates.In " Surface Active Agents and Detergents " (Vol I and II, Schwartz, Perry and Berch), provided further example.
Semi-polar nonionic surfactants
The nonionogenic tenside of semi-polarity type is another group nonionogenic tenside that can be used for the present composition.In general, semi-polar nonionic surfactants is high whipping agent and suds-stabilizing agent, and this can limit their application in the CIP system.Yet in the composition embodiment of the present invention that designs for high foamed cleaning method, semi-polar nonionic surfactants has effect fast.Semi-polar nonionic surfactants comprises amine oxide, phosphine oxide, sulfoxide and oxidation alkyl derivative thereof.
Amine oxide is the uncle's amine oxide corresponding to following general formula:
Figure A20048003130200331
Wherein arrow is the conventional expressing method of semi-polar linkage; R 1, R 2And R 3Can be aliphatic series, aromatics, heterocycle, alicyclic or its combination.In general, for the interested amine oxide of detergent applications, R 1Be about 8 alkyl to about 24 carbon atoms; R 2And R 3Be alkyl or hydroxyalkyl or its mixture of 1-3 carbon atom; R 2And R 3Can for example be connected to each other and go up, to form ring structure by oxygen or nitrogen-atoms; R 4Be alkylidene group or the hydroxy alkylidene that contains 2-3 carbon atom; The scope of n is 0 to about 20.
Useful water-soluble amine oxides tensio-active agent is selected from cocounut oil or tallow alkyl two (low alkyl group) amine oxide, its specific examples is a dimethyl dodecyl amine oxide, tridecyl dimethyl oxidation amine, CH3-(CH2)13N(CH3)2-O, pentadecyl dimethyl oxidation amine, cetyl dimethyl amine oxide, heptadecyl dimethyl oxidation amine, octadecyl dimethyl amine oxide, dodecyl dipropyl amine oxide, tetradecyl dipropyl amine oxide, hexadecyl dipropyl amine oxide, tetradecyl dibutyl amine oxide, octadecyl dibutyl amine oxide, two (2-hydroxyethyl) dodecyl amine oxide, two (2-hydroxyethyl)-3-dodecyl oxygen bases (dodecoxy)-1-hydroxypropyl amine oxide, dimethyl-(2-hydroxyl dodecyl) amine oxide, 3,6,9-three (octadecyl) dimethyl oxidation amine and 3-dodecyl oxygen base 2-hydroxypropyl two (2-hydroxyethyl) amine oxide.
Useful semi-polar nonionic surfactants also comprises the water soluble oxidized phosphine with following structure:
Figure A20048003130200332
Wherein arrow is the conventional expressing method of semi-polar linkage; R 1Be that the chain length scope is 10 alkyl to about 24 carbon atoms, alkenyl or hydroxyalkyl part; R 2And R 3Respectively do for oneself and be independently selected from the alkyl that contains 1-3 carbon atom or the moieties of hydroxyalkyl.
The example of useful phosphine oxide comprises dimethyl decyl phosphine oxide, dimethyl tetradecyl phosphine oxide, methylethyl tetradecyl phosphine oxide, dimethyl hexadecyl phosphine oxide, diethyl-2-hydroxyl octyl-decyl phosphine oxide, two (2-hydroxyethyl) dodecyl phosphine oxide and two (methylol) tetradecyl phosphine oxide.Useful herein semi-polar nonionic surfactants also comprises the water-soluble sulfoxide compound with following structure:
Figure A20048003130200341
Wherein arrow is the conventional expressing method of semi-polar linkage; R 1Be that carbonatoms is about 8 to about 28 alkyl or hydroxyalkyl part, 0-5 ehter bond and 0 is to about 2 hydroxyl substituents; R 2The moieties of forming by alkyl with 1-3 carbon atom and hydroxyalkyl.
The useful examples of these sulfoxides comprises dodecyl methyl sulfoxide; 3-hydroxyl tridecyl methyl sulfoxide; The 3-methoxytridecylmethysulfoxide sulfoxide; With 3-hydroxyl-4-dodecyl oxygen base butyl methyl sulfoxide.
The preferred semi-polar nonionic surfactants that is used for the present composition comprises dimethyl oxidation amine, for example lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, cetyl dimethyl amine oxide, its combination and analogue.
Silicone surfactant
Silicone surfactant can comprise the diakyl-polysiloxane of modification, for example dimethyl polysiloxane.Available one or more hydrophilic polyalkylene oxide base modified polyorganosiloxane hydrophobic grouping.This tensio-active agent can provide low surface tension, high wetting, high spreadability, froth breaking and good scrubbing.Silicone surfactant of the present invention comprises by hydrosilanes glycosylation reaction polyethers, typically the polyalkylene oxide base is grafted to the polydialkysiloxane on it, for example polydimethylsiloxane.This method causes the alkyl side to hang the multipolymer of (AP type), and wherein the polyalkylene oxide base connects along siloxane main chain by the Si-C key of a series of hydrolysis-stables.
The polydialkysiloxane product that these nonionics replace has following general formula:
Figure A20048003130200351
Wherein PE represents non-ionic group, for example-and CH 2-(CH 2) p-(EO) m(PO) n-Z, wherein EO represents oxyethane, and PO represents propylene oxide, x is that scope is about 0 to about 100 numeral, and y is that scope is the numeral of about 1-100, and m, n and p are that scope is about 0 to about 50 numeral, m+n 〉=1 and Z represent hydrogen or R, and wherein each R represents rudimentary (C independently 1-6) the straight or branched alkyl.Molecular weight (the M of this tensio-active agent n) be about 500-20,000.
Other siloxanes nonionogenic tenside has following formula:
Figure A20048003130200352
Wherein x representative scope is about 0 to about 100 numeral, and y representative scope is about 1 to about 100 numeral, and on behalf of scope, a and b be about 0 to about 60 numeral independently, and a+b 〉=1 and each R are H or lower straight or side chain (C independently 1-6) alkyl.Second group of nonionic siloxane tensio-active agent is alkoxy end-capped (AEB type), and it is not so preferred, because the Si-O-key provides limited resistance to hydrolysis under condition neutral or slightly slight alkalinity, but decomposes fast in sour environment.
Suitable tensio-active agent is sold with trade(brand)name SILWET , trade(brand)name TEGOPREN  or with trade(brand)name ABIL  B.A kind of useful tensio-active agent SILWET  L77 has following formula:
(CH 3) 3Si-O(CH 3)Si(R 1)O-Si(CH 3) 3
R wherein 1=-CH 2CH 2CH 2-O-[CH 2CH 2O] zCH 3Wherein z is 4-16, preferred 4-12, most preferably 7-9.
Other useful tensio-active agent comprises TEGOPREN 5840 , ABIL B-8843 , ABIL B-8852  and ABIL B-8863 .
Anion surfactant
Can be used for of the present invention equally is the surfactant that is categorized as anion surfactant, and this is because the electric charge on hydrophobic materials is negative; Perhaps wherein the hydrophobic part of molecule does not carry the tensio-active agent (for example, carboxylic acid) of electric charge (unless rising pH is to neutral or higher).Carboxylate radical, sulfonate radical, sulfate radical and phosphate radical are polarity (hydrophilic) solubilizing groups of finding in anion surfactant.With these polar group bonded positively charged ions (counter ion) in the middle of, sodium, lithium and potassium are given solubleness in the water; The ammonium ion of ammonium and replacement provides the solubleness in water and the oil; Calcium, barium and magnesium promote the solubleness in the oil.
Anion surfactant is good detersive surfactant, therefore advantageously adds in the heavy duty detergent composition.Yet in general, anion surfactant has high foam property, this character limited its use separately or under high density at cleaning system, use in the CIP circuit of for example strict foam control.In addition, anionic surfactant compound can be given special chemistry or the physicals except decontamination in said composition.Anion surfactant can be used as jelling agent or is used as the gelling or the thickened systems of part.Anion surfactant be good solubilizing agent and can be used for water-soluble growth encourage effect and cloud point control on.
Great majority in many commercial anion surfactants can be subdivided into five main chemical group and extra subgroup, and these are at " Surfactant Encyclopedia ", Cosmetics ﹠amp; Toiletries, be disclosed among Vol.104 (2) 71-86 (1989).First group comprises acylamino acid (and salt), for example acyl group gluamate, acyl group peptide, sarcosinate (for example, N-acyl sarcosinate), tartrate (for example, the fatty acid amide of N-acyl group tartaric acid salt and methylamino esilate) and analogue.Second group comprises carboxylic acid (and salt), for example paraffinic acid (and alkanoate), ester carboxylic acid (for example, succsinic acid alkane ester), ether carboxylic acid and analogue.The 3rd group comprises phosphoric acid ester and salt thereof.The 4th group comprises sulfonic acid (and salt), for example isethionate (for example acyl-hydroxyethyl sulfonate), alkylaryl sulphonate, alkylsulfonate, sulfosuccinic ester (for example monoesters of sulfo-succinic acid and diester) and analogue.The 5th group comprises sulfuric ester (and salt), for example sulfated alkyl ether, alkyl-sulphate and analogue.Although can use in the anion surfactant of these groups each, should be noted that in these anion surfactants some may be incompatible with enzyme at the present composition.For example, acylamino acid and salt may be incompatible with proteolytic enzyme, and this is because due to their the peptide structure.
The anion sulfate tensio-active agent that is suitable for using in the present composition comprises the primary and secondary alkyl-sulphate of straight chain and side chain, alkyl ethoxy sulfate, fatty oil base glycerol vitriol, alkylphenol oxyethane ether sulfate, C 5-C 17Acyl group-N-(C 1-C 4Alkyl) and-N-(C 1-C 2Hydroxyalkyl) vitriol of glucosamine sulfate and alkyl polysaccharide, for example vitriol of alkyl poly glucoside (nonionic non-sulfuric acid compound described herein).
Suitable example synthetic, the water soluble anion detergent compound comprises the ammonium of alkyl monokaryon aromatic sulfonic acid (for example the alkyl in straight or branched contains 5 alkyl benzene sulphonate (ABS)s to about 18 carbon atoms of having an appointment) and (for example replaces ammonium, single-, two/and trolamine) and basic metal (for example sodium, lithium and potassium) salt, the salt of for example alkylbenzene sulfonate, or alkyl toluene, dimethylbenzene, cumene and sulfocarbolic acid; Sulfonated alkyl naphathalene, diamyl machine naphthalenesulfonate and dinonylnaphthalene sulfonic acid salt and oxidation alkyl derivative.
The anionic carboxylate tensio-active agent that is suitable for using in the present composition comprises alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate's tensio-active agent and soap class (for example alkyl carboxyl).The secondary type soap class tensio-active agent (for example, alkyl carboxyl tensio-active agent) that can be used for the present composition comprise contain the carboxyl that is connected on the secondary carbon unitary those.Secondary carbon can be in ring structure, for example in the ring structure of the cyclohexane carboxylic acid salt that octyl group phenylformic acid or alkyl are replaced.Secondary type soap class tensio-active agent is not ether-containing key, ester bond or hydroxyl typically.In addition, they typically lack nitrogen-atoms in headgroup (both sexes part).Suitable secondary type soap class tensio-active agent typically contains 11-13 total carbon atom, but can have more carbon atom (for example, maximum 16).
Other anionic detergent that is suitable for using in the present composition comprises alkene sulfonate, long-chain olefin sulfonate for example, long-chain hydroxyl alkane sulfonate, or the mixture of alkene sulfonate and hydroxyl alkane sulfonate.Comprise alkyl-sulphate, poly-(ethyleneoxy group) ether sulfate of alkyl and aromatics poly-(ethyleneoxy group) vitriol, for example vitriol of oxyethane and nonylphenol or condensation product (each molecule has 1-6 oxygen base ethylidene usually) equally.Resinous acid and hydrogenated resin acid also are suitable, for example are present in or are derived from rosin, staybelite and resinous acid and hydrogenated resin acid in the tallow oil.
Depend on specific prescription and needs within it, select specific salt suitably.
In " Surface Active Agents and Detergents " (Vol I and II, Schwartz, Perry and Berch), provided the further example of suitable anion surfactant.Various this tensio-active agents are disclosed in the 58th row-Di 29 hurdles, the 23rd hurdle the 23rd row of the U.S. Patent No. 3929678 of authorizing people such as Laughlin on December 30th, 1975 equally usually.
In one embodiment, composition of the present invention comprises alkyl or alkylaryl sulphonate or replaces vitriol and sulfation product.In some embodiments, composition of the present invention comprises branched paraffin sulfonate, branch-alkylbenzene sulfonate, sulfonated, alkyl-sulphate, secondary alkane vitriol or sulfonate, or sulfosuccinate.
Cats product
If the electric charge on the hydrotropic agent part of surfactant molecule is positive, then this surfactant is categorized as positively charged ion.Be included in equally in this group is the cationic tensio-active agent (for example alkanamine) of hydrotropic agent neutral (unless reducing pH to approaching neutrality or lower) wherein.In theory, can be by containing " " structure R nX +Y -Any combination of element come synthesizing cationic tensio-active agent and it can comprise compound except nitrogen (ammonium), for example compound of phosphorus () and sulphur (sulfonium).In practice, the cats product field is taken as the leading factor by nitrogenous compound, may be because the synthetic route of cationic nitrogenous tensio-active agent is simple and directly and obtain the high yield of product, this makes them so expensive.
Cats product preferably includes, and is meant that more preferably containing at least one grows the hydrophobic grouping of carbochain and the nitrogen compound of at least one positively charged.Long carbochain group can be directly connected on the nitrogen-atoms by simple replacement, perhaps more preferably is connected on the nitrogen-atoms indirectly by one or more bridging functional groups in so-called interval alkanamine and amido amine.This functional group can make this molecule more hydrophilic and/or more water can disperse, easier of co-surfactant blend solubilising in water, and/or water soluble.In order to increase solubleness in the water, can introduce extra primary, second month in a season or uncle's amino, perhaps available low molecular weight alkyl season amino nitrogen.In addition, nitrogen can be the side chain of various degrees of unsaturation or saturated or unsaturated heterocycle or the part in the linear fraction.In addition, cats product can contain the complex bonds that has greater than a cationic nitrogen atom.
The surfactant compounds that is categorized as amine oxide, both sexes and amphiphilic surfactant itself typically is positively charged ion and the classification of tensio-active agent is intersected in acid pH solution in nearly neutrality.The behavior of polyoxy ethylization cats product in basic solution usually as nonionogenic tenside, and in acidic solution as cats product.
Therefore can illustrate the simplest cationic amine, amine salt and quaternary ammonium compound:
Wherein R represents chain alkyl, R, R " and R  can be long alkyl chain or less alkyl or aryl or hydrogen, X represents negatively charged ion.Amine salt and quaternary ammonium compound are because its high water solubility is useful.
Great majority in many commercial anion surfactants can be subdivided into four groups and the known or familiar extra subgroup of those skilled in the art, as at " SurfactantEncyclopedia ", and Cosmetics ﹠amp; Toiletries is described in Vol.104 (2) 86-96 (1989).First group comprises alkanamine and salt thereof.Second group comprises alkyl imidazoline.The 3rd group comprises ethoxylated amine.The 4th group comprises the season thing, for example alkyl benzyl dimethyl ammonium salt, alkylbenzene salt, heterocycle ammonium salt, tetraalkylammonium salt and analogue.Known cats product has various performances useful in the present composition.These required performances can comprise the detergency that is lower than composition under the neutral pH, antimicrobial efficient, the thickening or the gelling property of cooperating with other reagent, and similar performance.
The cats product that can be used for the present composition comprises having chemical formula R 1 mR 2 xY LThose of Z, wherein each R 1It is the organic group that contains straight or branched alkyl or alkenyl, described organic group randomly replaces with maximum three phenyl or hydroxyl and randomly with the isomer of maximum 4 following structures or these structures or mixture separates and described organic group contains 8-22 the carbon atom of having an appointment:
Figure A20048003130200392
R 1Base can additionally contain maximum 12 oxyethyl groups, and m is the numeral of 1-3.Preferably, when m was 2, intramolecularly was no more than a R 1Have 16 or more carbon atom, perhaps when m is 3, have greater than 12 carbon atoms.Each R 2Be alkyl or hydroxyalkyl or the benzyl that contains 1-4 carbon atom, and intramolecularly is no more than a R 2Be that benzyl and x are the numerals of 0-11, preferred 0-6.Any carbon atom position of on the Y base all the other is filled with hydrogen.
Y includes, but is not limited to following group,
Figure A20048003130200401
Figure A20048003130200402
About 1 to 12 of p=
About 1 to 12 of p=
Figure A20048003130200404
Or its mixture.Preferably, L is 1 or 2, and when L is 2, and the Y base is selected from has 1 to about 22 carbon atoms and two R of carbon single bond freely 1And R 2Homologue (preferred alkylidene group or alkenylene) part separately.Z is a water soluble anion, for example halogen ion, sulfate radical, methylsulfate, hydroxide radical or nitrate anion, especially preferred chlorion, bromide anion, iodide ion, sulfate radical or methylsulfate negatively charged ion, its quantity obtains electroneutral cationic components.
Amphoterics
Amphoterics contains alkalescence and acid hydrophilic radical and organic hydrophobic grouping simultaneously.These ion bodies can be herein for described any negatively charged ion of the tensio-active agent of other type or cation group.Basic nitrogen and acid carboxylic acid group are the typical functional groups as alkalescence and acid hydrophilic radical.In some tensio-active agents, sulfonate radical, sulfate radical, phosphonate radical or phosphate radical provide negative charge.
Amphoterics can broadly be described as the derivative of the aliphatic series second month in a season and tertiary amine; wherein aliphatic group can be a straight or branched; and wherein one of aliphatic substituting group contains 8-18 the carbon atom of having an appointment; with one contain the anionic water solubilizing group, for example carboxyl, sulfo group, sulfato, phosphate radical close or phosphoryl.Amphoterics is subdivided into two main groups well known by persons skilled in the art, and is disclosed in " Surfactant Encyclopedia ", Cosmetics ﹠amp; Toiletries, among Vol.104 (2) 69-71 (1989).First group comprises acyl group/dialkyl group ethylene diamine derivative (for example, 2-alkyl hydroxyethyl imidazoline derivative) and salt thereof.Second group comprises N-alkyl amino acid and salt thereof.Think that some amphotericses can meet this two class.
Can be by the synthetic amphoterics of method known to those skilled in the art.For example, by condensation long-chain carboxylic acid (or derivative) and dialkyl group quadrol and closed loop, thus Synthetic 2-alkyl hydroxyethyl imidazoline.By with posthydrolysis with by alkylation, for example, make the open loop of tetrahydroglyoxaline ring with chloracetic acid or ethyl acetate alkylation, come the amphoterics of derivatize commerce.In alkylation process, one or two carboxyalkyl and different alkylation reactions form tertiary amine and ehter bond, thereby obtain different tertiary amines.
Available long-chain imdazole derivatives has following general formula usually in the present invention:
(list) acetate (two) propionic salt both sexes sulfonate
Neutral pH-zwitter-ion
Wherein R is the acyclic hydrophobic grouping that contains 8-18 the carbon atom of having an appointment, M be in and the positively charged ion of anionic charge, normally sodium.The commercial promising tetrahydroglyoxaline deutero-amphoterics that can use in the present composition for example comprises: N-(cocamidopropyl ethyl)-N-(2-hydroxyethyl) alanine sodium, N-(cocamidopropyl ethyl)-N-(2-ethoxy-c acidic group) alanine sodium, N-(cocamidopropyl ethyl)-N-(2-hydroxyethyl) Sodium glycocollate, N-cocamidopropyl ethyl-N hydroxyethyl-N-carboxymethylamino sodium acetate, N-(cocamidopropyl ethyl)-N-(2-hydroxyethyl amino)-2-hydroxypropyl sodium sulfonate and N-(cocamidopropyl ethyl)-N-(2-ethoxy-c acidic group) alanine.By the dicarboxylic acid functionality in the both sexes dicarboxylic acid wherein is the preferred both sexes carboxylic acid of fatty tetrahydroglyoxaline production of oxalic acid and/or dipropionic acid.
More than the normal carboxymethylation compound of describing (glycinate) be called as trimethyl-glycine.Trimethyl-glycine is to be one group of special amphoterics discussing in the following amphiphilic surfactant part at title.
Easily pass through RNH 2(R=C wherein 8-C 18The straight or branched alkyl), aliphatic amide and halogenation carboxylic acid reaction, thereby preparation long-chain N-alkyl amino acid.The alkylation of primary amino causes the second month in a season and tertiary amine in the amino acid.Alkyl substituent can have extra amino, and described extra amino provides greater than a reactive nitrogen center.The N-alkyl amino acid of most of commerce is alkyl derivatives of Beta-alanine or β-N (2-propyloic) L-Ala.The commercial N-alkyl amino acid amphotericeledrolyte that uses among the present invention example comprise beta-amino dipropionic acid alkyl ester, RN (C 2H 4COOM) 2And RNHC 2H 4COOM.In these, R preferably contain have an appointment 8 to the acyclic hydrophobic grouping of about 18 carbon atoms and M be in and the positively charged ion of anionic charge.
Preferred amphoterics comprises those that are derived from the coconut product, for example Oleum Cocois or coco-nut oil fatty acid.The tensio-active agent of preferred these coconut derived comprises quadrol part, alkylolamide part, amino acid moiety, preferred glycine, or it is in conjunction with as its part-structure; Aliphatic substituting group with the individual carbon atom of about 8-18 (preferred 12).This tensio-active agent also can be regarded as alkyl both sexes dicarboxylic acid.Cocounut oil both sexes disodium beclomethasone is a kind of most preferred amphoterics, and can trade(brand)name Miranol TMFBS is available commercially from RhodiaInc., Cranbury, N.J..Another is most preferred to have the amphoterics of coconut derived of chemical name cocounut oil both sexes oxalic acid disodium with trade(brand)name Miranol TMC2M-SF Conc. sale (also available from Rhodia Inc., Cranbury, N.J.).
The typical case who has provided amphoteric type in authorizing the U.S. Patent No. 3929678 of Laughlin and Heuring on December 30th, 1975 enumerates the material with these tensio-active agents.In " Surface Active Agents and Detergents " (Vol.I and II, Schwartz, Perry and Berch), provided further example.
Amphiphilic surfactant
Amphiphilic surfactant can be regarded as the subgroup of amphoterics.Amphiphilic surfactant can broadly be described as the derivative of secondary and tertiary amine, the derivative of the heterocycle second month in a season and tertiary amine, or the derivative of quaternary ammonium, season  or uncle's sulfonium compound.Typically, amphiphilic surfactant comprises the quaternary ammonium of positively charged, or in some cases, sulfonium or  ion; Electronegative carboxyl; And alkyl.Amphiphilic surfactant contains positively charged ion and anionic group usually, and described positively charged ion becomes almost equal degree with anionic group in the isoelectric zone internal ionization of this molecule, and can just-form strong " inner salt " magnetism between the center of negative charge.The example of this amphiphilic synthetic surfactant comprises the derivative of aliphatic quaternary ammonium,  and sulfonium compound, aliphatic group wherein can be a straight or branched, wherein one of aliphatic substituting group contains 8-18 carbon atom and one and contains anionic water solubilizing group, for example carboxyl, sulfonate radical, sulfate radical, phosphate radical or phosphonate radical.Trimethyl-glycine and sultaine tensio-active agent are the amphiphilic surfactants that exemplifies that herein uses.
The general formula of these compounds is:
Figure A20048003130200431
R wherein 1The alkyl, alkenyl or the hydroxyalkyl that contain 8-18 carbon atom with 0-10 ethylene oxide moiety and 0-1 glyceryl part; Y is selected from nitrogen, p and s atom; R 2Be alkyl or the monohydroxy alkyl that contains 1-3 carbon atom; When Y was sulphur atom, x was 1, and when Y was nitrogen or phosphorus atom, x was 2, R 3Be that the alkylidene group of 1-4 carbon atom or hydroxy alkylidene or hydroxy alkylidene and Z are the groups that is selected from carboxylate radical, sulfonate radical, sulfate radical, phosphonate radical and phosphate groups.
Example with amphiphilic surfactant of structure listed above comprises: 4-[N, N-two (2-hydroxyethyl)-N-octadecyl ammonium] butane-1-carboxylate salt, 5-[S-3-hydroxypropyl-S-hexadecyl sulfonium base]-3-hydroxyl pentane-1-vitriol; 3-[P, P-diethyl-P-3,6,9-trioxa four is read alkane  yl] 2-hydroxy propane-1-phosphoric acid salt; 3-[N, N-dipropyl-N-3-dodecyloxy-2-hydroxypropyl ammonium]-propane-1-phosphonate; 3-(N, N-dimethyl-N-hexadecyl ammonium)-propane-sulfonate; 3-(N, N-dimethyl-N-hexadecyl ammonium)-2-hydroxyl-propane-1-sulfonate; 4-[N, N-two (2 (2-hydroxyethyl)-N (2-hydroxyl dodecyl) ammonium)-butane-1-carboxylate salt; 3-[S-ethyl-S-(3-dodecyloxy-2-hydroxypropyl) sulfonium base] propane-1-phosphoric acid salt; 3-[P, P-dimethyl-P-dodecyl  yl]-propane-1-phosphonate; And S[N, N-two (3-hydroxypropyl)-N-hexadecyl ammonium]-2-hydroxyl-pentane-1-vitriol.The alkyl that is included in the described detergent surfactant can be straight or branched and saturated or unsaturated alkyl.
The amphiphilic surfactant that is suitable for using in the present composition comprises the trimethyl-glycine of following formula:
Figure A20048003130200441
These tensio-active agent trimethyl-glycines are not typically demonstrating strong cation or negatively charged ion feature under extreme pH, they its etc. do not demonstrate the water solubility of minimizing in the electricity scope yet.Different with " outward " quaternary ammonium salt is that trimethyl-glycine and anion surfactant are compatible.The example of suitable trimethyl-glycine comprises cocamidopropyl propyl-dimethyl trimethyl-glycine; The hexadecyldimethyl benzyl ammonium trimethyl-glycine; C 12-14Amido propyl betaine; C 8-14Amide group hexyl diethyl betaines; 4-C 14-16Acyl group methyl nitrosourea base diethyl ammonium-1-carboxyl butane; C 16-18The amide group dimethyl betaine; C 12-16Amide group pentane diethyl betaines; And C 12-16Acyl group methyl nitrosourea base dimethyl betaine.
Can be used for sultaine of the present invention and comprise (R (the R that has chemical formula 1) 2N +R 2SO 3-) those compounds, wherein R is C 6-C 18Alkyl, each R 1Typically independent is C 1-C 3Alkyl, for example methyl, and R 2Be C 1-C 6Alkyl, for example C 1-C 3Alkylidene group or hydroxy alkylidene.
The typical case who has provided the amphiphilic type in authorizing the U.S. Patent No. 3929678 of Laughlin and Heuring on December 30th, 1975 enumerates the material with these tensio-active agents.In " Surface Active Agents and Detergents " (Vol.I and II, Schwartz, Perry and Berch), provided further example.
Surfactant composition
In practice of the present invention and purposes, above-described tensio-active agent can separately or be used in combination.Especially, nonionogenic tenside and anion surfactant can be used in combination.Semi-polar nonionic, positively charged ion, both sexes and amphiphilic surfactant can use together in conjunction with nonionic or anion surfactant.Above-mentioned example only is to find specifically enumerating of the many tensio-active agents of available within the scope of the invention.But the invention of aforementioned organic surface active agent compound preparation cost has any in several commercial required composition forms of disclosed purposes.Described composition comprises the carrying out washing treatment agent that is used for contaminated surface of conc forms, when the described carrying out washing treatment agent quantitative cooperating equipment dilution of passing ratio suitably, be dispersed or dissolved in the water, and when being transported on the target surface with the solution form, gel or foam will provide cleaning.Described clean agent is made up of a kind of product, perhaps comprises two kinds of product systems wherein using each ratio.Described product is the concentrated solution of liquid or emulsion typically.
Hydrotropic agent
Usually in prescription, use hydrotropic agent, to keep pure single-phase or aqueous composition.This reagent also can use in the present invention.The hydrotropy relate to material improvement wherein material tend to the performance of this solubility of substances in the insoluble liquid phase or miscibility within it.Provide the material of the hydrotropy to be called as hydrotropic agent, and compare, can use with relatively low concentration with the material for the treatment of solubilising.Hydrotropic agent improved formulations, result increase the solubleness of insoluble substance or produce micella or mixed micelle structure, thereby cause the stable suspension of insoluble substance.In the present invention, hydrotropic agent the most usefully maintain preparation process neutralization when using the place to disperse, fill a prescription in the uniform solution of each component.Hydrotropic agent solubilizing agent can be kept a single phase soln that each component distributes equably and be in moisture or non-moisture form in said composition.
Preferred hydrotropic agent solubilizing agent is with about 0.1 to about 30wt% concentration use and comprise for example small molecules anion surfactant and semi-polar nonionogenic tenside.The most preferred scope of hydrotropic agent solubilizing agent is about 1 to about 20wt%.Well-known relatively is that the hydrotropic agent material demonstrates hydrotropy energy in the chemical molecular type of wide region.Hydrotropic agent generally includes ether compound, alkylol cpd, anion surfactant, cats product and other material.A kind of important hydrotropic agent solubilizing agent that the present invention uses comprises the amine oxide material.The small molecules anion surfactant comprises aromatic sulfonic acid or sulfonation hydrotropic agent, for example C 1-5The Phenylsulfonic acid or the naphthene sulfonic acid that replace.This hydrotropic example is xylene monosulfonic acid or naphthene sulfonic acid or its salt.
The ionic surfactant pack of semi-polarity type is drawn together the amine oxide hydrotropic agent, for example corresponding to uncle's amine oxide of following general formula:
Wherein n is 0-25, and arrow is the conventional expressing method of semi-polar linkage; R 1, R 2And R 3Can be aliphatic series, aromatics, heterocycle, alicyclic or its combination.In general, for the interested amine oxide of detergent applications, R 1Be about 8 to the side chain of about 24 carbon atoms or the aliphatic series or the alkyl of straight chain; R 2And R 3Be selected from alkyl or hydroxyalkyl or its mixture of 1-3 carbon atom; R 4Be alkylidene group or the hydroxy alkylidene that contains 2-3 carbon atom; The scope of n is 0 to about 20.Useful water-soluble amine oxides hydrotropic agent is selected from alkyl two (low alkyl group) amine oxide, and its specific examples is C 10-14Iso-alkyl dimethyl oxidation amine, (Permethyl 99A. base) dimethyl oxidation amine-Barlox12i, positive decyl dimethyl oxidation amine, dimethyl dodecyl amine oxide, tridecyl dimethyl oxidation amine, CH3-(CH2)13N(CH3)2-O, pentadecyl dimethyl oxidation amine, cetyl dimethyl amine oxide, heptadecyl dimethyl oxidation amine, octadecyl dimethyl amine oxide, dodecyl dipropyl amine oxide, tetradecyl dipropyl amine oxide, hexadecyl dipropyl amine oxide, tetradecyl dibutyl amine oxide, octadecyl dibutyl amine oxide, two (2-hydroxyethyl) dodecyl amine oxide, two (2-hydroxyethyl)-3-dodecyloxies (dodecoxy)-1-hydroxypropyl amine oxide, dimethyl-(2-hydroxyl dodecyl) amine oxide and 3,6, Permethyl 99A. base dimethyl oxidation amine (Barlox12i) most preferably more than 9-three (octadecyl) the dimethyl oxidation amine.Usually can in the present composition, use other hydrotropic agent or coupler (coupler), to keep monophasic integrity of physics and stability in storage.For this reason, can use the known any amount of composition of those of ordinary skill in the prescription field, for example simple function and polyfunctional alcohol.These preferably contain have an appointment 1 to about 6 carbon atoms and 1 to about 6 hydroxyls.Example comprises ethanol, Virahol, n-propyl alcohol, 1,2-propylene glycol, 1,2-butyleneglycol, 2-methyl-2,4-pentanediol, sweet dew alcohol and glucose.Same available is senior dibasic alcohol, polyvalent alcohol, poly oxide, glycol ether and propylene glycol.Extra useful hydrotropic agent comprises an alkali metal salt of free acid and sulfolane aryl, for example alkylation diphenyl ether sulfonate, toluene, dimethylbenzene, cumene and phenol or phenol ether sulfonate or alkoxylate phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate (Dowfax material); Alkyl and dialkyl group naphthalenesulfonate and alkoxy derivative.Generally be not considered to be the material of strong surfactant types as hydrotropic these sulfonate materials.These materials are the sulfonate with hydrophobic grouping of connection, and described sulfonate is designed to provide hydrotropy energy, rather than surfactant properties.What should keep firmly in mind is that these materials generally are not considered to be surfactant composition.
Sequestering agent
Cleaning compositions of the present invention can comprise sequestering agent.In general, sequestering agent is the molecule of the common metal ion of finding in natural water of energy coordination (that is, bonding), disturbs the effect of other decontamination composition in the cleaning compositions to prevent metal ion.This sequestrant/sequestering agent also can serve as threshold agent (threshold agent) when comprising with significant quantity.About the further discussion of sequestrant/sequestering agent, referring to, Kirk-Othmer, Encyclopedia of Chemical Technology, the 3rd edition, the 5th volume, 339-366 page or leaf and the 23rd volume, 319-320 page or leaf.
Can in heterogeneous cleaning compositions of the present invention, use various sequestering agents, comprising organic phosphonate for example, aminocarboxylic acid, condensed phosphate, inorganic builders, multi-carboxylate polymer, two or tricarboxylic acid, its mixture or analogue.This sequestering agent and washing assistant are commercially available.In some embodiments, heterogeneous cleaning compositions of the present invention comprises about 5 to about 50wt%, and about 30 to about 50wt%, and about 10 to about 45wt%, or about sequestering agent of 20 to about 40wt%.In some embodiments, heterogeneous cleaning compositions of the present invention comprises the sequestering agent of about 20wt%, about 25wt%, about 30wt%, about 35wt% or about 40wt%.Said composition can comprise these scopes that change approximately of no use or any one in the content.
Suitable condensed phosphate comprises sodium orthophosphate and potassium, trisodium phosphate and potassium, tripoly phosphate sodium STPP and potassium, Sodium hexametaphosphate 99, for example tri-polyphosphate.In one embodiment, heterogeneous cleaning compositions of the present invention comprises condensed phosphate, and for example tripoly phosphate sodium STPP is as washing assistant, sequestrant or sequestering agent.
Be suitable for for example comprising as the polycarboxylate of sequestering agent, polyacrylic acid, toxilic acid/olefin copolymer, vinylformic acid/maleic acid, polymethyl acrylic acid, vinylformic acid-Sipacril 2739OF, the polyacrylamide of hydrolysis, the PMAm of hydrolysis, polymeric amide-the methacrylamide copolymer of hydrolysis, the polyacrylonitrile of hydrolysis, the polymethacrylonitrile of hydrolysis, vinyl cyanide-the methacrylonitrile copolymers of hydrolysis, polymaleic acid, poly-fumaric acid, the multipolymer of vinylformic acid and methylene-succinic acid, and analogue, in one embodiment, polycarboxylate comprises polyacrylate.
Two suitable or tricarboxylic acid comprises oxalic acid, citric acid or its salt.In one embodiment, oxalic acid can be used for being reduced in the content of iron in the set of applications compound or removes the de-iron dirt from goods to be cleaned.For example, oxalic acid can be the acid of control iron or the part of iron removing reagent.
In one embodiment, heterogeneous cleaning compositions of the present invention comprises condensed phosphate and polyacrylate or another polymkeric substance, and for example tripoly phosphate sodium STPP and polyacrylate are as sequestering agent or washing assistant.
Washing assistant can include organic phosphonates, for example organic phospho acid and an alkali metal salt thereof.Some examples of suitable organic phosphonate comprise:
1-hydroxyl ethane-1,1-di 2 ethylhexyl phosphonic acid: CH 3C (OH) [PO (OH) 2] 2
Amino three (methylene phosphonic acid): N[CH 2PO (OH) 2] 3
Amino three (methylene phosphonic acid) sodium salt:
Figure A20048003130200481
2-hydroxyethyl imino-two (methylene phosphonic acid):
HOCH 2CH 2N[CH 2PO(OH) 2] 2
Diethylenetriamine five (methylene phosphonic acid):
(HO) 2POCH 2N[CH 2CH 2N[CH 2PO(OH) 2] 2] 2
Diethylenetriamine five (methylene phosphonic acid) sodium salt: C gH (28-x)N 3Na xO 15P 5(x=7); Hexamethylene-diamine (tetramethylene phosphonic acid) sylvite: C 10H (28-x)N 2K xO 12P 4(x=6); Two (hexa-methylene) triamine (pentamethylene phosphonic acids): (HO 2) POCH 2N[(CH 2) 6N[CH 2PO (OH) 2] 2] 2With phosphoric acid H 3PO 3With other similar organic phosphonate, and composition thereof.
Sequestering agent can be or comprise the sequestering agent of aminocarboxylic acid type.The sequestering agent of suitable aminocarboxylic acid type comprises acid or its an alkali metal salt, for example Padil and salt thereof.Some examples comprise following:
N-hydroxyethylamino oxalic acid;
Hydroxyethylenediamine tetracetic acid, nitrilotriacetic acid(NTA) (NTA);
Methylglycine oxalic acid (MGDA);
Ethylenediamine tetraacetic acid (EDTA) (EDTA);
N-hydroxyethyl-ethylenediamine nitrilotriacetic (HEDTA);
Diethylene triaminepentaacetic acid(DTPA) (DTPA); With
Alanine-N, the N-oxalic acid;
The imino-diacetic succsinic acid;
And analogue; And composition thereof.
A kind of useful washing assistant/sequestrant or its salt comprise the polymeric phosphines yl carboxylic acid, comprising its salt and its derivative.Can be by making unsaturated carboxylic acid monomer for example vinylformic acid and the Hypophosporous Acid, 50 or derivatives thereof reaction of usually representing with following formula, thus prepare this material:
Figure A20048003130200491
R wherein 1Be group OX, wherein X is hydrogen or the straight or branched alkyl that contains 1-4 carbon atom; And R 3Be the straight or branched alkyl of a hydrogen or 1-8 carbon atom, the cycloalkyl of 5-12 carbon atom, phenyl, benzyl or-the OX group, wherein X is the straight or branched alkyl of hydrogen or 1-4 carbon atom.Also can use poly-phosphinocarboxylic acid's salt as mentioned above.A preferred embodiment of this material is Belsperse -161.
Sequestering agent can be or comprise biodegradable sequestering agent.Suitable biodegradable sequestering agent comprises methylglycine oxalic acid or its salt.This sequestering agent for example is purchased with trade(brand)name Trilon ES.
Enzyme
Cleaning compositions of the present invention can comprise one or more enzymes, and described enzyme can provide that required activity is protein-based for removing from substrate, carbohydrate-based or triglyceride level base dirt be for cleaning, decontamination and pre-soaking.Although do not limit the present invention, but the enzyme that is suitable for cleaning compositions of the present invention can work by degraded or the dirt residue that changes one or more types run on surface or textiles, thereby removes crude removal or dirt can be removed more by other component in tensio-active agent or the cleaning compositions.Can be attached to surface to be cleaned or the physical-chemistry force on the textiles by reducing dirt, that is, make dirt water soluble more,, improve soil release characteristics by not only degrading but also change the dirt residue.For example, one or more proteolytic enzyme can make the complex compound, the macro-molecular protein structure that are present in the dirt residue be dissociated into better simply short chain molecule by the decontaminating solution that contains described proteolytic enzyme, described short chain molecule itself is more prone to desorb from the surface, dissolving or or be more prone to remove.
Suitable enzyme comprises any suitable source, for example proteolytic enzyme, amylase, lipase, glucose enzyme, cellulase, peroxidase or its mixture in plant, animal, bacterium, fungi or yeast source.Preferred select to be subjected to such as pH activity and/or optimizing stability, thermostability with to the influence of the factors such as stability of activated detergent, washing assistant and analogue.About this point, preferred bacterium or fungal enzyme, for example bacterial amylase and proteolytic enzyme, and fungal cellulase.Preferred enzyme is proteolytic enzyme, lipase, amylase or its combination.
" detergency enzymes " as used herein be meant have cleaning, decontamination or or the enzyme with beneficial effect as the component in the composition in order to laundry, textiles, dish washing, original place cleaning, water shoot, ground, carpet, medical treatment or dental instruments, meat cutting instrument, hard surface, personal care or analogue.Suitable detergency enzymes comprises lytic enzyme such as proteolytic enzyme, amylase, lipase or its combination.
Usually in washing or pre-soaking operation process, enzyme is incorporated in the present composition with the significant quantity that is effectively cleaned.The significant quantity that is used to clean is meant material production cleaning to be cleaned, health and the preferred consumption that does not have the corrosion outward appearance.The significant quantity that is used to clean also can refer in substrate to produce cleaning, removes spot, scrubbing, brightens, the consumption of taste removal or vivid improvement effect.Typically, can be adopted as cleaning compositions about 0.1% to about 3wt%, preferred about 1% realizes this cleaning effect to the enzyme of about 3wt% consumption.Higher live vol also is an ideal in highly spissated cleaning prescription.
Can liquid or dried forms obtain commercial enzyme, Sumizyme MP for example, and with the thick aqueous solution or with classification select, purifying, processing and compounding form sell, and comprise usually and stablizer, damping fluid, cofactor (cofactor), impurity and about 2% to about 80wt% the organized enzyme of inert support bonded.Actual organized enzyme content depends on the preparation method and is not crucial, if said composition has required enzymic activity.For in method of the present invention and product, using the specific enzyme selects to depend on final working conditions, comprising physical form, use pH, the use temperature of product with wait the dirt type that digests, degrade or change.For any one group of given working conditions, can select enzyme so that the active and stable of the best to be provided.
Composition of the present invention preferably includes at least a proteolytic enzyme.Find further that astoundingly composition of the present invention not only stabilize proteins enzyme reaches the shelf-life of significant prolongation, and significantly improves the protease activities of digesting protein and improve scrubbing.In addition, at one or more extra enzymes, for example amylase, cellulase, lipase, peroxidase, endoglucanase and composition thereof under preferred lipase or amylase exist, the protease activity that improves occurs.
Can select enzyme according to cleaning compositions institute's target or the dirt type that on position to be cleaned or surface, exists.Although do not limit the present invention, think that amylase can be advantageously used in cleaning and contain starch, for example dirt of potato, pasta, oatmeal, infant food, gravy, chocolate or analogue.Although do not limit the present invention, think that proteolytic enzyme can be advantageously used in cleaning and contain protein, for example dirt of the scurf of blood, skin, mucus, grass, food (for example egg, milk, spinach, meat slag, tomato juice) or analogue.Although do not limit the present invention, think that lipase can be advantageously used in cleaning and contain fat, oil or wax, for example dirt of animal or plant fat, oil or wax (for example salad seasonings, butter, lard, chocolate, lipstick).Although do not limit the present invention, think that cellulase can be advantageously used in the dirt that cleaning contains cellulosic dirt or contains cellulosic fibre (it plays the effect of the attachment point of other dirt).
Important references document about enzyme is at " Industrial Enzymes " Scott, D., Kirk-Othmer Encyclopedia of Chemical Technology, the 3rd edition (editor Grayson, M. and EcKroth, D.) the 9th volume, 173-224 page or leaf, John Wiley ﹠amp; Sons, New York, 1980.
Proteolytic enzyme
The proteolytic enzyme that is suitable for the present composition can be derived from plant, animal or microorganism.Preferably, proteolytic enzyme is derived from microorganism, for example yeast, mould or bacterium.Preferred proteolytic enzyme is included in has active serine protease under the alkaline pH, it preferably is derived from for example bacterial strain of subtilis or Bacillus licheniformis of genus bacillus; These preferred proteolytic enzyme comprise subtilisin natural and reorganization.Proteolytic enzyme can be purified or can be component and or the agriotype or the variant (variant of chemistry or reorganization) of microorganism extracts.Preferred proteolytic enzyme both be not subjected to metal chelator (sequestering agent) or the mercaptan poisonous substance suppresses, also not by metal ion or reductive agent activation, has wide substrate specificity, being subjected to di-isopropyl fluoro phosphoric acid salt (DFP) suppresses, be a kind of inscribe peptase, molecular weight ranges is about 20,000 to about 40,000, and pH about 6 to about 12 times and temperature range be to have activity under about 20 ℃ to about 80 ℃.
The example of the proteolytic enzyme that can use in the present composition comprises (employing trade(brand)name) Savinase , is derived from the proteolytic enzyme of slow genus bacillus (Bacillus lentus) type, for example Maxacal , Opticlean , Durazym  and Properase ; With the proteolytic enzyme that is derived from Bacillus licheniformis, for example Alcalase  and Maxatase ; With the proteolytic enzyme that is derived from bacillus amyloliquefaciens, Primase  for example.Preferred commercially available proteolytic enzyme comprises those that sold by Novo Industries A/S (Denmark) with trade(brand)name Alcalase , Savinase , Primase , Durazym  or Esperase ; Those that sell by Gist-Brocades (Holland) with trade(brand)name Maxatase , Maxacal  or Maxapem ; Those that sell by GenencorInternational with trade(brand)name Purafect , Purafect OX and Properase; Those that sell by Solvay Enzymes with trade(brand)name Opticlean  or Optimase ; And analogue.Also can use the mixture of this proteolytic enzyme.For example, Purafect  is a kind of preferred Sumizyme MP (subtilisin) that uses in detergent composition of the present invention, and it can be used for lower cleaning temp program, for example about 30 ℃ to about 65 ℃; And Esperase  is a kind of about 50 ℃ of Sumizyme MPs of selecting to about 85 ℃ comparatively high temps decontaminating solution that are used for.Suitable decontamination proteolytic enzyme is disclosed in following patent publications: the GB1243784 of Novo, WO9203529A (enzyme/inhibitor system), WO9318140A and WO9425583 (the trypsinase shape proteolytic enzyme of reorganization); Procter ﹠amp; The WO9510591A of Gamble, WO9507791A (water-disintegrable proteolytic enzyme), WO95/30010, WO95/30011, WO95/29979 with absorption and increase of reduction; The WO95/10615 of GenencorInternational (subtilisin of bacillus amyloliquefaciens); EP130756A (protease A); EP303761 (proteolytic enzyme B); And EP130756A.Preferred at least 80% homology of employed misfolded proteins enzyme in the present composition preferably has at least 80% the sequence identity and the aminoacid sequence of the proteolytic enzyme in these reference.
In a preferred embodiment of the invention, the amount ranges that is present in the commercial Sumizyme MP in the present composition be about 0.1wt% of decontaminating solution to about 3wt%, preferably about 1% to about 3wt%, preferably the commercial enzyme product solution of about 2wt%.Typical commercially available detergency enzymes comprises the organized enzyme of about 5-10%.
Although it is easily in practice that the weight percentage of definite desired commercial Sumizyme MP is used for the preparation embodiment of the present invention's instruction, but the variation of commercial protease enriched material and environment additive on the spot and may require to be used for the more accurate analytical technology that proteolytic enzyme is analyzed to the negative impact of protease activity, so as in embodiment preferred quantification enzyme active and set up and pollute residue and remove the dependency of the stability of performance and enzyme; If with enriched material, then use diluting soln.The protease activities of using among the present invention is used activity unit easily, more particularly, expresses for unit with Kilo-Novo Protease Unit (KNPU), and this is that the well-known azo-casein of those skilled in the art is analyzed activity unit.Can be the publication of " The Use of Azoalbumin as a Substrate in the ColorimetricDetermination of Peptic and Tryptic Activity " at title, Tomarelli, R.M., Charney, J. and Harding, M.L. J.Lab.Clin.Chem, find the more detailed discussion of azo-casein analytical procedure in 34,428 (1949).
In a preferred embodiment of the invention, be present in the protease activities scope of using in the solution and be about 1 * 10 -5KNPU/gm solution is to about 4 * 10 -3KNPU/gm solution.
The mixture that naturally, can in the present invention, comprise different proteolytic enzyme.Although more than described various concrete enzymes, be appreciated that and use any proteolytic enzyme that to give composition desirable proteins enzymic activity, and in no case the proteolytic enzyme by concrete selection limits this embodiment of the present invention.
Amylase
The amylase that is suitable for the present composition can be derived from plant, animal or microorganism.Preferably, amylase is derived from microorganism, for example yeast, mould or bacterium.Preferred amylase comprises and is derived from genus bacillus, for example those of Bacillus licheniformis, bacillus amyloliquefaciens, subtilis or bacstearothermophilus (B.stearothermophilus).Amylase can be purified or can be component and or agriotype or variant (variant of chemistry or reorganization), the preferably variant more stable than the amylase of agriotype under washing or pre-soaking condition of microorganism extracts.
The diastatic example that can use in the present composition comprises those that sold by Gist-Brocades  (Holland) with trade(brand)name Rapidase; Those that sell by Novo with trade(brand)name Termamyl , Fungamyl  or Duramyl ; With the Purastar STL or the Purastar OXAM that sell by Genencor; And analogue.Preferred commercially available amylase comprises the stability-enhanced variant amylase of being sold by Novo with trade(brand)name Duramyl .Also can use diastatic mixture.
The amylase that is suitable for the present composition comprises: in WO95/26397, the PCT/DK96/00056 of Novo and the α-Dian Fenmei described in the GB1296839; With at J.Biol.Chem., 260 (11): 6518-6521 (1985); Among the WO9510603A of Novo, WO9509909A and the WO9402957; In the reference described in the WO9402597; With at the stability-enhanced amylase described in the WO9418314 of Genencor International.The employed variant α-Dian Fenmei of the present composition can at least 80% homology, preferably has at least 80% the sequence identity and the aminoacid sequence of the proteolytic enzyme in these reference.
With some amylase for example Termamyl  compare, the suitable amylase that can be used for the present composition has the stability of raising.The stability that improves is meant respectively when for example Termamyl  compares with suitable control starch enzyme, remarkable or measurable improvement of one or more following aspects: oxidative stability, for example under pH9-10 in buffered soln to the oxidative stability of hydrogen peroxide/tetra-acetylated ethylene diamine; Thermostability is for example in the common wash temperature thermostability under 60 ℃ according to appointment; And/or alkaline stability, for example alkaline stability under pH about 8 to about 11.Can be by well known to a person skilled in the art the method measurement stability.In 25 ℃-55 ℃ temperature range and in about 8 to about 10 pH scope, the suitable stability-enhanced amylase that can be used for the present composition has the specific activity than the specific activity high at least 25% of Termamyl .Can be by analytical procedure well known by persons skilled in the art and/or commercially available, for example Phadebas  I-amylase analytical procedure is measured amylase activity to be used for this comparison.
In one embodiment, the amount ranges that is present in the commercial amylases act in the present composition be about 0.1wt% of decontaminating solution to about 3wt%, preferably about 1% to about 3wt%, preferably the commercial enzyme product solution of about 2wt%.Typical commercially available detergency enzymes comprises the active amylase of about 0.25-5%.
Although it is easily in practice that definite desired diastatic weight percentage is used for the preparation embodiment of the present invention's instruction, but the variation of commercial amylases act enriched material and environment additive on the spot and may require to be used for the more accurate analytical technology that amylase is analyzed to the negative impact of amylase activity, so as in this embodiment quantification enzyme active and set up and pollute residue and remove the dependency of the stability of performance and enzyme; If with enriched material, then use diluting soln.Available known unit or by known amylase analytical procedure and/or commercially available analytical procedure, for example Phadebas  α-Dian Fenmei analytical procedure is expressed the diastatic activity of using among the present invention.
Naturally, can in the present invention, comprise different diastatic mixtures.Although more than described various concrete enzymes, be appreciated that and use any amylase that to give the required amylase activity of composition, and in no case the amylase by concrete selection limits this embodiment of the present invention.
Cellulase
The cellulase that is suitable for the present composition can be derived from plant, animal or microorganism.Preferably, cellulase is derived from microorganism, for example fungi or bacterium.Suitable cellulase comprises and is derived from fungi, and those of Humicola insolens, Humicola strain DSM 1800 for example perhaps produce the fungi (it belongs to zygosaccharomyces) of cellulase 212; With extract the hepatopancreas of the auricle spire (Dolabella Auricula Solander) that belongs to from sea mollusk truncation sea hare those.Cellulase can be purified or can be component and or the agriotype or the variant (variant of chemistry or reorganization) of extract.
The example of the cellulase that can use in the present composition comprises those that sold by Novo with trade(brand)name Carezyme  or Celluzyme , the perhaps Cellulase that is sold by Genencor; And analogue.Also can use the mixture of cellulase.U.S. Patent No. 4435307, GB-A-2075028, GB-A-2095275, DE-OS-2247832, WO9117243 and the WO9414951A (stable cellulase) of suitable cellulase: Novo are disclosed in following patent documentation.
In one embodiment, the amount ranges that is present in the plain enzyme of commercial fibres in the present composition be about 0.1wt% of decontaminating solution to about 3wt%, preferred about 1% to about 3wt% commercial enzyme product solution.Typical commercially available detergency enzymes comprises the organized enzyme of about 5-10%.
Although it is easily in practice that the weight percentage of definite desired cellulase is used for the preparation embodiment of the present invention's instruction, but the variation of plain enzyme enriched material of commercial fibres and environment additive on the spot and may require to be used for the more accurate analytical technology that cellulase is analyzed to the negative impact of cellulase activity, so as in this embodiment quantification enzyme active and set up the dependency of removing the stability of performance and enzyme with the pollution residue; If with enriched material, then use diluting soln.The activity of the cellulase that uses among the present invention is expressed by available known unit or by known or commercially available cellulase analytical procedure.
The mixture that naturally, can in the present invention, comprise different cellulases.Although more than described various concrete enzymes, be appreciated that and use any cellulase that to give the required cellulase activity of composition, and in no case the cellulase by concrete selection limits this embodiment of the present invention.
Lipase
The lipase that is suitable for the present composition can be derived from plant, animal or microorganism.In one embodiment, lipase is derived from microorganism, for example fungi or bacterium.Suitable lipase comprises and is derived from pseudomonas, Amur pseudomonas (Pseudomonasstutzeri) ATCC19.154 for example, perhaps Humicola, for example those of Humicola lanuginosa (it typically passes through recombinant production in aspergillus oryzae (Aspergillus oryzae)).Lipase can be purified or can be component and or the agriotype or the variant (variant of chemistry or reorganization) of extract.
The example of the lipase that can use in the present composition comprises with trade(brand)name lipase P " Amano " or " Amano-P " by Amano Pharmaceutical Co., Ltd., those that Nagoya Japan sells, perhaps those that sell by Novo with trade(brand)name Lipolase , and analogue.The commercially available lipase of other that can use in the present composition comprises Amano-CES, is derived from thickness look bacillus (Chromobacter viscosum), for example (it is available from Toyo Jozo Co. for the lipase of thickness look bacillus variant lipolyticum NRRLB3673, Tagata, Japan); Available from U.S.Biochemical Corp., the thickness look bacillus lipase of U.S.A. and Disoynth Co. and be derived from gladiolus pseudomonas (Pseudomonas gladioli) or the lipase of Humicola fine hair bacterium (Humicola lanuginosa).
Suitable lipase is sold by Novo with trade(brand)name Lipolase .The WO9414951A (stable lipase) of suitable lipase: Novo is disclosed in following patent documentation, WO9205249, RD94359044, GB1372034, on February 24th, 1978 are authorized Amano PharmaceuticalCo., Ltd. Japanese Patent Application Laid-Open 5320487, and EP341947.
In one embodiment, the amount ranges that is present in the commercial lipase in the present composition be about 0.1wt% of decontaminating solution to about 3wt%, preferred about 1% to about 3wt% commercial enzyme product solution.Typical commercially available detergency enzymes comprises the organized enzyme of about 5-10%.
Although it is easily in practice that the weight percentage of definite desired lipase is used for the preparation embodiment of the present invention's instruction, but the variation of commercial lipase enriched material and environment additive on the spot and may require to be used for the more accurate analytical technology that lipase is analyzed to the negative impact of lipase activity, so as in this embodiment quantification enzyme active and set up and pollute residue and remove the dependency of the stability of performance and enzyme; If with enriched material, then use diluting soln.The activity of the lipase that uses among the present invention is expressed by available known unit or by known or commercially available lipase analytical procedure.
The mixture that naturally, can in the present invention, comprise different lipase.Although more than described various concrete enzymes, be appreciated that and use any lipase that to give the required lipase activity of composition, and in no case the lipase by concrete selection limits this embodiment of the present invention.
Extra enzyme
The extra enzyme that is suitable for using in composition of the present invention comprises at, peroxidase, glucose enzyme and analogue.Suitable at is disclosed in the WO8809367A of Genencor.Known peroxidase comprises horseradish peroxidase, lignoenzyme and halo peroxidase, for example chloro or bromoperoxidase.The peroxidase that is suitable for composition is disclosed in the WO89099813A of Novo and WO8909813A.Peroxidase can be in conjunction with oxygen source, and for example percarbonate, perborate, hydrogen peroxide and analogue use.WO9307263A and WO9307260A at GenencorInternational, the WO8908694A of Novo, U.S. Patent No. 3553139 with people such as McCarty, people's such as Place U.S. Patent No. 4101457 discloses the extra enzyme that is suitable for being included in the present composition in people's such as the U.S. Patent No. 4507219 of Hughes and Hora the U.S. Patent No. 4261868.
Be suitable for the extra enzyme of the present composition, for example at or peroxidase can be derived from plant, animal or microorganism.Preferably, this enzyme is derived from microorganism.Enzyme can be purified or can be component and or the agriotype or the variant (variant of chemistry or reorganization) of extract.In a preferred embodiment of the invention, the amount ranges that is present in the commercial extra enzyme (for example at or peroxidase) in the present composition is about 0.1wt% extremely about 3wt%, preferably about 1% to about 3wt% the commercial enzyme product solution of decontaminating solution.Typical commercially available detergency enzymes comprises the organized enzyme of about 5-10%.
Although determine that the preparation embodiment that the weight percentage of desired extra enzyme (for example at or peroxidase) is used for the present invention's instruction is easily in practice, but the variation of commercial extra enzyme enriched material and environment additive on the spot and may require to be used for the more accurate analytical technology that lipase is analyzed to its active negative impact, so as in this embodiment quantification enzyme active and set up the dependency of removing the stability of performance and enzyme with the pollution residue; If with enriched material, then use diluting soln.The extra enzyme that uses among the present invention is expressed, for example at or Peroxidase activity by available known unit or by known or commercially available analytical procedure.
The mixture that naturally, can in the present invention, comprise different extra enzymes.Although more than described various concrete enzymes, be appreciated that and use any extra enzyme that to give the required enzymic activity of composition, and in no case the enzyme by concrete selection limits this embodiment of the present invention.
The stabilising system of enzyme
Composition of the present invention also can comprise the composition of stablizing one or more enzymes.For example, cleaning compositions of the present invention can comprise the water-soluble source of calcium and/or magnesium ion.Calcium ion is more effective than magnesium ion usually, and if use an only cationoid, then it is preferred herein.Composition, particularly liquid can comprise about 1 to about 30, preferred about 2 to about 20, more preferably from about 8 to about 12mmol calcium ion/liter final composition, but various variations are possible, and this depends on multiple factor, comprising multiplicity, type and the content of the enzyme that is added.Preferred water-soluble calcium or the magnesium salts of using is comprising for example calcium chloride, calcium hydroxide, calcium formiate, calcium malate, calcium maleate, calcium hydroxide and lime acetate; More generally, can use calcium sulfate or with the corresponding magnesium salts of the above calcium salt of enumerating.Further increase the content of calcium and/or magnesium yes useful, for example be used to promote the lubricating grease excision effect of the tensio-active agent of some types.
Some cleaning compositions, for example the stabilising system in the utensil washing composition can further comprise 0 to about 10%, preferred about 0.01% to about 6wt% chlorine bleaching scavenging agent, wherein add described chlorine bleaching scavenging agent with chlorine albic material attack enzyme in the water that prevents to be present in many supplies and make it inactivation, particularly under alkaline condition.Although the chlorine content in water may be less, typically scope is that about 0.5ppm is to about 1.75ppm, but for example in the dish washing process, obtainable chlorine may be relatively large in the water of the whole volumes that contact with enzyme, so enzyme may become problem to the stability of the chlorine in using.
Suitable chlorine cleaning agent negatively charged ion be well-known and obtain easily and if use, they can be the salt that contains ammonium cation and inferior sulfate radical, bisulfite, hyposulfurous acid root, thiosulfate anion, iodide etc.Can use oxidation inhibitor such as carbaminate, ascorbate salt etc. equally, organic amine such as ethylenediamine tetraacetic acid (EDTA) (EDTA) or its an alkali metal salt, monoethanolamine (MEA) and composition thereof.Equally, can comprise specific enzyme inhibition system, so that different enzymes has maximum consistency.Can optionally use other conventional scavenging agent such as hydrosulfate, nitrate, muriate, hydrogen peroxide cource as four hydrated sodium perborates, sodium perborate monohydrate and SPC-D and phosphoric acid salt, condensed phosphate, acetate, benzoate, Citrate trianion, formate, lactic acid salt, malate, tartrate, salicylate etc. and composition thereof.
In general, owing to can exercise the function of chlorine cleaning agent by the composition of listing independently with known function, therefore do not require and add independently chlorine cleaning agent, be not present in the embodiment that contains enzyme of the present invention unless on required degree, exercise the compound of this function; Even like that, adding scavenging agent only is for optimal results.In addition, the makers-up will use chemist's conventional skill to avoid using any enzyme scavenging agent or stablizer, and wherein said enzyme scavenging agent or stablizer are unacceptable in the consistency of when preparation and other reactive ingredients.About the use of ammonium salt, this salt can mix with said composition simply, but in storage process, it is easy to absorb water and/or discharges ammonia.Therefore, if exist, this material is protected with particle form requiredly, as described in people's such as Baginski the U.S. Patent No. 4652392.
Divalent ion
Cleaning compositions of the present invention can contain divalent ion, for example calcium and magnesium ion, and its content is the 0.05%-5wt% of composition weight, 0.1%-1wt%, perhaps about 0.25wt%.In one embodiment, calcium ion can be included in the composition of the present invention.Calcium ion can be for example with muriate, oxyhydroxide, oxide compound, formate or acetate, or the nitrate form adds, and preferably adds with the form of muriate, salt.
Polyvalent alcohol
Stable microbial preparation of the present invention or cleaning compositions also can comprise polyvalent alcohol.Polyvalent alcohol can for example provide extra stability of composition and hydrotropy energy.Suitable polyvalent alcohol comprises glycerine; Dibasic alcohol, for example ethylene glycol, propylene glycol or hexylene glycol; Sorbyl alcohol; Alkyl poly glucoside; And composition thereof.In one embodiment, polyvalent alcohol comprises propylene glycol.
Suitable alkyl poly glucoside according to the present invention as polyvalent alcohol comprises those with following formula:
(G) x-O-R
Wherein G is derived from the reducing sugar part of pentose or hexose for example that contains 5 or 6 carbon atoms, and R contains the fatty aliphatic group of 6-20 carbon atom and the polymerization degree (DP) that x is the glycan glycosides, the quantity of its representative monose repeating unit in the glycan glycosides.Preferably, x is about 0.5 to about 10.In one embodiment, R contains 10-16 carbon atom and x is 0.5-3.
In one embodiment, polyvalent alcohol can be the polyethers form.Suitable polyethers comprises polyoxyethylene glycol.Suitable polyethers comprises those that list with solvent or cosolvent form.
In some embodiments, composition of the present invention comprises about polyvalent alcohol of 2 to about 30wt%, about polyvalent alcohol of 2 to about 10wt%, about polyvalent alcohol of 5 to about 20wt%, about polyvalent alcohol of 5 to about 10wt%, or about polyvalent alcohol of 10 to about 20wt%.In some embodiments, stable microbial preparation of the present invention comprises about polyvalent alcohol of 2 to about 40wt%, about polyvalent alcohol of 2 to about 20wt%, about polyvalent alcohol of 2 to about 15wt%, about polyvalent alcohol of 2 to about 10wt%, about polyvalent alcohol of 3 to about 10wt%, about polyvalent alcohol of 4 to about 15wt%, or about polyvalent alcohol of 4 to about 8wt%, the polyvalent alcohol of about 4wt%, the polyvalent alcohol of about 8wt%, or the polyvalent alcohol of about 12wt%.Said composition can comprise these scopes that change approximately of no use or any one in the consumption.
Solvent or cosolvent
Can use solvent or cosolvent to improve the removal performance of certain dirt of the present invention.Preferred cosolvent is pure and mild aklylene glycol, two aklylene glycols, the list of three aklylene glycols and dialkyl ether etc.The alcohol that can be used as cosolvent in the present invention comprises methyl alcohol, ethanol, propyl alcohol and Virahol.Especially can be used for of the present invention is the list and the dialkyl ether of ethylene glycol and glycol ether, and they have obtained the popular name such as poly-glyme, cellosolve and Trivalin SF.The representative example of this group cosolvent comprises methylcyclohexane, diethylene glycol monobutyl ether, dibutyl carbitol, diglyme, triglyme etc.Can use the on-aqueous liquid solvent to change composition of the present invention.These comprise senior dibasic alcohol, poly-dihydric alcohol, poly oxide and glycol ether.Suitable material is propylene glycol, polyoxyethylene glycol, polypropylene glycol, diethylene glycol monoethyl ether, diglycol monotertiary propyl ether, diethylene glycol monobutyl ether, tripropylene glycol methyl ether, propylene glycol monomethyl ether (PM), dipropylene glycol methyl ether (DPM), propylene glycol methyl ether acetate (PMA), dipropylene glycol methyl ether acetic ester (CPMA), ethylene glycol n-butyl ether and ethylene glycol n-propyl ether.Other useful solvent is an ethylene oxide/propylene oxide, and liquid randam copolymer is as the Synalox  solvent series (for example, Synalox  50-50B) available from Dow Chemical.Other suitable solvent is a propylene glycol, for example PnB, DPnB and TPnB (by propylene glycol monobutyl ether, dipropylene glycol monobutyl ether and the tripropylene glycol monobutyl ether of Dow Chemical with trade(brand)name Dowanol  sale).Tripropylene glycol monomethyl ether " Dowanol TPM  " available from Dow Chemical also is suitable.
Treat to comprise non-VOCs or low VOCs, comprising DPnB, PnB, D-limonene, N-Methyl pyrrolidone, propylene glycol phenyl ether, ethylene glycol phenyl ether, tripropylene glycol methyl ether etc. with the suitable solvent that the present invention uses.
Souring agent
Use souring agent or alkali reagent to keep the suitable pH of sanitising agent of the present invention.Careful control pH can improve spatter property.Prepare employed acidic components of sanitising agent of the present invention or souring agent and comprise the acid that may be dissolved in the Aquo System of the present invention, so that regulate pH downwards.Preferably, can use common commercially available weak inorganic acid and organic acid in the present invention.Useful weak inorganic acid comprises phosphoric acid and thionamic acid.Useful weak organic acid comprises acetate, oxyacetic acid, citric acid, tartrate and analogue.Find that useful souring agent comprises organic and mineral acid, for example citric acid, lactic acid, acetate, oxyacetic acid, hexanodioic acid, tartrate, succsinic acid, propionic acid, toxilic acid, alkansulfonic acid, cycloalkanes sulfonic acid, and phosphoric acid and analogue or its mixture.
Extra alkali source
The basic material that can be used for regulating pH comprise weak and strong basic material these two.This material generally comprises highly basic such as sodium hydroxide, potassium hydroxide, an alkali metal salt such as yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus, concentrated crystal soda, Sodium Tetraborate, potassium borate, sodium phosphate and potassiumphosphate, organic bases is trolamine, tripropanol amine etc. for example, alkalimetal silicate, an alkali metal salt.
Extra alkali source can comprise potassium hydroxide or alkaline potassium salt such as salt of wormwood, saleratus, potassiumphosphate etc.
Thickening material or jelling agent
Suitable thickening can comprise do not contain with contact area in food or those of the inconsistent component of other sensitive product.In addition, thickening material should not suppress the growth of spore of the present invention.In general, the thickening material that can use in the present invention comprises natural gum for example xanthan gum, guar gum, modification guar gum or from other glue of plant mucilage; Modified adhesive; Polysaccharide base thickening material, for example alginate, starch and cellulose polymer compound (for example, carboxymethyl cellulose, Natvosol and analogue); Polyacrylate thickeners; Associative thickener; With hydrocolloid thickening material, for example pectin.In general, the concentration of employed thickening material is determined by viscosity required in the final composition in the present composition or the method.Yet, instructing as generality, the concentration range of the thickening material in the present composition is extremely about 3wt% of about 0.05wt%, about 0.1wt% is to about 2wt%, or about 0.1wt% is to about 0.5wt%.
Dyestuff
Composition of the present invention also can comprise dyestuff.Dyestuff advantageously is provided at the visibility of the product in packing, divider and/or the circuit to composition.Various dyestuffs are suitable, comprising ACID GREEN 25 and sun blue 86.
Use composition
The compositions and methods of the invention are suitable for removing complicated organic or lubricated smectic dirt and mineral contaminants from various substrates.Can not use composition of the present invention (promptly not having thinner, for example aqueous diluent), perhaps used water or other liquid medium dilute composition of the present invention with mixing, form the degreasing aqueous solution.In addition, can use grease removing composition of the present invention with the cleaning compositions of other preparation that is used for clean substrate as additive.
The organic of lubricating grease and the mineral contaminants cleaning compositions removed of the present invention can be used as the cleaning material that the additive of removing lubricating grease is used for preparing.This cleaning material is industrial common and comprise hard surface cleaners, and cloth-washing detergent is used for using all purpose cleaner that uses, ground cleaner, glass cleaner etc. in family and mechanism.By adding about 0.1 to about 20wt% composition of the present invention in the sanitising agent prescription of routine, composition of the present invention is used as additive.Material of the present invention, even when in the aqueous solution or in the prescription such as glass cleaner, hard surface cleaners, all purpose cleaner or cloth-washing detergent, diluting consumingly separately, can provide good especially lubricating grease to remove performance, it is almost the same with the enriched material material effective.
But full strength (pure, as promptly not exist under the situation of aqueous diluent) uses composition of the present invention.Composition of the present invention can be applied directly to typically at hard surface, for example on the lip-deep organic or lubricating grease dirt such as glass, metal, matrix material, timber.Tend to reduce the interface bonding of any dirt/hard surface and reduce the cohesion of complicated dirt and the viscosity that reduces the dirt material with organic or the lubricating grease dirt bonded present composition, thereby cause relatively easy physics to be removed.
Use any wt% content that composition can comprise composition listed above divided by amount of dilution, and can express with wt% or ppm.Especially, for borate and microorganism component or spore, content listed above is the content of concentrate composition.For example, use composition can comprise that any wt% content listed above is independently divided by 10,20,30,40,50,60,70,80,90,100,200,300,400,500,600,700,800,900,1000,2000,3000,4000,5000,6000,7000,8000,9000 or 10000.In one embodiment, dilution method is that the enriched material of 2oz is increased to 1 gallon and uses composition.
Foam
In one embodiment, composition of the present invention can with mixing diluents, be formed on the use composition that uses in the foam maker.Can for example use foam applying device, for example the foam maker of pot type foam maker or air-breathing wall installation for example uses the foam maker nozzle that triggers atomizer, realizes that foamy applies.Can be by in 15 gallons foam to be exerted pressure container, the interior placement of stainless steel pressure container that for example has 15 Gallon Capacities of mixing auger oar used composition, thereby realizes that foamy applies.Can trigger atomizer by foam then and distribute this foam composition.The foam maker that wall is installed can use air to discharge foam from jar or pipeline.In one embodiment, the air of compression can be expelled in the mixture, then by foam applying device, for example the foam maker of pot type foam maker or air-breathing wall installation is applied on the object.
Can used according to the inventionly comprise and cause that air and foam composition mix and produce those heads of foamy composition with the mechanical foaming head that provides foam to generate.That is to say that the mechanical foaming head causes that air and foam composition mix in mixing chamber, pass opening then to generate foams.
Suitable mechanical frothing head that can be used according to the invention comprises available from PompanoBeach, the Airspray International of Florida, Inc and available from those of ZellerPlastik (branch office of Crown Cork and Seal Co.).In U.S. Patent No. D-452822, U.S. Patent No. D-452653, U.S. Patent No. D-456260 and the U.S. Patent No. 6053364 suitable mechanical foaming head that can be used according to the invention is being disclosed for example.Mechanical foaming head that can be used according to the invention comprises by applying those heads that finger pressure drives to the triggering device or desire drives, to cause foam composition and air mixed and to produce foams.That is to say, but people's finger pressure depression of trigger, thereby in traction foam composition and the air admission head and cause foam composition and air mixed and produce foams.
Use the method for the present composition
In one embodiment, cleaning compositions is applied directly on the serious dirt settling, makes and soften dirt and promote dirt to remove.In case make composition improve the removeability of dirt, then sanitising agent can easily adopt rinse step to remove with the dirt of being removed.In one embodiment, this method comprises and saves rinsing.That is to say, can apply composition of the present invention and not have the rinsing surface.Contain nonionogenic tenside, nonionic siloxane tensio-active agent, anion surfactant and the hydrotropic present composition and can directly contact, oily organic or lubricating grease dirt for removing with hard surface.Depend on substrate, this composition can comprise sequestrant in addition, so that end formulation comprises nonionogenic tenside and nonionic siloxane tensio-active agent, anion surfactant, hydrotropic agent solubilizing agent and sequestrant.Can be on non-corrosive basically surface, for example use these compositions on the timber of plastics, timber, coating, stainless steel, matrix material, fabric, cement and other.
In one embodiment, method of the present invention comprises the method for cleaning hard surfaces.This method can comprise apply contain spore or bacterium, borate, about nonionogenic tenside of 0.5 to about 35wt% and about silicone surfactant of 0.1 to about 35wt% cleaning compositions to the surface.This method can comprise apply said composition to ground, water shoot or it is in conjunction with last.
In one embodiment, method of the present invention comprises the method for cleaning floor.This method can comprise the frictional coefficient that increases ground.This method can comprise the mortar that cleans the tile floor.The cleaning mortar can comprise makes it show the nature color.This method comprises and applies stable spore composition of the present invention to ground.In one embodiment, this method does not comprise (for example saving) rinsing.In one embodiment, method of the present invention can comprise remove the film that slides from the earth material (for example ceramic tile) effectively when moistening.This method can comprise the cleaning floor material and increase its frictional coefficient.
In one embodiment, the method for cleaning hard surfaces of the present invention can comprise and applies composition of the present invention to bathroom surfaces, for example on wall, ground or the furniture.Bathroom surfaces can be shower wall or surface.Bathroom surfaces can be the wall of tiling.The composition that uses on vertical surface can comprise the tensio-active agent of thickening material, wetting agent or foaming.Applying composition can comprise on the vertical surface and make the composition foaming.In one embodiment, composition of the present invention comprises thickening material or wetting agent, but their auxiliary compositions are retained on level or the vertical surface.
In one embodiment, method of the present invention can comprise apply composition of the present invention have to thereon lubricating grease or oil the surface on.This surface comprises ground, parking lot, the pad that is open to traffic, garage floor, ground, parking slope and analogue.
In one embodiment, method of the present invention comprises with composition sprayed of the present invention or this surface of spraying.
In one embodiment, method of the present invention comprises and applies stable microbial composite to the surface and keep the long time period of this surface moisture, and for example 1 or 2 hour until about 8-16 hour.Can for example by spraying, realize keeping surface moisture by applying composition repeatedly.Can realize keeping surface moisture by making this surface and contacting the long time period with the wetting sponge of said composition, rag or mop.Can realize keeping surface moisture by applying the microbial composite of lasting stability.The microbial composite of lasting stability can remain on this surface and make this surface keep moist.For example, the composition of the composition of thickening and some foaming can remain on this surface and make this surface keep moist.Compare with composition dry or evaporation, long-term existence composition of the present invention can provide cleaning faster.
With reference to following embodiment, will understand the present invention better.These embodiment work done in the manner of a certain author are the representational specific embodiments of the present invention, and are not intended to be limiting scope of the present invention.
Embodiment
Embodiment 1-borate stabilised microorganism composition
Prove composition stable microbial preparation of the present invention, specifically digest the spore composition of lubricating grease.
Materials and methods
This experimental evaluation is under the situation of ageing and not ageing composition, by the aerobic plate count of the various cleaning compositions productions that contain microbial spores.Those compositions that contain spore alive produce the bacterial colony with lipolytic activity, and described bacterial colony causes the dark areas in dull and stereotyped growth medium.Dark areas comes from the generation of free fatty acids.Contrast comprises spore or the bacterium in the bacterium cleaning compositions that is suspended in water and routine.
This test method is according to " Lipolytic Microorganisms ", Compendium Of Methods for the Microbiological Examination of Foods, the 3rd edition, 1992, the 183 pages standard scheme.In brief, preparation steatolysis agar plate.Inoculate this flat board and make it dry with the test bacterial suspension.Nutrient agar medium is poured on the surface of inoculating.At room temperature cultivate this flat board, make bacterial growth, and detect the outward appearance of steatolysis bacterium colony.By identifying the steatolysis bacterium colony around the faint blue zone.
In this embodiment, prepare and test following composition:
1 2 3 4 5 6 7
Water 26 28 28 30 54 56 56
Boric acid 10 10 10 10
Alkanolamine 19 19 19 19 2 2 2
Polyvalent alcohol 8 8 8 8 8 8 8
Nonionogenic tenside 8 8 8 8 8 8 8
Silicone surfactant 3 3 3 3 3 3 3
Amphoterics 5 5 5 5 5 5 5
Anion surfactant 8 8 8 8 8 8 8
Hydrotropic agent 11 11 11 11 11 11 11
The spore blend 2 2 2 2
Proteolytic enzyme 2 2 2 2
All consumptions are in wt%
Reference composition 8 is included in the 2wt% spore blend in the water.Reference composition 9 is included in the 2wt% proteolytic enzyme in the water.Reference composition 10 is included in 2wt% spore blend in the water and the proteolytic enzyme of 2wt%.
Dilute each composition to the growth of 2wt% in order to bacteria tested.
The result
Table 1-3 has reported in above-described composition, in control formula and in commercially available prescription, the test result of spore blend viablity.
Table 1
(formula number) explanation Aerobic steatolysis plate count (CFU/mL)
Water+2% spore blend 5.1×10 4
Water+2% proteolytic enzyme <1
Water+2% spore blend+2% proteolytic enzyme 9.8×10 3
(1) amine borate+2% spore blend+2% proteolytic enzyme 4.7×10 4
(2) amine borate+2% spore blend 7.6×10 4
(3) amine borate+2% proteolytic enzyme 1.7×10 2*
(4) amine borate <1
(5) there is not borate+2% spore blend+2% proteolytic enzyme 2.3×10 4
(6) there is not borate+2% proteolytic enzyme 1.3×10 2*
(6) there is not borate+2% spore blend 2.5×10 4
*=sample between crossed contamination
Table 2
(formula number) explanation Aerobic plate count result (CFU/mL)
(1) freshly prepd amine borate+2% spore blend+2% proteolytic enzyme 1.7×10 4
(1) 6 days amine borate of ageing+2% spore blend+2% proteolytic enzyme 2.1×10 4
(5) freshly prepd do not have borate+2% spore blend+2% proteolytic enzyme 2.5×10 4
(5) ageing 6 days does not have borate+2% spore blend+2% proteolytic enzyme 2.0×10 3
Do not know the 2% commercial spore blend that contains sanitising agent of time 5.0×10 2
The 2% commercial spore blend that contains sanitising agent at 4 monthly ages 3.6×10 3
Water+2% spore blend 3.0×10 4
Table 3
(formula number) explanation Aerobic plate count result (CFU/mL)
(1) the amine borate in 10 weeks of ageing+2% spore blend+2% proteolytic enzyme 2.1×10 4
(1) the amine borate in 5 weeks of ageing+2% spore blend+2% proteolytic enzyme 1.4×10 4
(1) the amine borate in 4 weeks of ageing+2% spore blend+2% proteolytic enzyme 2.0×10 4
(5) 4 weeks of ageing does not have borate+2% spore blend+2% proteolytic enzyme 1.3×10 4
(5) 5 weeks of ageing does not have amine borate+2% spore blend+2% proteolytic enzyme 2.4×10 3
The commercial ground cleaner that contains 2 parts of spores, freshly prepd enriched material 3.8×10 5
Conclusion
Spore and the bacterium itself of the bacterium of the stable digestion of amine borate lubricating grease.For the concentrate composition that contains amine borate and spore blend, observe the stability of increase.For example, about 1 the logarithmic bacterial activity of sample loss in 6 day age of prescription 5 (not boracic hydrochlorates).Unforeseeable is that the sample in 6 day age of prescription 1 (it comprises amine borate) keeps bacterial activity completely.That is to say that it keeps the activity as freshly prepd sample.
The deterioration of bacterial activity is significant in the sanitising agent that contains commercial spore blend (it is the boracic hydrochlorate not).About 1 the logarithmic bacterial activity of the sample loss at 4 monthly ages.Do not know about 2 the logarithmic bacterial activities of sample loss of time.
Unforeseeable is that amine borate (it may have limited solubleness) is soluble in having the composition of silicone surfactant.
Embodiment 2-contains the borate compositions stabilised microorganism preparation of polyvalent alcohol
Identity basis the present invention and comprise borate and the two composition stable microbial preparation of polyvalent alcohol specifically digests the spore composition of lubricating grease.
Materials and methods
Adopt the borate counter ion (for example alkanolamine) and the polyvalent alcohol (for example propylene glycol) of various concentration, prepare composition according to the general formulation of listing among the embodiment 1.By after the preparation composition, measuring lipolytic activity, measure the stability of composition at different time.Said composition contains the spore blend of 2wt% usually.Dilute each composition to the growth of 2wt%, this as described in example 1 above the same in order to bacteria tested.
In this embodiment, prepare and test following composition:
11 12 13 14 15 16 17 18 19 20
Water 50 44 38 31 48 36 58 55 49 43
Boric acid 2 4 6 8 4 8 2 4 6 8
Alkanolamine 5 9 14 18 9 18 5 9 14 18
Polyvalent alcohol 8 8 8 8 4 4
Nonionogenic tenside 8 8 8 8 8 8 8 8 8 8
Silicone surfactant 3 3 3 3 3 3 3 3 3 3
Amphiphilic surfactant 5 5 5 5 5 5 5 5 5 5
Anion surfactant 8 8 8 8 8 8 8 8 8 8
Hydrotropic agent 11 11 11 11 11 11 11 8 8 8
The spore blend 2 2 2 2 2 2 2 2 2 2
Proteolytic enzyme 1
pH100% 9.7 10 10.3 10.1 10.1 10.5 10.1 10 10.4 10.5
pH1% 9.2 9.3 9.5 9.3 9.3 9.5 9.5 9.4 9.4 9.5
All consumptions are in wt%
The result
Table 4-8 has reported the test result in composition 11-20 miospore blend viablity.
The not aged composition of table 4-
(formula number) explanation Aerobic plate count result (CFU/mL) Growth decline (logarithm)
(11) 2% boric acid+5%MEA+8% propylene glycol 4.5×10 4 NA
(12) 4% boric acid+9%MEA+8% propylene glycol 3.0×10 3 NA
(13) 6% boric acid+14%MEA+8% propylene glycol 2.2×10 4 NA
(14) 8% boric acid+18%MEA+8% propylene glycol 2.0×10 4 NA
(15) 4% boric acid+9%MEA+4% propylene glycol 2.4×10 4 NA
(16) 8% boric acid+18%MEA+4% propylene glycol 2.8×10 4 NA
(17) 2% boric acid+5%MEA 5.4×10 4 NA
(18) 4% boric acid+9%MEA 5.0×10 4 NA
(19) 6% boric acid+14%MEA 2.7×10 4 NA
(20) 8% boric acid+18%MEA 3.4×10 4 NA
The composition in table 5-4 weeks of ageing
(formula number) explanation Aerobic plate count result (CFU/mL) Growth decline (logarithm)
(11) 2% boric acid+5%MEA+8% propylene glycol 2.2×10 5 -
(12) 4% boric acid+9%MEA+8% propylene glycol 9.4×10 4 -
(13) 6% boric acid+14%MEA+8% propylene glycol 1.2×10 5 -
(14) 8% boric acid+18%MEA+8% propylene glycol 1.2×10 5 -
(15) 4% boric acid+9%MEA+4% propylene glycol 3.2×10 5 -
(16) 8% boric acid+18%MEA+4% propylene glycol 1.0×10 5 -
(17) 2% boric acid+5%MEA 1.9×10 5 -
(18) 4% boric acid+9%MEA 2.5×10 4 0.3
(19) 6% boric acid+14%MEA 4.8×10 4 -
(20) 8% boric acid+18%MEA 1.0×10 5 -
The composition in table 6-8 weeks of ageing
(formula number) explanation Aerobic plate count result (CFU/mL) Growth decline (logarithm)
(11) 2% boric acid+5%MEA+8% propylene glycol 2.1×10 4 0.33
(12) 4% boric acid+9%MEA+8% propylene glycol 3.0×10 4 -
(13) 6% boric acid+14%MEA+8% propylene glycol 2.2×10 3 1.0
(14) 8% boric acid+18%MEA+8% propylene glycol 3.4×10 4 -
(15) 4% boric acid+9%MEA+4% propylene glycol 3.3×10 4 -
(16) 8% boric acid+18%MEA+4% propylene glycol 1.3×10 4 0.33
(17) 2% boric acid+5%MEA 1.8×10 4 0.48
(18) 4% boric acid+9%MEA 2.7×10 4 0.27
(19) 6% boric acid+14%MEA 5.0×10 3 0.72
(20) 8% boric acid+18%MEA 6.0×10 3 0.75
The composition in table 7-12 weeks of ageing
(formula number) explanation Aerobic plate count result (CFU/mL) Growth decline (logarithm)
(11) 2% boric acid+5%MEA+8% propylene glycol 1.1×10 4 0.61
(12) 4% boric acid+9%MEA+8% propylene glycol 5.2×10 3 -
(13) 6% boric acid+14%MEA+8% propylene glycol 5.4×10 2 1.61
(14) 8% boric acid+18%MEA+8% propylene glycol 1.4×10 2 2.15
(15) 4% boric acid+9%MEA+4% propylene glycol 6.8×10 3 0.55
(16) 8% boric acid+18%MEA+4% propylene glycol 1.5×10 1 3.27
(17) 2% boric acid+5%MEA 2.4×10 3 1.35
(18) 4% boric acid+9%MEA 3.2×10 3 1.19
(19) 6% boric acid+14%MEA 5.1×10 2 1.72
(20) 8% boric acid+18%MEA <1×10 1 3.53
The composition in table 8-16 weeks of ageing
(formula number) explanation Aerobic plate count result (CFU/mL) Growth decline (logarithm)
(11) 2% boric acid+5%MEA+8% propylene glycol 6.2×10 3 0.86
(12) 4% boric acid+9%MEA+8% propylene glycol 2.0×10 3 0.18
(15) 4% boric acid+9%MEA+4% propylene glycol 5.8×10 2 1.62
Conclusion:
After the ageing composition reached for 8 weeks, only slightly descending of bacterial growth taken place.After 12 weeks of ageing, observe descending more significantly of bacterial growth.For example, for composition no 13,14,16,17,18,19 and 20, the decline of bacterial growth is more than or equal to 1 logarithm.This means that composition no 11,12 and 15 demonstrates maximum stability after 12 weeks of ageing.These results prove borate (for example, alkanolamine borate) resistant spore blend.
Interesting is that each composition exhibiting that does not contain polyvalent alcohol goes out greater than 1 logarithmic decline.This shows that polyvalent alcohol helps the resistant spore blend.
Interesting is, composition of the present invention in addition at pH greater than 9.5, for example under the pH10 and even under pH10.5 the resistant spore blend.For example, composition 12 resistant spore blend under about pH10 reached for 16 weeks.
Embodiment 3-is borate compositions stabilised microorganism preparation under alkaline pH
Identity basis the present invention and comprise borate and the two composition stabilised microorganism preparation under the alkaline pH of wide region of polyvalent alcohol specifically digests the spore composition of lubricating grease.
Materials and methods
Adopt the pH that changes, prepare composition according to the general formulation of listing among the embodiment 1.By after the preparation composition, measuring lipolytic activity, measure the stability of composition at different time.Said composition contains the spore blend of 2wt% usually.Dilute each composition to the growth of 2wt%, this as described in example 1 above the same in order to bacteria tested.
In this embodiment, prepare and test following composition:
21(pH7) 22(pH7.5) 23(pH8) 24(pH8.5) 25(pH9)
Water 55 55 54 53 53
Boric acid 4 4 4 4 4
Alkanolamine 2 2.5 3 4 4.5
Polyvalent alcohol 4 4 4 4 4
Nonionogenic tenside 8 8 8 8 8
Silicone surfactant 3 3 3 3 3
Amphoterics 5 5 5 5 5
Anion surfactant 8 8 8 8 8
Hydrotropic agent 11 11 11 11 11
The spore blend 2 2 2 2 2
All consumptions are in wt%
The result
Table 9 and 10 has been reported the test result in composition 21-25 miospore blend viablity.
Show the average of 9-steatolysis microorganism count (CFU/mL)-copy board
Composition Not ageing 4 weeks of ageing 8 weeks of ageing 14 weeks of ageing 14 weeks (24 hours) *
21pH7 1.9×10 3 4.4×10 3 1.4×10 3 1.3×10 3 1.8×10 3
22pH7.5 3.2×10 3 7.8×10 3 5.4×10 2 1.3×10 2 1.2×10 3
23pH8 1.2×10 3 7.4×10 3 2.6×10 3 2.0×10 3 2.1×10 3
24pH8.5 2.0×10 4 7.5×10 3 1.2×10 3 1.4×10 3 9.0×10 2
25pH9 2.1×10 3 1.4×10 4 2.4×10 3 1.7×10 3 2.0×10 3
* 14 weeks of enriched material ageing, the use composition ageing of dilution 24 hours
The growth decline (with logarithm is unit) of table 10-after ageing
Composition Not ageing 4 weeks of ageing 8 weeks of ageing 14 weeks of ageing 14 weeks (24 hours) *
21pH7 NA - 0.13 0.16 0.02
22pH7.5 NA - 0.77 0.39 0.42
23pH8 NA - - - -
24pH8.5 NA 0.43 1.22 1.15 1.35
25pH9 NA - - 0.09 0.02
* 14 weeks of enriched material ageing, the use composition ageing of dilution 24 hours
Conclusion
For the ageing at least about 14 weeks, the present composition of boracic hydrochlorate and polyvalent alcohol provides effective stability under pH7-9 the spore blend.
Embodiment 4-is added with the stable microbial composite of lipase
Preparation is according to the present invention and comprise the composition of borate, polyvalent alcohol and lipase, and shows it is stable and effective cleaning agent (composition 26 and 27).The composition (28-31) that the composition that contains these lipase comprises the composition of following dosage and contains extra lipase can comprise the composition of following dosage:
26 27 28 29 30 31 32 33
Water 27 64 60 56 52 48 64 52
Boric acid 10 5 5 5 5 5 5 5
Alkanolamine 18 9 9 9 9 9 9 8
Polyvalent alcohol 8 4 8 12 16 20 4 12
Nonionogenic tenside 8 4 4 4 4 4 4 4
Silicone surfactant 3 1 1 1 1 1 1.3 1.3
Amphoterics 5 3 3 3 3 3 3 3
Anion surfactant 8 4 4 4 4 4 4 4
Hydrotropic agent 11 3 3 3 3 3 3 3
Sequestering agent 4
The spore blend 2 1 1 1 1 1 1 1
Lipase 2 1 1 1 1 1 1 2
All consumptions are in wt%
The microbial composite that embodiment 5-is stable increases the sliding resistance on ground
The composition that shows according to the present invention and comprise borate, polyvalent alcohol and lipase is effective for the sliding resistance of remarkable increase tile floor.
Materials and methods
Every day is to the tile floor, specifically applies the use diluent that contains composition 33 (2oz/gal or 1.6% enriched material) on the clinker tile ground and do not have rinsing.Sliding resistance when measurement is dry and moistening in the time period in 6 weeks in the kitchen in 5 restaurants.Comprise in this 6 week and measuring in 2 all base measurements and 4 weeks after applying composition 33.Before with composition of the present invention cleaning (for example among the baseline time section and before), every day is with conventional commercially available floor cleaning composition cleaning floor.
According to ASTM F1679-02, use Britain xL variable angle of inclination tribometer, measure sliding resistance with frictional coefficient (COF) form.Scheme is as described below.In the kitchen in each restaurant, select 15 clinker tiles.In the main track route of being concerned about and zone (for example, near frying pan), select every 5 blocks of ceramic tiles.Estimate the COF of the 15 blocks of identical ceramic tiles in each restaurant weekly.The COF of each ceramic tile measures 4 times, measures on one of 90 4 directions spending of being separated by each time.Under dry and moistening situation, measure each ceramic tile.For each restaurant, on average under each condition, measure 60 times and get the result's in 5 restaurants mean value.
The result
Fig. 1 shows weekly in one of 5 restaurants the gained result for the COF (sliding resistance) of 15 blocks of ceramic tiles.By the test duration section in 4 weeks, the COF of dry ceramic tile is improved to 0.81 from average baselining value 0.60.By the test duration section in 4 weeks, the COF of moistening ceramic tile is improved to 0.56 from average baselining value 0.38.These increased values are significant and degree of confidence surpasses 99%.
Conclusion
For the surface of easy cunning, for example the ground in the kitchen, restaurant significantly increases frictional coefficient according to composition of the present invention.
The microbial composite cleaning mortar that embodiment 6-is stable
Demonstration is according to the present invention and comprise that the composition of borate, polyvalent alcohol and lipase is effective for the mortar between the cleaning ceramic tile.
Measure and method
Described the same with embodiment 5, to the tile floor, specifically apply the use diluent that contains composition 33 (2oz/gal or 1.6% enriched material) on the clinker tile ground and do not have rinsing.Before applying composition of the present invention and afterwards, take pictures to ceramic tile.
The result
The photo explanation of Fig. 2 A and 2B, composition of the present invention cleans the mortar on the inner casing brick flooring of kitchen, restaurant.The ground of Fig. 2 A explanation before applying composition of the present invention.Fig. 2 B has illustrated the ground after applying composition of the present invention.
Fig. 3 has illustrated with an a part of ground of conventional cleaning compositions (left side) cleaning and a part that cleans with composition 33.Composition 33 cleans mortar, and conventional composition does not have.
Conclusion
Composition of the present invention cleans the ceramic tile mortar more effectively than conventional composition.
The stable composition thing cleaning floor that embodiment 7-is stable
Demonstration is according to the present invention and comprise that the composition of borate, polyvalent alcohol and spore is effective for cleaning floor.
Materials and methods
To the tile floor, specifically apply the use diluent that contains composition 34 (2oz/gal or 1.6% enriched material) on the clinker tile ground and do not have rinsing.Before applying composition of the present invention and afterwards, estimate ground.
34
Water 43
Boric acid 10
Alkanolamine 19
Polyvalent alcohol 5
Nonionogenic tenside 5
Silicone surfactant 2
Amphoterics 3
Anion surfactant 5
Hydrotropic agent 7
The spore blend 1
All consumptions are in wt%
The result
Composition 34 is cleaned ground.
Conclusion
The composition of composition ratio routine of the present invention is cleaning floor more effectively.
Should be noted that in this specification sheets and appended claim employed odd number " ", " being somebody's turn to do " and " this (a, an, the) " comprise plural form, unless this content clearly refers else.Therefore, for example contain the mixture that should comprise two or more compounds with reference to the composition of " a kind of compound ".Shall also be noted that term " or " usually with comprise " and/or " implication use, unless this content clearly refers else.
All public publications in this manual and patent application are the expressions that belongs to those skilled in the art in the invention's level.
With reference to various concrete and embodiment preferred and technical descriptions the present invention.Yet, should be appreciated that and can make many changes and modification, and keep within the spirit and scope of the present invention simultaneously.
Claims
(according to the modification of the 19th of treaty)
1. cleaning compositions, it comprises:
Spore, bacterium or fungi; With
The alkanolamine borate.
2. the composition of claim 1, wherein the pH of said composition is more than or equal to 8.
3. the composition of claim 1 further comprises polyvalent alcohol.
4. the composition of claim 3, wherein polyvalent alcohol comprises propylene glycol.
5. the composition of claim 1 further comprises the water of maximum about 65wt%.
6. the composition of claim 1, wherein the alkanolamine borate comprises monoethanolamine ammonium borate, di-alcohol ammonium borate, three ethanol ammonium borates or its combination.
7. the composition of claim 1 comprises about 5 to about 35wt% alkanolamine borate.
8. the composition of claim 1, its miospore or bacterium comprise microbial spores.
9. the composition of claim 1 further comprises about nonionogenic tenside of 0.003 to about 35wt%.
10. the composition of claim 9, wherein ionic surfactant pack is drawn together:
Contain (EO) at least y(PO) zNon-ionic block copolymer, wherein y and z are 2 to 100 independently;
C with 2-15mol oxyethane 6-24The alkylphenol alkoxide;
C with 2-15mol oxyethane 6-24The alcohol alkoxide;
Alkoxylated amines with 2-20mol oxyethane;
Or its mixture.
11. the composition of claim 1 further comprises about silicone surfactant of 0.0005 to about 35wt%.
12. the composition of claim 11, wherein silicone surfactant comprises the epoxy alkyl with about 2-100mol oxirane that siloxane main chain and at least one side are hung.
13. the composition of claim 12, wherein the epoxy alkyl of side extension comprises (EO) n, wherein n is 3-75.
14. the composition of claim 1 further comprises about anion surfactant of 0.003 to about 35wt%.
15. the composition of claim 14, wherein anion surfactant comprises:
Linear alkylbenzene sulfonate;
Sulfonated;
Alkyl-sulphate;
Secondary sulfonated alkane;
Sulfosuccinate; Or
Its mixture.
16. the composition of claim 1 further comprises about hydrotropic agent of 0.001 to about 20wt%.
17. the composition of claim 16 comprises about hydrotropic agent of 0.1 to about 20wt%.
18. the composition of claim 16, wherein hydrotropic agent comprises:
C 6-24Alkyl dimethyl amine oxide;
Alkylation phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate;
Or its mixture.
19. the composition of claim 1 further comprises:
About nonionogenic tenside of 0.5 to about 35wt%; With
About silicone surfactant of 0.1 to about 35wt%.
20. the composition of claim 19, wherein:
Ionic surfactant pack is drawn together:
Contain (EO) at least y(PO) zNon-ionic block copolymer;
C with 2-15mol oxyethane 6-24The alkylphenol alkoxide;
C with 2-15mol oxyethane 6-24The alcohol alkoxide;
Alkoxylated amines with 2-20mol oxyethane;
Or its mixture;
Silicone surfactant comprises the epoxy alkyl with about 2-100mol oxirane that siloxane main chain and at least one side are hung; With
The weight ratio of nonionogenic tenside and nonionic siloxane tensio-active agent is that per 1 part of silicone surfactant is about 0.1 to about 10 weight part nonionogenic tensides.
21. the composition of claim 1 further comprises:
About nonionogenic tenside of 0.5 to about 35wt%;
About silicone surfactant of 0.1 to about 35wt%;
About anion surfactant of 0.5 to about 35wt%; With
About hydrotropic agent of 0.1 to about 20wt%.
22. the composition of claim 21, wherein:
Ionic surfactant pack is drawn together:
Contain (EO) at least y(PO) zNon-ionic block copolymer;
C with 2-15mol oxyethane 6-24The alkylphenol alkoxide;
C with 2-15mol oxyethane 6-24The alcohol alkoxide;
Alkoxylated amines with 2-20mol oxyethane;
Or its mixture;
Silicone surfactant comprises the epoxy alkyl with about 2-100mol oxirane that siloxane main chain and at least one side are hung;
The weight ratio of nonionogenic tenside and nonionic siloxane tensio-active agent is that per 1 part of silicone surfactant is about 3 to about 7 weight part nonionogenic tensides;
Anion surfactant comprises alkanol ammonium alkylbenzene sulfonate; With
Hydrotropic agent comprises:
C 6-24Alkyl dimethyl amine oxide;
Alkylation phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate;
Or its mixture.
23. the composition of claim 21 further comprises:
One or more solvents of significant quantity;
One or more enzymes of significant quantity;
One or more antiseptic-germicides of significant quantity;
One or more sequestrants of significant quantity;
Or its mixture.
24. the composition of claim 1 further comprises detergency enzymes.
25. the composition of claim 24, wherein detergency enzymes comprises proteolytic enzyme, amylase, lipase, cellulase, peroxidase, glucose enzyme or its mixture.
26. a cleaning compositions, it comprises:
Microbial spores; With
Borate;
Said composition is substantially free of sodium ion.
27. the composition of claim 26, wherein said composition pH more than or equal to 8.
28. the composition of claim 26 further comprises polyvalent alcohol.
29. the composition of claim 28, wherein polyvalent alcohol comprises propylene glycol.
30. the composition of claim 26 further comprises the water of maximum about 65wt%.
31. the composition of claim 26, wherein borate comprises alkali metal borate, alkanolamine borate or its combination.
32. the composition of claim 31, wherein borate comprises monoethanolamine ammonium borate, di-alcohol ammonium borate, three ethanol ammonium borates or its combination.
33. the composition of claim 31, wherein borate comprises potassium borate.
34. the composition of claim 33, wherein potassium borate comprises the combination of potassium hydroxide and boric acid.
35. the composition of claim 26 comprises about borate of 5 to about 35wt%.
36. the composition of claim 26 further comprises:
About nonionogenic tenside of 0.5 to about 35wt%; With
About silicone surfactant of 0.1 to about 35wt%.
37. the composition of claim 36, wherein:
Ionic surfactant pack is drawn together:
Contain (EO) at least y(PO) zNon-ionic block copolymer;
C with 2-15mol oxyethane 6-24The alkylphenol alkoxide;
C with 2-15mol oxyethane 6-24The alcohol alkoxide;
Alkoxylated amines with 2-20mol oxyethane;
Or its mixture;
Silicone surfactant comprises the epoxy alkyl with about 2-100mol oxirane that siloxane main chain and at least one side are hung; With
The weight ratio of nonionogenic tenside and nonionic siloxane tensio-active agent is that per 1 part of silicone surfactant is about 0.1 to about 10 weight part nonionogenic tensides.
38. the composition of claim 26 further comprises:
About nonionogenic tenside of 0.5 to about 35wt%;
About silicone surfactant of 0.1 to about 35wt%;
About anion surfactant of 0.5 to about 35wt%; With
About hydrotropic agent of 0.1 to about 20wt%.
39. the composition of claim 38, wherein:
Ionic surfactant pack is drawn together:
Contain (EO) at least y(PO) zNon-ionic block copolymer;
C with 2-15mol oxyethane 6-24The alkylphenol alkoxide;
C with 2-15mol oxyethane 6-24The alcohol alkoxide;
Alkoxylated amines with 2-20mol oxyethane;
Or its mixture;
Silicone surfactant comprises the epoxy alkyl with about 2-100mol oxirane that siloxane main chain and at least one side are hung;
The weight ratio of nonionogenic tenside and nonionic siloxane tensio-active agent is that per 1 part of silicone surfactant is about 3-7 weight part nonionogenic tenside;
This anion surfactant comprises alkanol ammonium alkylbenzene sulfonate; With
Hydrotropic agent comprises:
C 6-24Alkyl dimethyl amine oxide;
Alkylation phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate;
Or its mixture.
40. the composition of claim 26 further comprises detergency enzymes.
41. comprising applying, the method for a cleaning hard surfaces, this method contain following cleaning compositions to described surface:
Spore or bacterium;
Borate;
About nonionogenic tenside of 0.5 to about 35wt%; With
About silicone surfactant of 0.1 to about 35wt%.
42. comprising, the method for claim 41, this method apply said composition in ground, water shoot or its combination.
43. a method that cleans mortar, this method comprise apply contain following substances cleaning compositions to mortar:
Spore or bacterium;
Borate;
About nonionogenic tenside of 0.5 to about 35wt%; With
About silicone surfactant of 0.1 to about 35wt%.
44. comprising, the method for claim 43, this method apply composition to the surface of tiling.
45. comprising, the method for claim 44, this method apply composition to the tile floor.

Claims (49)

1. cleaning compositions, it comprises:
Spore, bacterium or fungi; With
The alkanolamine borate.
2. the composition of claim 1, wherein the pH of said composition is more than or equal to 8.
3. the composition of claim 1 further comprises polyvalent alcohol.
4. the composition of claim 3, wherein polyvalent alcohol comprises propylene glycol.
5. the composition of claim 1 further comprises the water of maximum about 65wt%.
6. the composition of claim 1, wherein the alkanolamine borate comprises monoethanolamine ammonium borate, di-alcohol ammonium borate, three ethanol ammonium borates or its combination.
7. the composition of claim 1 comprises about 5 to about 35wt% alkanolamine borate.
8. the composition of claim 1, its miospore or bacterium comprise microbial spores.
9. the composition of claim 1 further comprises about nonionogenic tenside of 0.003 to about 35wt%.
10. the composition of claim 9, wherein ionic surfactant pack is drawn together:
Contain (EO) at least y(PO) zNon-ionic block copolymer, wherein y and z are 2 to 100 independently;
C with 2-15mol oxyethane 6-24The alkylphenol alkoxide;
C with 2-15mol oxyethane 6-24The alcohol alkoxide;
Alkoxylated amines with 2-20mol oxyethane;
Or its mixture.
11. the composition of claim 1 further comprises about silicone surfactant of 0.0005 to about 35wt%.
12. the composition of claim 11, wherein silicone surfactant comprises the epoxy alkyl with about 2-100mol oxirane that siloxane main chain and at least one side are hung.
13. the composition of claim 12, wherein the epoxy alkyl of side extension comprises (EO) n, wherein n is 3-75.
14. the composition of claim 1 further comprises about anion surfactant of 0.003 to about 35wt%.
15. the composition of claim 14, wherein anion surfactant comprises:
Linear alkylbenzene sulfonate;
Sulfonated;
Alkyl-sulphate;
Secondary sulfonated alkane;
Sulfosuccinate; Or
Its mixture.
16. the composition of claim 1 further comprises about hydrotropic agent of 0.001 to about 20wt%.
17. the composition of claim 16 comprises about hydrotropic agent of 0.1 to about 20wt%.
18. the composition of claim 16, wherein hydrotropic agent comprises:
C 6-24Alkyl dimethyl amine oxide;
Alkylation phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate;
Or its mixture.
19. the composition of claim 1 further comprises:
About nonionogenic tenside of 0.5 to about 35wt%; With
About silicone surfactant of 0.1 to about 35wt%.
20. the composition of claim 19, wherein:
Ionic surfactant pack is drawn together:
Contain (EO) at least y(PO) zNon-ionic block copolymer;
C with 2-15mol oxyethane 6-24The alkylphenol alkoxide;
C with 2-15mol oxyethane 6-24The alcohol alkoxide;
Alkoxylated amines with 2-20mol oxyethane;
Or its mixture;
Silicone surfactant comprises the epoxy alkyl with about 2-100mol oxirane that siloxane main chain and at least one side are hung; With
The weight ratio of nonionogenic tenside and nonionic siloxane tensio-active agent is that per 1 part of silicone surfactant is about 0.1 to about 10 weight part nonionogenic tensides.
21. the composition of claim 1 further comprises:
About nonionogenic tenside of 0.5 to about 35wt%;
About silicone surfactant of 0.1 to about 35wt%;
About anion surfactant of 0.5 to about 35wt%; With
About hydrotropic agent of 0.1 to about 20wt%.
22. the composition of claim 21, wherein:
Ionic surfactant pack is drawn together:
Contain (EO) at least y(PO) zNon-ionic block copolymer;
C with 2-15mol oxyethane 6-24The alkylphenol alkoxide;
C with 2-15mol oxyethane 6-24The alcohol alkoxide;
Alkoxylated amines with 2-20mol oxyethane;
Or its mixture;
Silicone surfactant comprises the epoxy alkyl with about 2-100mol oxirane that siloxane main chain and at least one side are hung;
The weight ratio of nonionogenic tenside and nonionic siloxane tensio-active agent is that per 1 part of silicone surfactant is about 3 to about 7 weight part nonionogenic tensides;
Anion surfactant comprises alkanol ammonium alkylbenzene sulfonate; With
Hydrotropic agent comprises:
C 6-24Alkyl dimethyl amine oxide;
Alkylation phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate;
Or its mixture.
23. the composition of claim 21 further comprises:
One or more solvents of significant quantity;
One or more enzymes of significant quantity;
One or more antiseptic-germicides of significant quantity;
One or more sequestrants of significant quantity;
Or its mixture.
24. the composition of claim 1 further comprises detergency enzymes.
25. the composition of claim 24, wherein detergency enzymes comprises proteolytic enzyme, amylase, lipase, cellulase, peroxidase, glucose enzyme or its mixture.
26. a cleaning compositions, it comprises:
Spore or bacterium; With
Borate;
Said composition is substantially free of sodium ion.
27. the composition of claim 26, wherein said composition pH more than or equal to 8.
28. the composition of claim 26 further comprises polyvalent alcohol.
29. the composition of claim 28, wherein polyvalent alcohol comprises propylene glycol.
30. the composition of claim 26 further comprises the water of maximum about 65wt%.
31. the composition of claim 26, wherein borate comprises alkali metal borate, alkanolamine borate or its combination.
32. the composition of claim 31, wherein borate comprises monoethanolamine ammonium borate, di-alcohol ammonium borate, three ethanol ammonium borates or its combination.
33. the composition of claim 31, wherein borate comprises potassium borate.
34. the composition of claim 33, wherein potassium borate comprises the combination of potassium hydroxide and boric acid.
35. the composition of claim 26 comprises about borate of 5 to about 35wt%.
36. the composition of claim 26, its miospore or bacterium comprise microbial spores.
37. the composition of claim 26 further comprises:
About nonionogenic tenside of 0.5 to about 35wt%; With
About silicone surfactant of 0.1 to about 35wt%.
38. the composition of claim 37, wherein:
Ionic surfactant pack is drawn together:
Contain (EO) at least y(PO) zNon-ionic block copolymer;
C with 2-15mol oxyethane 6-24The alkylphenol alkoxide;
C with 2-15mol oxyethane 6-24The alcohol alkoxide;
Alkoxylated amines with 2-20mol oxyethane;
Or its mixture;
Silicone surfactant comprises the epoxy alkyl with about 2-100mol oxirane that siloxane main chain and at least one side are hung; With
The weight ratio of nonionogenic tenside and nonionic siloxane tensio-active agent is that per 1 part of silicone surfactant is about 0.1 to about 10 weight part nonionogenic tensides.
39. the composition of claim 26 further comprises:
About nonionogenic tenside of 0.5 to about 35wt%;
About silicone surfactant of 0.1 to about 35wt%;
About anion surfactant of 0.5 to about 35wt%; With
About hydrotropic agent of 0.1 to about 20wt%.
40. the composition of claim 39, wherein:
Ionic surfactant pack is drawn together:
Contain (EO) at least y(PO) zNon-ionic block copolymer;
C with 2-15mol oxyethane 6-24The alkylphenol alkoxide;
C with 2-15mol oxyethane 6-24The alcohol alkoxide;
Alkoxylated amines with 2-20mol oxyethane;
Or its mixture;
Silicone surfactant comprises the epoxy alkyl with about 2-100mol oxirane that siloxane main chain and at least one side are hung;
The weight ratio of nonionogenic tenside and nonionic siloxane tensio-active agent is that per 1 part of silicone surfactant is about 3-7 weight part nonionogenic tenside;
Anion surfactant comprises alkanol ammonium alkylbenzene sulfonate; With
Hydrotropic agent comprises:
C 6-24Alkyl dimethyl amine oxide;
Alkylation phenyl ether stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate;
Or its mixture.
41. the composition of claim 26 further comprises detergency enzymes.
42. comprising applying, the method for a cleaning hard surfaces, this method contain following cleaning compositions to described surface:
Spore or bacterium;
Borate;
About nonionogenic tenside of 0.5 to about 35wt%; With
About silicone surfactant of 0.1 to about 35wt%.
43. the method for claim 42, this method comprise apply said composition to ground, water shoot or it is in conjunction with last.
44. a cleaning compositions, it comprises:
Spore or bacterium; With
Borate.
45. a method that increases the hard surface frictional coefficient, this method comprise apply contain following substances cleaning compositions to the surface:
Spore or bacterium;
Borate;
About nonionogenic tenside of 0.5 to about 35wt%; With
About silicone surfactant of 0.1 to about 35wt%.
46. the method for claim 45, this method comprise apply said composition to ground, water shoot or it is in conjunction with last.
47. comprising applying, a method that cleans mortar, this method contain following cleaning compositions to mortar:
Spore or bacterium;
Borate;
About nonionogenic tenside of 0.5 to about 35wt%; With
About silicone surfactant of 0.1 to about 35wt%.
48. comprising, the method for claim 47, this method apply composition to the surface of tiling.
49. comprising, the method for claim 48, this method apply composition to the tile floor.
CN 200480031302 2003-10-24 2004-10-18 Stable compositions of spores, bacteria, and/or fungi Pending CN1871336A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
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US60/514,370 2003-10-24
US10/956,135 2004-10-01

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108347947A (en) * 2015-10-30 2018-07-31 以Z生物科学公司名义营业的Z益生菌公司 Probiotic composition and application thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5449619A (en) * 1992-04-16 1995-09-12 Sybron Chemical Holdings, Inc. Drain opener formulation
GB2324092A (en) * 1997-04-09 1998-10-14 Reckitt & Colman Inc Composition for the treatment of foodstuff waste comprising protease, amylase, lipase and cellulase
US6425959B1 (en) * 1999-06-24 2002-07-30 Ecolab Inc. Detergent compositions for the removal of complex organic or greasy soils

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108347947A (en) * 2015-10-30 2018-07-31 以Z生物科学公司名义营业的Z益生菌公司 Probiotic composition and application thereof

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