CN1105173C - Dingy fabric clean-up with amylase enzyme in detergent compsns. - Google Patents

Dingy fabric clean-up with amylase enzyme in detergent compsns. Download PDF

Info

Publication number
CN1105173C
CN1105173C CN96197143A CN96197143A CN1105173C CN 1105173 C CN1105173 C CN 1105173C CN 96197143 A CN96197143 A CN 96197143A CN 96197143 A CN96197143 A CN 96197143A CN 1105173 C CN1105173 C CN 1105173C
Authority
CN
China
Prior art keywords
composition
amylase
acid
detergent
detergent composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN96197143A
Other languages
Chinese (zh)
Other versions
CN1197478A (en
Inventor
K·普拉莫德
T·W·霍尔纳
R·奥塔尼
A·C·贝克
S·赖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=26668893&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=CN1105173(C) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of CN1197478A publication Critical patent/CN1197478A/en
Application granted granted Critical
Publication of CN1105173C publication Critical patent/CN1105173C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/662—Carbohydrates or derivatives
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/75—Amino oxides

Abstract

The present invention relates to detergent compositions comprising an oxidative stability-enhanced amylase and a protease at a level from 0.0001 % to 0.5 %, preferably from 0.001 % to 0.2 %, more preferably from 0.005 % to 0.1 % pure protease enzyme by weight of total composition. Such compositions provide improved cleaning and stains removal performances.

Description

Remove the fabric blackening with the amylase in the detergent composition
Technical field
The present invention relates to the detergent composition of granular, liquid or strip, that said composition contains is a certain amount of, special selection, especially improved the amylase to the fabric washing performance of dark stain and dirt.This detergent composition preferably also contains other enzyme and tensio-active agent.
Background of invention
Have been found that: the amylase in detergent composition provides unexpected effective cleaning performance.These amylase show that make new advances and benefit unexpected cleaning blackening and keep the advantage of whiteness.
It has been recognized that amylase provides the effect of removing starch food resistates or starch film from bowl dish, dish and glassware in the dishwashing composition.The general starch enzyme that is used for dishwashing is the TERMAMYL that can obtain from Novo Nordisk S/A RTherefore, although amylase is known to the effect of starch stain, contains the laundry component of amylase and tensio-active agent in preparation by this way and still exist sizable technical problem aspect the human consumer has excellent properties to other dirt that cleans starch soil and run in laundry applications the needs so that satisfy.In addition, such detergent composition must provide has fabulous value and safety, environmentally acceptable product, and this product is stayed and is washed fabric, especially has easily under blackening and the not infringement condition on those fabrics of dark dirt not having.Therefore, exist exploitation and contain the needs that are designed to the effective especially diastatic detergent composition of removing blackening.
An object of the present invention is to provide and contain diastatic improved laundry composition, this amylase provides effective removal blackening and total effect of cleaning benefit.Another object of the present invention is to use the laundry composition of starch-containing enzyme and tensio-active agent that the method for keeping fabric whiteness is provided.In another aspect of the present invention, its objective is the laundry composition that full preparation is provided, thus amylase and additionally mix the cleaning performance that provides excellent wherein through the component of selecting.As what seen from following disclosure, this paper has reached these and other objects.
Background technology
The WO/94/02597 of disclosed Novo Nordisk A/S described and was mixed with the diastatic cleaning combination of mutant on February 3rd, 1994.Also referring to August in 1994 disclosed Genecor on the 18th WO94/18314A and April 20 nineteen ninety-five disclosed Novo Nordisk A/S WO95/10603.
The suitable amylase that is used for this invention composition comprises α and βDian Fenmei.α-Dian Fenmei is known and at US5003257 in the prior art; EP252666; WO91/00353; FR2676456; EP285123; EP525610; EP368341; With disclosed those amylase among the british patent specification No.1296839 (Novo).
Summary of the invention
Made us now unexpectedly finding: amylase, particularly, provide unexpected, excellent removing blackening recently by those amylase of conventional gene engineering development, keep whiteness and total cleaning performance.Such performance specification is as follows, but is not restriction: have fabulous dirt to remove to pillowcase, T-shirt and the stocking sole.
The present invention relates to the detergent composition of liquid, granular or strip, said composition provides especially effectively fabric face cleaning.The invention still further relates to and use such detergent composition method of cleaning fabrics.
A kind ofly be washed especially effectively laundry detergent composition of blackening fabric to cleaning and brightening, said composition contains:
A. detergent surfactant, this tensio-active agent is selected from: negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionics and its combination, and the amount of this tensio-active agent serves as about 1%-about 40% with the weight of composition; With
B. one or more amylase, its amount is the active amylase of the about 2mg of the about 0.001mg-of every gram composition, and with compare with the analogous composition of starch-containing enzyme not, this amylase has improved the whiteness of using the dark fabric that the washing soln that formed by described detergent composition washs effectively.
Thereby the invention still further relates to laundering of textile fabrics keeps or increases whiteness and the method for removing blackening is provided, described method comprises: make the fabric that needs whiteness and remove blackening and contact by containing the aqueous solution that tensio-active agent and diastatic detergent composition form, this detergent composition contains the tensio-active agent and the amylase of such concentration, promptly make and compare, increased the whitening performance of described composition with not containing diastatic analogous composition.
The invention still further relates to laundering of textile fabrics so that the method for the reduction smell relevant with dirt and stain, described method comprises: make the stain of needs control smell and dirt fabric and contact by containing the aqueous solution that tensio-active agent and diastatic detergent composition form, described detergent composition exists with such concentration, compare with reducing with the relevant smell of the dirty fabric that does not contain the washing of diastatic analogous composition, it makes and has reduced the smell relevant with stain with described dirt.
At last, keep or increase whiteness and the method for removing blackening is provided thereby the present invention relates to laundering of textile fabrics, described method comprises: make the fabric that needs whiteness and remove blackening and contact in cycles of washing repeatedly or contact sufficiently long for some time and make fabric show to brighten with not too dark by containing the aqueous solution that tensio-active agent and diastatic detergent composition form.
Unless otherwise indicated, all umbers, percentage ratio and ratio herein all represented with weight percentage.The relevant part of all references is incorporated herein by reference.
Detailed Description Of The Invention
Detergent composition herein preferably contains the nonphosphate detergent for washing clothes of the fine cleaning fouling performance of having of amylase and tensio-active agent.For purposes of the invention, term " liquid " is meant the detergent composition of any suitable liquid form, for example, and structurized liquid, isotropic liquid, gel etc.
Laundry detergent composition herein provides remarkable and effective fabric face cleaning, and is especially true to blackening under wide laundry wash temperature scope.The example of blackening generally is at pillowcase, those blackenings that the T-shirt and the stocking sole are found.The temperature of laundry washings is preferably between about 95 ℃ of about 5-, for this washing benefit, preferably between about 60 ℃ of about 10-.
Bound by theory not it is believed that dark dirt and stain are fatty dirt and particulate fouling blended result.The fat dirt comprises with human or animal's skin contact and is deposited on lipoid, protein and pigment on the fabric.Most of lipid from sebiferous gland as sebum secretion.Break by skin cells from the protein of skin chips and pigment and to discharge.Particulate fouling comprises most airborne dirt and floor/ground dust.It is believed that sebum is the main dirt that exists on the substrate, and its removal is important, because the fat that does not have to remove works to keep the matrix of particulate fouling.In addition, thus it is believed that the compound oxidation that is present in the sebum impels the fabric yellowing.Particulate fouling comprises table soil and the product that produces during the petroleum products incomplete combustion.As employed in this article, " removing blackening " be meant detergent composition pass through one or repeatedly washing remove above-mentioned dark dirt and assemble, thereby the ability that causes appearance of fabrics suitably to improve.
It is monitoring through the whiteness of cycles of washing after scouring and thread bare fabric repeatedly that whiteness keeps.Washing composition with superperformance has good whiteness and keeps distributing, and promptly it guarantees that the whiteness that is washed fabric during the full cycle of washing and wearing and tearing remains on high level.
As employed in this article, " whitening performance " is meant and comprises that certain diastatic laundry detergent composition through selecting produces the relative capacity of removing blackening and/or whiteness maintenance effect.
Removing the performance of blackening can measure according to Hunter whiteness value (W), and this value is calculated according to following formula:
W=(7L 2-40Lb)/700 wherein, L, a, b are determined by tristimulus meter reading and represent 3 based on using Hei-Bai (L), red-green (a), and the axle of the opposition color grade system of the theory of Huang-indigo plant (b) sensation observation color.The W value is high more, and whiteness performance and removing blackening are good more.See " outward appearance mensuration " (The Measurement ofAppearance) of R.S.Hunter and R.W.Harold, the 2nd edition, New York John Wiley in 1987; The ASTM standard (ASTM Standards on Color andAppearance Measurement) that Sons publication and color and outward appearance are measured, the 3rd edition, ASTM, Philadelphia, Pennsylvania in 1991.
Amylase-detergent composition of the present invention contains the about 2mg of the about 0.001mg-of every gram composition, the active amylase of the about 1mg of preferably about 0.01-.Explanation is in addition, and composition herein generally contains about 0.2% (weight) of the 0.0001%-that has an appointment, the organized enzyme of preferred 0.001%-0.1% (weight).In another aspect of the present invention, detergent composition herein contains the organized enzyme of the 0.15%-that has an appointment about 0.2% (weight).
The suitable amylase that is used for the present composition comprises α and βDian Fenmei.α-Dian Fenmei is known in the prior art and is included in US5003257; EP252666; WO91/00353; WO96/05295; FR2676456; EP285123; EP525610; With disclosed those amylase among the EP368341.Preferred amylase comprises Termamyl R(Novo Nordisk) and BAN R(Novo Nordisk).Termamyl RBe described among the british patent specification No.1296839 (Novo).
The present invention's amylase very preferably is included in has the stability of improvement, those amylase that especially have improved oxidative stability in the washing composition.Usually, stable enhanced amylase can be from Novo Nordisk A/S, or obtains from Genencor International.
Preferred herein amylase has from one or more subtilis amylase, and especially the genus bacillus α-Dian Fenmei is used site-directed mutagenesis deutero-general character, with a kind of, two or more amylase strains whether be in the middle of precursor irrelevant.Methionine(Met) (Met) is considered to the residue that most probable is modified and uses any naturally occurring L-aminoacid replacement.
As noted, " oxidative stability enhanced " amylase is preferred for herein.Such amylase is described as follows without limitation:
(a) according to above introduce on February in 1994 3 disclosed Novo Nordisk A/S the amylase of WO/94/02597, as being further specified by mutant, wherein use L-Ala or Threonine (preferred Threonine), substituent is to be referred to as TERMAMYL by being positioned at (R)The methionine residue of Bacillus licheniformis α-Dian Fenmei 197 positions, or similar parent amylase, for example the same source position mutation of bacillus amyloliquefaciens, subtilis or bacstearothermophilus constitutes.
(b) stability-enhanced amylase comprises Purafact Ox Am R, as GenencorInternational by the stable enhanced amylase of C.Mitchinson described in the paper of going up being entitled as of submitting to " sludge proof α-Dian Fenmei (Oxidatively Resistant α-Amylases) " 13-17 day in March, 1994 in the 207th American Chemical Society country's meeting (American Chemical Society National Meeting) and on August 18th, the 1994 disclosed WO94/18314A.Wherein mentioning the amylase that improves oxidative stability is made from Bacillus licheniformis NCIB8061 by Genencor.Methionine(Met) (Met) is considered to the residue that most probable is modified.8,15,197,256,304,366 and 438 replace Met one at a time and have caused specific mutant, particularly importantly M197L and M197T, and the M197T varient is the varient of stably express; Also referring to the WO96/05295 of GenencorInternational, the document discloses has M197T, the amylase of M15T and W138Y mutation.
(c) particularly preferably be herein and in intermediate parent body, have amylase mutation other modification, that can obtain from NovoNordisk A/S.Be disclosed in these amylase among the WO9510603 that publishes April nineteen ninety-five with trade(brand)name Duramyl (R)Be known and they are supplied the merchant and are referred to as QL37+M197T.
Can use any other oxidative stability enhanced amylase, for example from known available diastatic chimeric, hybrid or simple mutant parent form are by the site-directed mutagenesis deutero-.
Detergent surfactant-composition of the present invention also can comprise the water soluble detergent tensio-active agent of about 40% (weight) of about 1-, and this tensio-active agent is selected from: negatively charged ion, nonionic, positively charged ion, zwitter-ion, amphoterics and its mixture.The detergent surfactant of about 2-about 25% (weight) is that about 15% (weight) of preferred and about 5-is most preferred.The example of preferred surfactants comprises amine tensio-active agent, C 11-13Linear alkylbenzene sulfonate, C 12-16Alkyl-sulphate and/or methyl ester sulfonate.In one embodiment, preferred surfactants is an amine.
Useful herein detergent surfactant is listed among US3664961 (Norris, on May 23rd, 1972 promulgation) and the US3919678 people such as (, issued on December 30th, 1975) Laughlin, and these two pieces of documents are incorporated herein by reference.Be the illustrative example of detergent surfactant useful in this composition below.
A class preferred surfactants that is used for herein comprises according to formula R 1R 2R 3The primary amine of N, wherein R 1And R 2All are H, R 3Be C 4-C 18, preferred C 6-C 12Alkyl chain, R 3Alkyl chain can be straight or branched and can disconnect with being up to 12 ethylene oxide moieties, most preferably with being up to 5 ethylene oxide moieties disconnections.According to the preferred amine of following formula herein is positive alkylamine.The suitable amine that is used for herein can be selected from: 1-hexylamine, 1-octylame, lauryl amine, palmitamide, stearylamine, oleyl amine, coconut alkylamine, tallow alkyl amine.
Other suitable primary amine comprises according to formula R 1R 2R 3The amine of N, wherein R 1And R 2All are H, R 3Be R 4X (CH 2) n, X is-O-,-C (O) NH-or-NH-, R 4Be C 4-C 18, preferred C 6-C 12Alkyl chain and R 4Can be straight or branched, n be between 1-5.According to the preferred amine of following formula herein be: 3-isopropoxy propylamine, 3-(2-methoxy ethoxy)-propylamine and 2-(2-amino ethoxy)-ethanol, C 8-C 10Octyloxy propylamine, 2-ethyl hexyl oxy propylamine, lauryl amido propylamine and coconut amido propylamine.
The suitable tertiary amine that is used for herein comprises having formula R 1R 2R 3The tertiary amine of N, wherein R 1And R 2All not H, R 1And R 2Be C 1-C 8Alkyl chain or
Figure C9619714300081
, wherein x is between 1-6; R 3Or C 4-C 18, preferred C 6-C 12Alkyl chain, perhaps R 3Be R 4X (CH 2) n, wherein X is-O-,-C (O) NH-or-NH-, R 1Be C 4-C 18, n is between 1-5, and R 5Be H or C 1-C 2Alkyl.R 3, R 4C preferably 6-C 12Alkyl chain and can be straight or branched; R 3Alkyl chain can disconnect with being up to 12 ethylene oxide moieties, most preferably disconnects with being up to 5 ethylene oxide moieties.
The suitable tertiary amine that is used for herein comprises: coconut alkyl dimethyl amine, dimethyl oil base amine, hexadecyl three (vinyloxy group) dimethyl amine, two (2-hydroxyethyl) amine of tallow alkyl, two (2-hydroxyethyl) amine of stearyl-and two (2-hydroxyethyl) amine of oleoyl.
In above-mentioned all amine, preferable material is the trialkylamine of selling with trade(brand)name ADOGEN, the amine of the long chain alkyl dimethyl amine of selling with trade(brand)name ARMEEN and the ethoxylation of selling with trade(brand)name ETHOMEEN.The most preferred amine that is used for this paper composition is: 1-hexylamine, 1-octylame, 1-decyl amine, 1-lauryl amine.For odor property it is desirable to especially dodecyl dimethyl amine (ARMEEN DM12D) and two hydroxyethyl-coconut alkylamine (ETHOMEEN C/12, BEROL307) and oleyl amine (BEROL28), lauryl amido propylamine and the coco group amido propylamine of 7 times of ethoxylations.
Other suitable amine comprises the tertiary amine with following formula: R wherein 1Be C 4-C 10, preferred C 8-C 10Alkyl; N is 2-4, and preferred n is 3; R 2Be C 1-C 4Or
Figure C9619714300092
, wherein x is 1-5, R 3Be H or C 1-C 2Alkyl.
Amphoterics comprises: heterocyclic secondary and the aliphatic series of tertiary amine or the derivative of aliphatic derivatives, wherein the aliphatic series part can be a straight or branched, and one of them aliphatic substituting group contains 8-18 the carbon atom of having an appointment and contains the anionic water solubilizing group with at least one aliphatic substituting group.
The water-soluble salt of higher fatty acid, i.e. " soap " is useful anion surfactant in the composition of this paper.It comprises: alkali metal soap for example contains about 24 carbon atoms of the 8-that has an appointment, and preferably contains sodium, potassium, ammonium and the alkylammonium salt of the higher fatty acid of about 18 carbon atoms of the 12-that has an appointment.Soap can be made by the direct saponification of fat and oil or by the neutralization of free fatty acids.Useful especially is sodium and sylvite from Oleum Cocois and tallow derived fatty acid mixture, i.e. tallow and coconut sodium or potash soap.
Useful anion surfactant also comprises the salt of water soluble, preferably has basic metal, ammonium and the pure ammonium salt of the organosulfur reaction product that contains about 20 carbon atom alkyls of about 10-and sulfonic acid or sulfate group in its molecular structure.(the moieties that in term " alkyl ", comprises acyl group.) example of this class synthetic surfactant is: sodium alkyl sulfate and alkylsurfuric acid potassium, especially by sulfation higher alcohols (C 8-C 18Carbon atom) those pure those vitriol that obtain that for example obtain by glyceryl ester reduction with tallow or Oleum Cocois; With sodium alkyl benzene sulfonate and potassium, wherein this alkyl contains about 15 carbon atoms of the 9-that has an appointment, and is the straight or branched configuration, for example at those of type described in US2220099 and the US2477383.Valuable especially is linear alkylbenzene sulfonate, and wherein the average carbon atom number in the alkyl group is about 11-13, is abbreviated as C 11-13LAS.
Other anion surfactant herein is the alkyl glycerylether sodium sulfonate, particularly from the sodium sulfonate of the ether of tallow and Oleum Cocois deutero-higher alcohols; Coco-nut oil fatty acid coconut monoglyceride and sodium sulfate; Per molecule contain about 10 ethylene oxide units of the 1-that has an appointment and wherein alkyl contain the alkylphenol oxyethane ether sodium sulfate or the potassium of about 12 carbon atoms of the 8-that has an appointment; Per molecule contain about 10 ethylene oxide units of the 1-that has an appointment and wherein alkyl contain the alkyl epoxy ethane ether sodium sulfate or the potassium of about 20 carbon atoms of the 10-that has an appointment.
The useful anion surfactant of herein other comprises: contain in fatty acid group and have an appointment 6-20 carbon atom and contain the water-soluble salt of ester of the α-alpha-sulfonated fatty acid of 1-10 the carbon atom of having an appointment in ester group; In acyl group, contain and have an appointment 2-9 carbon atom and contain the water-soluble salt of the 2-acyloxy alkane-1-sulfonic acid of about 23 carbon atoms of the 9-that has an appointment at moieties; Contain the have an appointment alkene of 12-20 carbon atom and the water-soluble salt of paraffin sulfonate; Have an appointment 1-3 carbon atom and contain the β-alkoxyalkyl sulfonate of 8-20 the carbon atom of having an appointment at moieties with in alkyl, containing.
Water miscible nonionogenic tenside also is useful in composition of the present invention.Such non-ionic material comprises: by the compound that alkylene oxide group (hydrophilic) and organic hydrophobic compound (it can be aliphatic series or alkyl aromatic in nature) condensation are produced.Can easily regulate and thereby the length of the polyalkylene oxide groups of any specific hydrophobic group condensation obtains having equilibrated water-soluble cpds between the hydrophilic and hydrophobic part of required degree.
Suitable ionic surfactant pack is drawn together: the polyethylene oxide condensation compound of alkylphenol for example has the alkylphenol that contains alkyl about 6-15 carbon atom, the straight or branched configuration and the condensation product of every mole of alkylphenol 3-12 moles of ethylene oxide.
Preferred nonionic is to contain the fatty alcohol of straight or branched configuration of 8-22 carbon atom and the water-soluble and water dispersible condensation product of every mol of alcohol 3-12 moles of ethylene oxide.Particularly preferably be the condensation product of the 4-8 moles of ethylene oxide of the alcohol of the alkyl that contains 9-15 the carbon atom of having an appointment and every mol of alcohol.
Nonionogenic tenside very preferably is the polyhydroxy fatty acid amide of following formula: R wherein 1Be H, or R 1Be C 1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R 2Be C 5-31Alkyl and Z have to contain at least 3 polyhydroxy alkyls that are directly connected to the straight-chain alkyl chain of the hydroxyl on this chain, or its oxyalkylated derivative.Preferably, R 1Be methyl, R 2It is straight chain C 11-15Alkyl or C 16-18Alkyl or alkenyl chain, for example coconut alkyl or its mixture and Z in reductive amination process from reducing sugar such as glucose, fructose, maltose, lactose-derived.
Semi-polar nonionic surfactants comprises: contain an about 10-18 carbon atom alkyl part and two and be selected from alkyl and the hydroxyalkyl water-soluble amine oxides partly that contains about 3 carbon atoms of the 1-that has an appointment; Contain an about 10-18 carbon atom alkyl part and two and be selected from alkyl and the hydroxyalkyl water soluble oxidized phosphine partly that contains 1-3 the carbon atom of having an appointment; With contain an about 10-18 carbon atom alkyl part and one and be selected from alkyl and the hydroxyalkyl water-soluble sulfoxide partly that contains 1-3 the carbon atom of having an appointment.
Zwitterionics comprises: the derivative of quaternary ammonium, Phosphonium and the sulfonium compound of aliphatic series, one of them aliphatic substituting group contains 8-18 the carbon atom of having an appointment.
Be applicable to that cationic detersive tensio-active agent in the laundry detergent composition of the present invention is to have those of a long chain hydrocarbon groups.The example of such cats product comprises: ammonium surfactant is alkyl trimethyl ammonium halide and have those tensio-active agents of following formula for example:
[R 2(OR 3) y] [R 4(OR 3) y] 2R 5N +X -R wherein 2Be alkyl or the alkyl benzyl that in alkyl chain, has about 18 carbon atoms of about 8-, each R 3Be selected from :-CH 2CH 2-,-CH 2CH (CH 3)-,-CH 2CH (CH 2OH)-,-CH 2CH 2CH 2-and its mixture; Each R 4Be selected from: C 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, by connecting two R 4The benzyl ring structure that group forms ,-CH 2CHOH-CHOHCOR 6CHOHCH 2OH-, wherein R 6Be that hexose or molecular weight are lower than about 1000 hexose polymkeric substance and R when y is not 0 6Be hydrogen; R 5With R 4Identical or R wherein 2+ R 5Total carbon atom number be not more than about 18 alkyl chain; Each y is that the sum of 0-about 10 and this y value is 0-about 15; With X be any compatible negatively charged ion.
Cats product very preferably be have following formula, in the present composition useful water-soluble quaternary ammonium compound:
R 1R 2R 3R 4N +X -(i) R wherein 1Be C 8-C 16Alkyl, each R 2, R 3And R 4Be C independently of one another 1-C 4Alkyl, C 1-C 4Hydroxyalkyl, benzyl and-(C 2H 40) xH, wherein the value of x is that 2-5 and X are negatively charged ion.R 2, R 3Or R 4In no more than one be benzyl.
Be used for R 1The preferred alkyl chain length be C 12-C 15, especially, wherein this alkyl is the mixture from Oleum Cocois or palm-kernel fat deutero-chain length, or synthetic or OXO is pure synthesizes to synthesize deutero-by alkene.Be used for R 2, R 3And R 4Preferred group be that methyl and hydroxyethyl and negatively charged ion X can be selected from: halogenide, methyl-sulfuric acid root, acetate moiety and phosphate anion.
The example that is used for suitable formula (i) quaternary ammonium compound herein is:
Coco group trimethyl ammonium muriate or bromide;
Coco group methyl dihydroxy ethyl ammonium muriate or bromide;
Decyl triethyl ammonium muriate;
Decyl dimethyl hydroxyethyl ammonium muriate or bromide;
C 12-15Dimethyl hydroxyethyl ammonium muriate or bromide;
Coco group dimethyl hydroxyethyl ammonium muriate or bromide;
Myristyl trimethyl ammonium Methylsulfate;
Lauryl dimethyl hexadecyldimethyl benzyl ammonium muriate or bromide;
Lauryl dimethyl (vinyloxy group) 4Ammonium muriate or bromide;
Cholinesterase (compound of formula (i), wherein R 1Be CH 2-CH 2-O-C (O)-CH 12-14Alkyl and R 2, R 3, R 4Be methyl);
Dialkylimidazolium quinoline [compound of formula (i)].
Other useful in this article cats product also is described among US4228044 (Cambre, promulgation on October 14th, 1980) and the EP000224.
When wherein containing sometimes, laundry detergent composition of the present invention generally contains about 25% (weight) of 0.2-, the above-mentioned cats product of about 10% (weight) of preferably about 1-.
Additive component-herein composition can randomly comprise one or more other detergent additives materials or help or strengthen cleaning performance, handle substrate that will be washed or other material (for example spices, tinting material, dyestuff etc.) that improves the detergent composition aesthetics.Be the illustrative example of such additive material below.
Optional clean washing assistant-can choose and preferably include about 80% (weight) of 1-, the clean washing assistant of about 70% (weight) of preferably about 20-herein wantonly.Can use inorganic and organic washing-assisting detergent.Preferred washing assistant comprises those washing assistants that are selected from lipid acid, Citrate trianion, carbonate, silicate, vitriol, phosphoric acid salt, silico-aluminate and its mixture.
Inorganic clean washing assistant includes, but are not limited to: the poly-phosphate of basic metal, ammonium and alkanol ammonium (illustrating with tri-polyphosphate, pyrophosphate salt and glassy polymer metaphosphate), phosphonate, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.Also can use the borate washing assistant, and contain the washing assistant that forms borate material, this material produces borate (hereinafter being generically and collectively referred to as " borate washing assistant ") under washing composition storage or wash conditions.Preferably, planning to be lower than about 50 ℃, especially be lower than and use non-borate washing assistant in the present composition that uses under about 40 ℃ wash conditions.
The example of silicate-like builder is an alkalimetal silicate, especially SiO 2: Na 2The O ratio is 1.6: 1-3.2: those silicate and the layered silicate of 1 scope, for example at the lamina sodium silicate described in the US4664839 (H.P.Rieck, promulgation on May 12nd, 1987), the document is incorporated herein by reference.Yet other silicate also is useful.
The example of carbonate builders is as disclosed alkaline-earth metal and alkaline carbonate on November 15th, 1973 disclosed German patent application number 2321001 (disclosure of the document is incorporated herein by reference), comprise yellow soda ash and concentrated crystal soda and with the mixture of calcium carbonate superfine powder.
The silico-aluminate washing assistant is useful in the present invention.The silico-aluminate washing assistant comprises the formula M that sees service z(zAlO 2SiO 2) those, wherein M is the ammonium of sodium, potassium, ammonium or replacement, z is 1 for about 0.5-about 2 and y; The magnesium ion exchange capacity of this material is the anhydrous silico-aluminate of every gram about 50 millinormal CaCO at least 3Hardness.Preferred silico-aluminate is the zeolite builders with following formula: Na z[(AlO 2) z(SiO 2) y] xH 2O, wherein z and y are at least 6 integer, and the mol ratio of z and y is that 1.0-about 0.5 and x are the integers of about 15-about 264.Useful herein preferred synthetic crystallization aluminosilicate ion exchange material can obtain with title zeolite A, zeolite P (B) and X zeolite.
The object lesson of poly-phosphate is an alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, and trisodium phosphate and potassium and ammonium, sodium orthophosphate and potassium, the polymerization degree is at the Sodium polymetaphosphate of about 21 scopes of about 6-and the salt of phytinic acid.
Be preferred for organic detergent washing assistant of the present invention and comprise having a plurality of carboxylate group, multi-carboxylate's compound of preferred at least 3 carboxylate radicals.
Generally the multi-carboxy acid salt washing agent is joined in the composition, but also can add with the form of neutralized salt with sour form.When using with salt form, basic metal for example sodium, potassium and lithium or alkanol ammonium salts is preferred.
The important multi-carboxy acid salt washing agent of one class comprises the ether multi-carboxylate.Useful ether multi-carboxylate's example comprises that these two pieces of documents are incorporated herein by reference as disclosed oxygen di-succinate in US3128287 (Berg, on April 7th, 1964 promulgation) and US3635830 people such as (, issued on January 18th, 1972) Lamberti.
In the present invention as the ether multi-carboxylate's of washing assistant object lesson also comprise have general formula CH (A) (COOX)-CH (COOX)-O-CH (COOX)-CH (COOX) those multi-carboxylates (B), wherein A is H or OH; B be H or-O-CH (COOX)-CH 2(COOX); With X be the salifiable positively charged ion of H or shape.The suitable example of these washing assistants is disclosed among the US4663071 (people such as Bush, promulgation on May 5th, 1987).
Suitable ether multi-carboxylate also comprises ring compound, alicyclic compound especially, and those disclosed in US3923679, US3835163, US4158635, US4120874 and US4102903 for example, these documents all are incorporated herein by reference.
Other useful clean washing assistants comprise the multipolymer of ether hydroxypolycarboxylic acid salt and maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxy methoxy-succinic acid.
Other useful clean washing assistant also comprises tartrate monosuccinic acid salt or tartrate disuccinate.
Organic multi-carboxy acid salt washing agent also comprises the ammonium salt of various basic metal, ammonium and the replacement of polyacetic acid.Example comprises sodium, potassium, lithium, ammonium and the substituted ammonium salt of ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA).
The multi-carboxylate also comprises: for example mellitic acid, succsinic acid, oxygen di-succsinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxy methoxy-succinic acid and its water-soluble salt.
The Citrate trianion washing assistant, for example citric acid and its water-soluble salt (especially sodium salt) are also operable multi-carboxy acid salt washing agents in this paper composition.
Other multi-carboxy acid salt washing agent comprises the carboxylic acidifying carbohydrate that is disclosed among the US3723322 (Diehl, promulgation on March 28th, 1973), and the document is incorporated herein by reference.
Also being suitable in the detergent composition of the present invention is to be disclosed in 3 among the US4566984 (Bush, on January 28th, 1986 promulgation), 3-dicarboxyl-4-oxa--1, and 6-adipate and relevant compound, the document is incorporated herein by reference.Useful succsinic acid washing assistant comprises C 5-C 20Alkyl succinic acid and its salt.The succinate washing assistant preferably comprises the form use of sodium, potassium, ammonium and alkanol ammonium salts with its water-soluble salt.
The example of useful washing assistant also comprises the multipolymer of carboxymethoxyl sodium malonate and potassium, carboxy methoxy-succinic acid salt, suitable-hexanaphthene-hexacarboxylic acid salt, suitable-pentamethylene-the tetracarboxylic acid hydrochlorate, water miscible polyacrylate and maleic anhydride and vinyl methyl ether or ethene.
Other suitable multi-carboxylate is the polyacetal carboxylation who is disclosed among the US4144226 (people such as Crutchfield, promulgation on March 13rd, 1979), and the document is incorporated herein by reference.
The multi-carboxy acid salt washing agent also is disclosed among the US3308067 (Diehl, promulgation on March 7th, 1967), and the document is incorporated herein by reference.Such material comprises the aliphatic carboxylic acid for example homopolymer of toxilic acid, methylene-succinic acid, methylfumaric acid, fumaric acid, equisetic acid, citraconic acid and methylene radical propanedioic acid and the water-soluble salt of multipolymer.
Also can use other organic washing-assisting detergent known in the art.For example, lipid acid be can use, monocarboxylic acid and its water-soluble salt also are referred to as with long chain hydrocarbon groups.They comprise usually the material that is referred to as " soap ".The general C that uses 10-C 20Chain length.Alkyl can be saturated or undersaturated.
Preferably, clean washing assistant herein is selected from the salt of carbonic acid, silicic acid, sulfuric acid, phosphoric acid, silicoaluminate and citric acid, particular certain cancers and its mixture.
Auxiliary enzymes-optional and preferred component comprises auxiliary enzymes.Described auxiliary enzymes comprises and is selected from following enzyme: proteolytic enzyme, lipase, cellulase, hemicellulase, peroxidase, glucoamylase, at, polygalacturonase, zytase, reductase enzyme, oxydase, oxidation of phenol enzyme, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase, malanases, beta-glucanase, alglucerase or its mixture.It is most preferred that proteolytic enzyme, lipase, peroxidase, cellulase and its mixture." auxiliary enzymes " is meant one or more enzymes in the composition of joining except amylase.
The consumption of auxiliary enzymes in composition changes according to the type and the predetermined purposes of enzyme.Usually, be benchmark with the actives, preferably use about 1.0% (weight) of about 0.0001-, more preferably from about these auxiliary enzymes of about 0.5% (weight) of 0.001-as composition weight.
Can use the purifying of these enzymes or purified form not.Comprising the enzyme of producing by chemistry or genetically altered mutant according to definition, for example is the mutation near the structure enzyme.
Lipase-the lipase that can randomly consider to be included in the cleaning composition of the present invention comprises as disclosed in English Patent 1372034, by the microorganism of pseudomonas, for example Situ Ci Shi aeruginosa atcc 19.154 produce those.Lipase comprises that the antibody with the lipase of being produced by microorganism Pseudomonas fluorescens IAM1057 demonstrates those lipase of positive immunological cross-reaction.This lipase can be from Amano Pharmaceutical Co.Ltd., Nagoya, and Japan obtains with trade(brand)name LipaseP " Amano " (hereinafter referred to as " Amano-P ").Lipase comprises M1 Lipase RAnd Lipomax R(Gist-Brocades) and Lipolase R(Novo).
The add-on of lipase in detergent composition is generally the organized enzyme (in detergent composition weight) of 0.0001%-2%.
According to the preferred component of detergent composition of the present invention is D96L lipase mutation from the natural lipase of Humicola lanuginosa deutero-.The preferred Humicola lanuginosa strain DSM 4106 that uses.The amount that this enzyme preferably joins in the present composition is every liter of about 8500LU of the about 50LU-of washings.More preferably the amount of mutation D96L is every liter of about 7500LU of the about 100LU-of washings and every liter of about 5000LU of the about 150LU-of washings most preferably.
The mutation of D96L lipase is meant as in the described lipase mutation of patent application WO92/05249, promptly wherein is changed into leucine (L) from aspartic acid (D) residue of the natural lipase of Humicola lanuginosa at 96.According to this nomenclature mo, described aspartic acid with 96 positions is substituted by leucine and is expressed as: D96L.
In order to determine the activity of enzyme D96L, use standard LU to measure (analytical procedure, NovoNordisk inside AF 95/6-GB 1991.02.07).Use glue-Sudan Gum-arabic as emulsifying agent by tributyrin (Merck) emulsification being prepared the substrate of D96L.Use the pH saturation method to measure lipase activity at pH7.1 unit lipase activity (LU/mg) is defined as per minute and discharges the needed amount of 1 micromole's lipid acid.
When comparing with wild-type lipase, the D96L mutation of natural Humicola lanuginosa lipase has the additional advantage that remarkable benefit is provided aspect the whiteness maintenance.
Proteolytic enzymeThe amount of-optional the proteolytic enzyme that exists is enough to provide the activity of every gram composition 0.001-0.1Anson unit (AU).This proteolytic enzyme can be animal, plant or microorganism (preferably) source.The serine protease of bacterial origin more preferably.Can use the purifying or the enzyme of purified form not.Comprising the proteolytic enzyme of producing by chemistry or genetically altered mutant according to definition, for example is the mutation near the structure enzyme.Particularly preferably be the bacterial serine proteolytic enzyme that obtains from bacillus, subtilis and/or Bacillus licheniformis as proteolytic enzyme.Commercially available protein enzyme in suitable the be included in present composition comprises Alcalase , Biosam , Esperase , Durazym , Svainase , Maxatase , Maxacat And Maxapem 15 (Maxacal of protein engineering); Purafect With subtilysin BPN and BPN '.
Proteolytic enzyme also comprises the bacterial serine proteolytic enzyme of modification, for example at those proteolytic enzyme described in the european patent application series number 87303761.8 (specifically being the 17th, 24 and 98 page) of application on April 28th, 1987, this enzyme is referred to as " proteolytic enzyme B " herein, with at those proteolytic enzyme described in the 29 days October in 1986 of the Venegas disclosed european patent application 199404, it is meant the bacterial serine proteolytic enzyme of modification, and this enzyme is referred to as " protease A " in this article.More preferably be referred to as the enzyme of " proteolytic enzyme C " herein, this enzyme is the mutation of the alkaline serine protease that obtains from bacillus, wherein replace arginine at 27 Methionins, replace valine at 104 tyrosine, replace aspartic acid and replace Threonine at 123 Serines at 274 L-Ala.Proteolytic enzyme C has narration in 16 days Mays in 1991 corresponding to WO91/06637 among the disclosed EP90915958:4, and the document is incorporated herein by reference.Also comprise the mutation of general modification, the particularly mutation of proteolytic enzyme C herein.
Preferred proteolytic enzyme is selected from: Svainase , Esperase , Maxacal , Purafect , BPN ', protease A and proteolytic enzyme B and its mixture.The bacterial serine proteolytic enzyme that obtains from subtilis and/or Bacillus licheniformis is preferred.
The proteolytic enzyme of particularly preferred herein being referred to as " proteolytic enzyme D " is the carbonylic hydrolase variant with the aminoacid sequence that does not in fact have discovery, it be by following mode from precursor carbonylic hydrolase deutero-: by to being equivalent at described carbonylic hydrolase+amino-acid residue of 76 positions, preferably, numbering according to the bacillus amyloliquefaciens subtilysin, also be equivalent to be selected from+99, + 101, + 103, + 104, + 107, + 123 ,+27 ,+105, + 109, + 126 ,+128 ,+135, + 156, + 166 ,+195 ,+197, + 204, + 206 ,+210 ,+216, + 217, + 218 ,+222 ,+260, + 265, and/or+one or more amino-acid residues of 274 positions are with different aminoacid replacement, as applying on October 13rd, 1994 people such as A.Baeck, the U.S. Patent Application Serial that name is called " cleaning combination (Protease-Containing Cleaning Compositions) that contains proteolytic enzyme " is that the document all is incorporated herein by reference described in the patent application of 08/322676 common submission.
The cellulase that can be used among the present invention comprises bacterium or fungal cellulase.Preferably, their best pH is between 5-9.5.Suitable cellulase is disclosed among people's such as Barbesgoard the US 4435307, and it discloses the fungal cellulase of producing from Humicola insolens.Suitable cellulase also is disclosed in GB-A-2075028; Among GB-A-2095275 and the DE-OS-2247832.
The example of such cellulase is by Humicola insolens (thermophilic grey detritus enzyme variant) bacterial strain, particularly the cellulase of Humicola strain DSM 1800 productions.
Other suitable cellulase is that to come from molecular weight be 5.5 for about 50KDa, iso-electric point and contains the cellulase of 415 amino acid whose Humicola insolens.Specially suitable cellulase is to have the cellulase that color is safeguarded benefit.The example of such cellulase is at the cellulase described in the European Patent Application No. 91202879.2 (Novo) of application on November 6th, 1991.
Peroxidase uses with oxygen source such as percarbonate, perborate, persulphate, hydrogen peroxide etc.They are used for " solution bleaching ", prevent promptly that during washing operation the dyestuff removed from substrate or pigment transfers on other substrate the washings.Peroxidase is known in this area, and comprises, for example, horseradish peroxidase, lignoenzyme and halo peroxidase be chloro and bromoperoxidase for example.The detergent composition that contains peroxidase is disclosed in, for example in the European patent application EP 91202882.6 of PCT International Application No. WO 89/099813 and on November 6th, 1991 application.
The amount that described cellulase and/or peroxidase join in the detergent composition is generally, and the organized enzyme amount is the 0.0001%-2% of detergent composition weight.
That suitable in addition is keratanase [EC 3.1.1.50], and this enzyme can be considered to a kind of special lipase, does not promptly need the lipase of interface activation.Keratanase joined in the detergent composition be described in: for example WO-A-88/09367 (Genencor) has suffered.The add-on of keratanase in detergent composition is generally, and the organized enzyme amount is the 0.0001%-2% of detergent composition weight.
Enzyme stabilizers-can water miscible calcium and/or magnesium ion source that above-mentioned ion offers enzyme be stablized the enzyme that is used for herein by existence in final composition.If (only use one type of cationic word, calcium ion is more effective a little and be preferred in this article than magnesium ion usually.) in addition,, can provide stability: the US4537706 that sees Severson by there being various other prior art disclosed stablizer, especially borates.General washing composition, especially liquid washing agent, every liter of final composition comprise that about 1-is about 30, and preferably about 2-is about 20, more preferably from about 5-about 15 and the most preferably from about calcium ion of the about 12mmol of 8-.The amount that this can exist according to enzyme and its change a little to the irritability of calcium or magnesium ion.Should select the content of calcium or magnesium ion like this, it makes at the washing assistant that allows in the composition after the complexings such as lipid acid, more a spot of enzyme that can be used for is always arranged.Can use any water miscible calcium or magnesium salts as calcium or magnesium ion source, include, but not limited to calcium chloride, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formiate and lime acetate, and corresponding magnesium salts.Because the calcium in enzyme slurries and prescription water, so a spot of calcium ion, the about 0.4mmol/ of about usually 0.05-rises and also often is present in the composition.In solid detergent composition, prescription can comprise that the water-soluble calcium ion source of q.s is so that provide above-mentioned amount in washing liquid.In another selectable method, natural water hardness is just enough.
Should be appreciated that the calcium of above-mentioned content and/or magnesium ion are enough to provide enzyme stability.More calcium and/or magnesium ion can be joined in the composition to provide additional removal greasy performance.Therefore, as a general suggestion, composition herein generally includes water-soluble calcium or the magnesium ion source of about 0.05-about 2% (weight), perhaps two kinds of ion sources.Certainly, its amount can change according to the type and the amount of the enzyme that uses in composition.
Composition herein also can be selectively, but preferably contain various other stablizers, especially borate type stablizer.Usually, the amount that such stablizer uses in composition is about 0.25-about 10%, preferred about 0.5-is about 5%, and more preferably from about the boric acid of 0.75-about 3% (weight) or other can form the borate compound (is benchmark calculating with boric acid) of boric acid in composition.Boric acid is preferred, although other compounds for example boron oxide, borax and other alkali metal borate (for example just-, partially-and sodium pyroborate, and sodium pentaborate) be suitable for.Also can use the boric acid (for example phenyl-boron dihydroxide, butane boric acid and right-bromophenylboronic acid) of replacement to replace boric acid.
Other component-be applicable to that other component in the present composition can comprise: for example, water, spices, carrier, hydrotropic agent, processing aid, whitening agent, amendment are for example forged silicon-dioxide, polyoxyethylene glycol, dyes and dyestuffs, and the peroxy acid of system.(preferred molecular weight is between 5000-10000 for the polyoxyethylene glycol of about 0.5-about 5% (weight) that the preferred component amount of being is a composition, most preferably 8000), the spices of the fluorescent brightening of about 0.01-about 0.7% (weight) and/or brightening agent and about 0.01-about 1.0% (weight).High if desired whipability so can be with profoamer C for example 10-C 16Alkanolamide joins in the composition, and its amount is generally 1%-10%.C 10-C 14Monoethanolamine and diglycollic amide have illustrated this general class A foam A secondary accelerator.It also is favourable using such profoamer with the blistered additional surfactants of height for example above-mentioned amine oxide, trimethyl-glycine and sultaine.If desired, can add for example MgCl of soluble magnesium salts 2, MgSO 4Deng, its amount is generally 0.1%-2%, removes greasy performance so that additional foam is provided and strengthens.
The various washing components that use in the present composition randomly can also be adsorbed on described component on the porous hydrophobic matrix, apply described matrix with hydrophobic coating then and further stablize.Preferably, before being adsorbed into porous matrix, should washing component and mix with tensio-active agent.In use, the washing component discharges from matrix and enters aqueous cleaning solution, and it plays its predetermined washing function in aqueous cleaning solution.
In order to illustrate in greater detail this technology, with porous hydrophobic silicon-dioxide (trade mark is SIPERNAT D10, DeGussa) with contain 3%-5%C 13-15The protein enzyme solution of ethoxylated alcohol (EO7) nonionogenic tenside mixes.Usually, enzyme/surfactant soln is 2.5 times of silica weight.Under agitation the powder that obtains is dispersed in the silicone oil (can use the various silicone oil of viscosity) at 500-12500.With the silicone oil dispersion liquid emulsification of gained or with other method it is joined in the final detergent base.In this way; can " protect " to be used for the component that washing composition comprises liquid laundry detergent compositions for example above-mentioned enzyme, SYNTHETIC OPTICAL WHITNER, bleach-activating agent, bleaching catalyst, light activating agent, dyestuff, white dyes, fabric conditioner and hydrolyzable tensio-active agent.
Liquid detergent composition can contain water and other solvent as carrier.It is suitable coming illustrational lower molecular weight uncle or secondary alcohol with methyl alcohol, ethanol, propyl alcohol and Virahol.For making surface active agent solubilization, monohydroxy-alcohol is preferred, but also can use polyvalent alcohol, for example contains those (for example, 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol) of about 6 carbon atoms of 2-and about 6 hydroxyls of 2-.Said composition can contain 5%-90%, such carrier of general 10%-50%.
Another optional component is a suds suppressor, for example siloxanes, and silicon-dioxide-mixture of siloxanes.Siloxanes can represent with alkylating silicone materials, and generally uses silicon-dioxide, for example various types of aerosils and xerogel and water drain silica with finely divided form.These materials can be used as particle and add, and wherein suds suppressor is incorporated in the impermeable carrier of water-soluble or water dispersible, essentially no surface-active washing composition advantageously, releasedly.In addition, can or be dispersed in the liquid vehicle and suds suppressor dissolving and use by being sprayed on one or more other components.
Preferred silicone foam control agent is disclosed among people's such as Bartollota the US3933672.Other useful especially suds suppressor is the silicone suds suppressor that is described in the self-emulsifying among the German patent application DTOS2646126 (on April 28th, 1977 is open).The example of this compound is DC-544, can buy from Dow Corning, and it is siloxanes-glycol multipolymer.Particularly preferred Foam Control is the suds suppressor system that contains silicone oil and 2-alkyl-chain triacontanol mixture.Suitable 2-alkyl-alkanol is can be with trade(brand)name Isofol 12 2-butyl-octanol of buying.
Such suds suppressor system is described in the common unsettled European Patent Application No. 92870174.4 of application on November 10th, 1992.
Particularly preferred silicone foam control agent is described in the common unsettled European Patent Application No. 92201649.8.Described composition can contain and the non-porous silicon-dioxide of forging system Aerosil for example Bonded siloxanes/silica mixture.
The consumption of above-mentioned suds suppressor is generally the 0.001%-2% (weight) of composition, preferred 0.01%-1% (weight).
Can use other component that is used for detergent composition, for example the spices of soil-suspending agent, dirt release agent, white dyes, friction agent, sterilant, tarnish inhibitor, tinting material and/or encapsulate or non-encapsulate.
Specially suitable cover material is a water-soluble capsule, and it is by polysaccharide with such as forming at the matrix of the polyol described in the GB1464616.
Other suitable water-soluble cover material comprises such as the dextrin at the starch acid ester derivative of the replacement dicarboxylic acid of the gelationization never described in the US3455838.These acid esters dextrin are preferably from for example wax shape corn, wax shape Chinese sorghum, sago, tapioca (flour) and the yam starch preparation of such starch.The suitable example of described cover material comprises the N-Lok that is made by National Starch.This N-Lok cover material is made up of the W-Gum and the glucose of modification.By add group that simple function replaces for example octenyl succinic acid anhydride with this starch conversion.
Suitable herein anti redeposition agent and soil-suspending agent comprise derivatived cellulose, for example the poly carboxylic acid of methylcellulose gum, carboxymethyl cellulose and Natvosol and homopolymerization or copolymerization or its salt.This base polymer comprises above-mentioned polyacrylate and copolymer of maleic anhydride and acrylic acid as washing assistant, and the multipolymer of maleic anhydride and ethene, methylvinylether or methacrylic acid, and maleic anhydride constitutes at least 20% (mole) of this multipolymer.The consumption of these materials is generally the 0.5%-10% of composition weight, more preferably 0.75%-8%, most preferably 1%-6%.
Preferred white dyes is an anionic property, its example is: 4,4 '-two-(2-diethanolamino-4-anilino-s-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium salt, 4,4 '-two-(2-morpholino-4-anilino-s-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 4 '; 4 "-two-(2,4-hexichol amido-s-triazine-6-base is amino) stilbene-2-sulfonic acid one sodium, 4 '; 4 "-two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 4,4 '-two-(4-phenyl-2,1,3-triazole-2-yl) stilbene-2:2 '-disulfonic acid disodium, 4,4 '-two-(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazine-6-base is amino) stilbene-2:2 '-disulfonic acid disodium, 2 (stilbene radicals-4 "-(naphtho--1 '; 2 ': 4; 5)-1; 2; 3-triazole-2 "-sodium sulfonate and 4,4 '-two-(2-sulfo group styryl) biphenyl.
Other useful polymeric material is a polyoxyethylene glycol, and particularly molecular weight is 1000-10000, more preferably 2000-8000 and most preferably from about 4000 those.Their consumption is 0.20%-5% (weight), more preferably 0.25%-2.5% (weight).The multi-carboxylate of these polymkeric substance and above-mentioned homopolymerization or copolymerization keeps for improving whiteness, the fabric ash deposition and when having transition metal impurity the cleaning performance to clay, protein and oxidable dirt all be of great value.
Useful dirt release agent is terephthalic acid and ethylene glycol and/or the unitary conventional multipolymer of propylene glycol or the terpolymer of various arrangements in the present composition.The example of polymkeric substance is disclosed among the US4116885 and US4711730 and European Patent Application No. 0272033 of common transfer like this.Particularly preferred polymkeric substance according to EP-A-0272033 has following formula: (CH 3(PEG) 43) 0.75(POH) 0.25[(T-PO) 2.8(T-PEG) 0.4] T (POH) 0.25((PEG) 43CH 3) 0.75Wherein PEG is-(OC 2H 4) O-, PO is (OC 3H 60) and T be (pcOC 6H 4CO).
Also very usefully as terephthalic acid dimethyl ester, sulfoisophthalic acid dimethyl ester, ethylene glycol and 1, the modified poly ester of the random copolymers of 2-propylene glycol, this end group mainly are made up of the monoesters of ethylene glycol and/or propylene glycol sulfosalicylic acid ester and time strategic point.Purpose is to obtain at two ends by the end capped polymkeric substance of sulfosalicylic acid ester group, and " mainly " in this article refers to herein that the major part of described multipolymer is end capped by the sulfosalicylic acid ester group.Yet some multipolymer is not end capped fully, so its end group can be by ethylene glycol and/or propane-1, and the monoesters of 2-glycol is formed, and its " inferior strategic point " is made up of above-mentioned substance.
The polyester of Xuan Zeing contains the terephthalic acid dimethyl ester of 46% (weight) of having an appointment herein, the propane of about 16% (weight)-1, the 2-glycol, the ethylene glycol of about 10% (weight), the sulfosalicylic acid dimethyl ester of about 13% (weight) and the sulfoisophthalic acid of about 15% (weight), its molecular weight is about 3000.This polyester and its preparation method at length are described among the EPA311342.
Fabric softener can be joined according in the laundry detergent composition of the present invention.These fabric softeners are inorganic or organic types.The example of inorganic softening agent is the smectic clays that is disclosed among GB-A-1400898 and the US5019292.The organic fabric softening agent comprise as disclosed water miscible tertiary amine in GB-A1514276 and EP-B0011340 and its be disclosed in the single C12-C14 quaternary ammonium salt among EP-B-0026527 and the EP-B-0026528 and as be disclosed in the mixture of two long-chain acid amides among the EP-B-0242919.The useful organic component of in the fabric sofetening system other comprises as being disclosed in the high molecular weight polyethylene oxide material in EP-A-0299575 and 0313146.
The content of smectic clays is generally in the scope of 5%-15% (weight), and more preferably 8%-12% (weight), this material mix in the residuum that component joins prescription as doing.The organic fabric softening agent for example add-on of water-soluble tertiary amine or two long-chain acid amides materials is 0.5%-5% (weight), general 1%-3% (weight), and the add-on of high molecular weight polyethylene oxide material and water-soluble cationic material is 0.1%-2% (weight), general 0.15%-1.5% (weight).These materials generally join the spraying drying part of composition, although add as do mixing particle in some cases, perhaps being sprayed to as melt liquid may be more convenient on other solid constituent of composition.
The present invention also relates to a kind of dyestuff that is suppressed at dissolving that fabric washing operating period of comprising yarn dyed fabric runs into and suspension and transfer to the method for another fabric from a fabric.
Can contain 0.001%-10% (weight) according to detergent composition of the present invention, preferred 0.01%-2% (weight), more preferably the polymeric dye transfer inhibitor of 0.05%-1% (weight).Transfer to from yarn dyed fabric on the fabric that wherein is washed in order to suppress dyestuff, generally described polymeric dye transfer inhibitor is joined in the detergent composition.These polymkeric substance had before the fugitive dye that washs out from yarn dyed fabric has an opportunity to be attached to other goods in the washing with regard to the complexing or the ability of adsorbing these dyestuffs.
Specially suitable polymeric dye transfer inhibitor is multipolymer, polyvinyl pyrrolidone polymers, Ju Yi Xi oxazolidinone and the polyvinyl imidazol of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole, or its mixture.
The polyamine N-oxide pllymers that is suitable for contains the unit of following structural formula:
Figure C9619714300231
Wherein P is a polymerizable unit, wherein the R-N-O group can be connected on the polymerizable unit, or wherein this R-N-O group forms the part of polymerizable unit or both combinations; A is NC (O), CO 2, C (O) ,-O-,-S-,-N-; X is 0 or 1; R be aliphatic series, ethoxylation aliphatic series, aromatics, heterocycle or alicyclic group or its arbitrary combination, the nitrogen-atoms of this N-O group can connect on it or wherein the nitrogen-atoms of this N-O group be the part of these groups.
This N-O group can be the part of this polymerizable unit (P), maybe can be connected on the polymeric skeleton, or both combinations.
The polyamine N-oxide that suitable wherein N-O group forms a polymerizable unit part comprises that R wherein is selected from the polyamine N-oxide of aliphatic series, aromatics, alicyclic or heterocyclic group.
The described polyamine N-oxide of one class comprises that the nitrogen-atoms of N-O group wherein forms this class polyamine N-oxide of this R-group part.Preferred polyamine N-oxide compound is that wherein R is for example polyamine N-oxide of pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and its derivative of heterocyclic group.
Another kind of described polyamine N-oxide comprises that the nitrogen-atoms of N-O group wherein is connected to the polyamine N-oxide on this R-group.
Other suitable polyamine N-oxide is that this N-O group is connected to the polyamine N-oxide on the polymerizable unit.
The preferred type of these polyamine N-oxide is the polyamine N-oxide with general formula (I), and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen-atoms of this N-O functional group is the part of described R group.
This class examples of substances is that wherein R is for example polyamine oxide compound of pyridine, pyrroles, imidazoles and its derivative of heterogeneous ring compound.
Another kind of preferred polyamine N-oxide compound is the polyamine oxide compound with general formula (I), and wherein R is aromatics, heterocycle or alicyclic group, and wherein the nitrogen-atoms of this N-O functional group is connected on the described R group.
This class examples of substances is that wherein R can be for example polyamine oxide compound of phenyl of aromatic group.
Can use any polymer backbone, as long as the amine oxide polymkeric substance that forms is water miscible and has the dye transfer inhibition activity.The example of suitable polymeric skeleton is polyethylene base class, polyalkylene class, polyester, polyethers, polymeric amide, polyimide, polyacrylate and its mixture.
The amine of amine n-oxide polymkeric substance of the present invention and the ratio of amine n-oxide generally are 10: 1-1: 1000000.Yet the quantity that is present in the amine oxide group in the polyamine oxide polymer can change by suitable copolymerization or by suitable N-oxidisability.Preferably, the ratio of amine and amine n-oxide is 2: 3-1: 1000000.More preferably 1: 4-1: 1000000, most preferably 1: 7-1: 1000000.In fact polymkeric substance of the present invention comprises that wherein a kind of monomer type is amine n-oxide and other monomer types or amine n-oxide or is not the random or segmented copolymer of amine n-oxide.The unitary PKa of the amine oxide of polyamine N-oxide＜10, preferred PKa＜7, more preferably PKa＜6.
Can obtain the polyamine oxide compound with any polymerization degree almost.The polymerization degree is not conclusive, as long as this material has needed water-soluble and dye suspension ability.
Usually, molecular-weight average is in the scope of 500-1000000; Preferred 1000-50000; More preferably 2000-30000; 3000-20000 most preferably.
The average molecular weight range that can be used for the present invention's N-vinyl imidazole N-vinyl pyrrolidone polymer is 5000-1000000, preferred 20000-200000.
The polymkeric substance according to detergent composition of the present invention of being used for very preferably comprises and is selected from N-vinyl imidazole N-vinylpyrrolidone copolymer, the molecular-weight average of wherein said polymkeric substance is in the scope of 5000-50000, more preferably 8000-30000, most preferably 10000-20000.
Average molecular weight range be by as Barth H.G. and Mays J.W. at chemical analysis (Chemical Analysis), the determination of light scattering described in the 113rd volume " modernism of polymer characterization (ModernMethods of Polymer Characterization) ".
The molecular-weight average of N-vinyl imidazole N-vinylpyrrolidone copolymer very preferably is at the scope of 5000-50000, more preferably 8000-30000, most preferably 10000-20000.
This N-vinyl imidazole N-vinylpyrrolidone copolymer is characterised in that to have described average molecular weight range, and fabulous dye transfer inhibition activity is provided, and the cleaning performance of detergent composition to preparation does not have adverse influence simultaneously.
The N-vinyl imidazole of N-vinyl imidazole N-vinylpyrrolidone copolymer of the present invention and the mol ratio of N-vinyl pyrrolidone are 1-0.2, more preferably 0.8-0.3, most preferably 0.6-0.4.
Detergent composition of the present invention also can use molecular-weight average about 400000 for about 2500-, preferably about 5000-about 200000 and more preferably from about 5000-about 50000 and the most preferably from about Polyvinylpyrolidone (PVP) of 5000-about 15000 (" PVP ").Suitable polyvinylpyrrolidone can be from ISP Corporation, New York, NY and Montreal, Canada is with ProductName PVP K-15 (viscosity molecular weight is 10000), PVP K-30 (molecular-weight average is 40000), PVP K-60 (molecular-weight average is 160000) and PVP K-90 (molecular-weight average is 360000) buy.What other was suitable can comprise Sokalan HP165 and Sokalan HP12 from the polyvinylpyrrolidone that BASF Cooperation buys; Polyvinylpyrrolidone is known (see, for example, EP-A-262897 and EP-A-256696) to the technician of detergent applications.
Detergent composition of the present invention also can use Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.The molecular-weight average of described Ju Yi Xi oxazolidinone is about 400000 for about 2500-, and preferably about 5000-is about 200000, more preferably from about 5000-about 50000 and most preferably from about 5000-about 15000.
Detergent composition of the present invention also can use polyvinyl imidazol as the polymeric dye transfer inhibitor.The molecular-weight average of described polyvinyl imidazol alkane ketone is about 400000 for about 2500-, and preferably about 5000-is about 200000, more preferably from about 5000-about 50000 and most preferably from about 5000-about 15000.
Preferred preparation like this detergent composition herein, it makes and is used for during the moisture cleaning operation that the pH of washing water is between about 6.5-about 11, preferably between about 7.5-11.The technology of controlling pH with the consumption of recommending comprises use buffer reagent, alkali, acid etc., and well known to those skilled in the art.
Liquid detergent composition is joined in the washings, and its amount is generally the 1/4-1 cup.
The present invention also provides and has been in the suds by making the fabric method of cleaning fabrics that contacts with the washings of the detergent composition mentioned above that contains significant quantity.For good cleaning, preferably in washing machine, provide stirring.The preferred fabric drying that then in the clothes drying machine of routine, will wet of washing.The about 7000ppm of the preferably about 500-of the significant quantity of the liquid detergent composition in washing machine, the more preferably from about about 3000ppm of 1000-.
Following embodiment has illustrated composition of the present invention, but is not meant restriction or limits this in addition
Scope of invention.
In detergent composition, the component symbol of abbreviation has following implication:
Dummy suffix notation
The amine surface be selected from coconut alkyl dimethyl amine, dimethyl oil base amine,
Promoting agent hexadecyl three (vinyloxy group) dimethyl amine, tallow
Two (2-hydroxyethyl) amine of alkyl, stearyl-are two
Two (the 2-hydroxyls of (2-hydroxyethyl) amine and oleoyl
The base ethyl) amine and its mixture
The LAS straight chain C 12Sodium alkyl benzene sulfonate
TAS tallow alkyl sodium sulfate
AS C 8-C 18Sodium alkyl sulfate
The C of SAS sodium-salt form 12-C 14Secondary (2,3) alkyl-sulphate
APG formula C 12-(glucosyl) xThe alkyl polyglycoside surfactivity
Agent, wherein x is 1.5
AEC formula C 12The alkyl ethoxy carboxylic acid of oxyethyl group (2) carboxylate salt
Salt surfactant
The sad secondary soap surfactant of SS formula 2-butyl
The C that is mainly of 25EY and average Y moles of ethylene oxide condensation 12
-C 15Straight chain primary alcohol
The C that is mainly of 45EY and average Y moles of ethylene oxide condensation 14
-C 15Straight chain primary alcohol
The C of XYEZS and the condensation of every mole of average Z moles of ethylene oxide 1x
-C 1YSodium alkyl sulfate
Nonionic by BASF Gmbh with trade(brand)name Plurafax LF404
The average degree of ethoxylation that live to sell on the surface is 3.8 and average third oxygen
Property agent base degree is 4.5 C 13-C 15Mixed ethoxylated/
Propoxylated fatty alcohol
CFAA C 12-C 14Alkyl N-methyl glucose amide
TFAA C 16-C 18Alkyl N-methyl glucose amide
Silicate amorphous silicic sodium (SiO 2: Na 2O is than=2.0)
NaSKS-6 formula δ-Na 2Si 2O 5Toxilic acid/acrylic copolymer of 1: 4 of crystalline layered silicate carbonate Carbon Dioxide na phosphates tripoly phosphate sodium STPP MA/AA, mean molecule
Amount is that about 80000 polyacrylates are by BASF GmbH putting down with trade(brand)name PA30 sale
Average molecular weight is 8000 polyacrylate homopolymer zeolite A formula Na 12(AlO 2SiO) 12.27H 2The primary particle diameter of O is 1
-10 microns hydrated sodium aluminosilicate Citrate trianion citrate trisodium dihydrate citric acid citric acid perborate anhydrous sodium perborate monohydrate SYNTHETIC OPTICAL WHITNER, empirical formula is
NaBO 2.H 2O 2PB4 anhydrous sodium perborate tetrahydrate percarbonate empirical formula is 2Na 2CO 3.3H 2O 2Anhydrous sodium perborate
SYNTHETIC OPTICAL WHITNER TAED tetra acetyl ethylene diamine paraffin is sold with trade(brand)name Winog70 by Wintershall
The paraffin oil zytase by Novo Nordisk A/S with trade(brand)name Pulpzyme
HB or SP431 or Lyxasan (Gist-
Brocades) or Optipulp or Xylanase
(Solvay) the zytase proteolytic enzyme of Xiao Shouing by Novo Nordisk A/S with trade(brand)name Savinase
The protease protein enzyme D that sells is according to bacillus amyloliquefaciens subtilysin numbering, and is slow
Slow genus bacillus subtilisin BPN ' variants N76D/S103A
The proteolytic enzyme amylase of/V104I by Novo Nordisk A/S with trade(brand)name Termamyl
The amylase lipase of selling by Novo Nordisk A/S with trade(brand)name Lipolase Pin
The lipolytic enzyme of selling
D96L lipase is from the natural lipase of Humicola lanuginosa deutero-
Mutation
The peroxidase peroxidase
Cellulase by Novo Nordisk A/S with trade(brand)name Carezyme
Or Celluzyme The cellulase of selling
The CMC Xylo-Mucine
HEDP 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid
DETPMP by Monsanto with trade(brand)name Dequest 2060 Sell
Diethylenetriamine five (methylene phosphonic acid)
The PVP polyvinyl pyrrolidone polymers
Quadrol-the N of EDDS sodium-salt form, N '-disuccinic acid sodium, [S, S]
Isomer
Suds suppressor 25%Mpt50 ℃ paraffin, 17% hydrophobic dioxy
Change silicon, 12% of 58% paraffin oil or particle form
Siloxanes/silicon-dioxide, 18% stearyl alcohol, 70%
The starch cumene sodium sulfonate
The SCS cumene sodium sulfonate
The vitriol anhydrous sodium sulphate
The HMWPEO high molecular weight polyethylene oxide
The Polyglycerine Stearinsaeure of PGMS commodity Radiasurf248 by name
Ester
TAE25 tallow alcohol ethoxylate (25)
Among the embodiment, the content of the enzyme of all references is all represented with % organized enzyme (with composition weight meter) below.
Example I
Evaluation is according to the diastatic scourability in the nonphosphate liquid washing agent of following composition preparation:
Material Wt.%
C 12-C 14Alkyl N-methyl glucose amide 3.0
NaC25AE2.5S 17.0
Neodol 23-9 1.0
Citric acid washing assistant 2.0
Lipid acid washing assistant 3.0
Ethane 3.0
Propylene glycol 5.0
NaOH 3.0
Sodium formiate 0.05
Borax 2.5
Ethylene methacrylic amine 1.0
Proteinase-10 .2
Amylase *0.2
Siloxanes antifoams 0.1
PEI 189 E15-18 (four ethylidene, five imines of ethoxylation) 1.0
Water and accessory constituent to 100%
Replace amylase: Termamyl with following listed amount with following amylase , Genecor Purafact Ox Am , and Duramyl
Carrying the hardness that adds 5 pounds of fabrics of making dirty naturally and 64 liters 95 in the formula automatic washing machine to the top is the municipal water of 6 grain/gallons.In each washing machine, add 1/2 glass and have diastatic liquid washing agent.
Allow washing machine finish conventional washing and rinse cycle then, and with the fabric drying machine drying of testing.This process repeats 4 times.
After 4 circulations are finished,, fabric is placed on irradiation under the suitable light for the relatively removal of dirt and stain.This fabric demonstrates improved whiteness.
Example II
By being prepared as follows the heavy-filth liquid fabric cleaning composition of the present invention that is applicable to pre-treatment stain fabric and is applicable to washing machine washing method:
I II III IV V
Amine 10.0 15.0 5.0 10.0 5.0
24AS 20.0 20.0 20.0 20.0 20.0
SS 5.0 5.0 5.0 5.0 5.0
Citrate trianion 1.0 1.0 1.0 1.0 1.0
12E 3 13.0 13.0 13.0 13.0 13.0
Monoethanolamine 2.5 2.5 2.5 2.5 2.5
Proteolytic enzyme 0.005 0.01 0.1 0.0 0.005
Amylase 0.005 0.05 0.2 0.0004 0.01
Cellulase 0.0 0.04 0.004 0.001 0.0
Water/propylene glycol/ethanol (100: 1: 1)
Amylase comprises: Termamyl , Genecor Purafact Ox Am , and Duramyl
EXAMPLE III
By being prepared as follows heavy-filth liquid fabric cleaning composition of the present invention:
I II III IV
LAS acid form - - 25.0 -
C 12-14Alkenyl succinic 3.0 8.0 10.0 -
Citric acid 10.0 15.0 2.0 2.0
25AS acid form 8.0 8.0 - 15.0
25AE2S acid form - 3.0 - 4.0
25AE7 - 8.0 - 6.0
25AE3 8.0 - - -
CFAA - - - 6.0
DETPMP 0.2 - 1.0 1.0
Lipid acid - - - 10.0
Oleic acid 1.8 - 1.0 -
Ethanol 4.0 4.0 6.0 2.0
Propylene glycol 2.0 2.0 6.0 10.0
Zytase 0.05 0.0 0.05 0.0
Amylase 0.005 0.01 0.2 0.0001
Coconut alkyl dimethyl hydroxyethyl ammonium chloride - - 3.0 -
Smectic clays - - 5.0 -
PVP 1.0 2.0 - -
Perborate - 1.0 - -
Phenolsulfonate - 0.2 - -
Peroxidase - 0.01 - -
NaOH pH7.5 pH7.5 pH7.5 pH7.5
Water/accessory constituent To 100% To 100% To 100% To 100%
Amylase comprises: Termamyl , Genecor Purafact Ox Am , and Duramyl
EXAMPLE IV
By being prepared as follows heavy-filth liquid fabric cleaning composition of the present invention:
I II III
CFAA 5.0 4.5 3.9
25AS acid form 15.0 13.0 7.5
25AE2S acid form 9.0 8.0 11.0
Amine tensio-active agent C 8-10Amine 2.0 2.0 2.5
The lipid acid washing assistant 5.0 4.0 3.5
Citric acid 4.0 3.5 3.0
Cellulase 0.27 0.0 0.05
Lipase 0.15 0.0 0.075
Proteolytic enzyme D 0.05 0.05 -
Proteolytic enzyme - - 0.1
Zytase 0.05 0.05 0.05
Amylase 0.015 0.05 0.1
Sequestrant 1.0 1.0 0.75
Soil release polymers 0.2 0.25 0.15
Dispersion agent 0.25 0.7 1.2
Water/accessory constituent To 100%
Amylase comprises: Termamyl , Genecor Purafact Ox Am , and Duramyl
EXAMPLE V
By being prepared as follows particle fabric cleaning composition of the present invention:
A B
LAS 22.0 22.0
Phosphoric acid salt 23.0 23.0
Carbonate 23.0 23.0
Silicate 14.0 14.0
Zeolite A 8.2 8.2
DETPMP 0.4 0.4
Sodium sulfate 5.5 5.5
Proteolytic enzyme 0.01 0.02
Cellulase 0.001 -
Amylase * 0.01 0.1
Water/accessory constituent To 100% To 100%
*Amylase comprises: Termamyl , Genecor Purafact Ox Am , and Duramyl
The moisture crutcher mixture of the detergent composition component that preparation heat and alkali are stable and spraying drying and do mixed other component, make they contain shown in component in the form of content.
Example VI
By being prepared as follows particle fabric cleaning composition of the present invention:
A B
LAS 12.0 12.0
Zeolite A 26.0 26.0
SS 4.0 4.0
SAS 5.0 5.0
Citrate trianion 5.0 5.0
Sodium sulfate l7.0 17.0
Perborate 16.0 l6.0
TAED 5.0 -
Proteolytic enzyme 0.06 0.03
Amylase * 0.0l 0.2
Water/accessory constituent To 100% To 100%
*Amylase comprises: Termamyl , Genecor Purafact Ox Am , and Duramyl
The moisture crutcher mixture of the detergent composition component that preparation heat and alkali are stable and spraying drying and do mixed other component, make they contain shown in component in the form of content.
Example VII A
By being prepared as follows useful especially particle fabric cleaning composition of the present invention in painted fabric washing:
LAS 11.4 10.7
TAS 1.8 2.4
TFAA - 3.0
45AS 3.0 5.0
45E7 4.0 -
25E3S - 3.0
68E11 1.8 1.8
Citrate trianion 14.0 15.0
Citric acid 3.0 2.5
Zeolite A 32.5 32.1
Na-SKS-6 - 9.0
MA/AA 5.0 5.0
DETPMP 1.0 0.2
Zytase 0.01 -
Proteolytic enzyme 0.02 0.02
D96L 0.0005 0.01
Amylase * 0.03 0.2
Silicate 2.0 2.5
Vitriol 3.5 5.2
PVP 0.3 0.5
Poly-(4-vinylpridine)-N-oxide compound/vinyl imidazole and vinylpyrrolidone copolymers - 0.2
Perborate 0.5 1.0
Peroxidase 0.01 0.01
Phenolsulfonate 0.1 0.2
Water/accessory constituent To 100% To 100%
*Amylase comprises: Termamyl , Genecor Purafact Ox Am , and Duramyl
The moisture crutcher mixture of the detergent composition component that preparation heat and alkali are stable and spraying drying and do mixed other component, make they contain shown in component in the form of content.
Example VII A I
Preparation contains the laundry bars that is applicable to the dirty fabric of hand washing of following component:
Component Weight %
Linear alkylbenzene sulfonate 30
Phosphoric acid salt (as tripoly phosphate sodium STPP) 7
Yellow soda ash 20
Trisodium phosphate 7
The coconut single ethanol amide 2
Zeolite A (0.1-10 micron) 5
Carboxymethyl cellulose 0.2
Polyacrylate (MW 1400) 0.2
The N-acyl caprolactam 5
Sodium perborate tetrahydrate 10
Whitening agent, spices 0.2
Amylase 0.05
CaSO 4 1
MgSO 4 1
Water 4
Filler * Surplus to 100%
Amylase comprises: Termamyl , Genecor Purafact Ox Am , and Duramyl
*Can be selected from for example CaCO of suitable material 3, talcum, clay, silicate etc.
Extruding washing composition laundry bars in the producing apparatus of normally used conventional soap in this area or detergent bar.
Example I X
By being prepared as follows dense granule shape fabric cleaning composition:
I II III
Component wt％ wt％ wt％
LAS - 8.0 -
TAS - 2.0 -
45AS 8.0 10.0
25E3S 2.0 0.5 3.0
25E5 - 5.0 5.0
25E3 5.0 - -
TFAA 2.5 - 2.5
Coconut alkyl dimethyl hydroxyethyl ammonium chloride - 1.0 -
Zeolite A 17.0 15.0 25.0
NaSKS-6 12.0 10.0 12.0
Citric acid 3.0 2.0 3.0
Trisodium Citrate - - 10.0
Carbonate 7.0 8.0 7.0
MA/AA 5.0 1.0 5.0
CMC 0.4 0.4 0.4
Poly-(4-vinylpridine)-N-oxide compound 0.2 - 0.2
Proteolytic enzyme 0.05 0.03 0.05
Lipase * 0.002 0.004 0.002
Cellulase 0.001 - 0.001
Amylase 0.01 0.006 0.006
TAED 6.0 3.0 -
Percarbonate 22.0 20.0 -
NACA-OBS - 3.0 -
EDDS 0.3 0.2 0.3
The particulate state suds suppressor 3.5 3.0 3.5
Water/accessory constituent (vitriol) To 100%
*Lipase is selected from: Lipolase TMOr Lipolase Ultra TM(being called DL 96L), the two is all provided by Novo Nordisk.
Embodiment X
By being prepared as follows high-density dense granule shape fabric detergent composition:
I II III
Component wt％ wt％ wt％
AS 7.4 5 16
AES 0.8 - -
LAS 12 21 10
AE 3 3 3
Polyhydroxy fatty acid amide 1 - -
Cationic quaternary ammonium compound 1 1 1
Amylase 0.001 0.05 0.1
Biosam Proteolytic enzyme 0.001 0.005 -
Zeolite 17 7 27
Na SKS-6 6 3.3 -
Citric acid 1 - -
The multi-carboxylate 3 7 2
Sequestrant 0.4 - 0.6
Carbonate 18 10 28
Silicate 4 11 0.5
Perborate 11 4 29
Nonanoly acyloxy benzene sulfonate 2.5 3 -
TAED 4.8 - 5
Soil release polymers 0.3 0.3 0.3
PEG 0.8 - 1.5
Foam Control 0.3 0.2 0.3
Vitriol Surplus Surplus Surplus
Amylase comprises: Termamyl , Genecor Purafact Ox Am , and Duramyl

Claims (9)

1. one kind is washed dark fabric especially effective laundry detergent composition simultaneously to cleaning and brightening, and said composition contains:
A. detergent surfactant, this tensio-active agent is selected from: negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionics and its combination, and the amount that this tensio-active agent exists is the 1%-40% of composition weight; With
B. one or more amylase, the amount of its existence is the active amylase of every gram composition 0.001mg-2mg.
2. according to the detergent composition of claim 1, wherein
A. detergent surfactant accounts for the 2%-25% (weight) of composition, and is nonionic or anion surfactant; With
B. active amylase is the active amylase of every gram composition 0.01mg-1mg.
3. according to the detergent composition of claim 2, wherein by using any naturally occurring 197 L-amino acid or diastatic replacement of similar parent that is positioned at Bacillus licheniformis to strengthen this amylase with the source position mutation.
4. according to the detergent composition of claim 3, wherein
A. Threonine or the diastatic replacement with the source position mutation of similar parent that is positioned at 197 methionine residue of Bacillus licheniformis by use strengthens this amylase;
B. this tensio-active agent is selected from: amine, C 11-13Linear alkylbenzene sulfonate, C 12-16The combination of alkyl-sulphate, methyl ester sulfonate and these tensio-active agents; With
C. said composition also amount be the detergent builders of the 20%-70% of composition weight.
5. according to the detergent composition of claim 4, wherein said composition also amount be the clean washing assistant that is selected from lipid acid, Citrate trianion, carbonate, silicate, vitriol, phosphoric acid salt, silico-aluminate and its combination of the 20%-70% of composition weight.
6. according to the detergent composition of claim 5, wherein said composition also contains proteolytic enzyme.
7. according to the detergent composition of claim 1, said composition is a particle form.
8. according to the detergent composition of claim 1, said composition is a liquid form.
9. a laundering of textile fabrics is so that the method for the reduction smell relevant with dirt and stain, and described method comprises: the fabric that makes the band stain of needs control smell and dirt contacts with the aqueous solution that tensio-active agent and diastatic detergent composition form that contains by claim 1.
CN96197143A 1995-07-24 1996-07-18 Dingy fabric clean-up with amylase enzyme in detergent compsns. Expired - Fee Related CN1105173C (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US133895P 1995-07-24 1995-07-24
US60/001,338 1995-07-24
US1742596P 1996-05-08 1996-05-08
US60/017,425 1996-05-08

Publications (2)

Publication Number Publication Date
CN1197478A CN1197478A (en) 1998-10-28
CN1105173C true CN1105173C (en) 2003-04-09

Family

ID=26668893

Family Applications (1)

Application Number Title Priority Date Filing Date
CN96197143A Expired - Fee Related CN1105173C (en) 1995-07-24 1996-07-18 Dingy fabric clean-up with amylase enzyme in detergent compsns.

Country Status (10)

Country Link
EP (1) EP0842254B1 (en)
JP (1) JP2001519831A (en)
CN (1) CN1105173C (en)
BR (1) BR9609721A (en)
CA (1) CA2227752C (en)
CZ (1) CZ19698A3 (en)
DE (1) DE69618465T2 (en)
HU (1) HUP9901584A3 (en)
MX (1) MX9800746A (en)
WO (1) WO1997004067A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6725490B2 (en) 2001-11-06 2004-04-27 The Procter & Gamble Company Complex motion toothbrush

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HUP9903559A3 (en) * 1996-08-01 2000-08-28 Procter & Gamble Detergent compositions comprising improved amylase for dingy fabric clean-up
US6060441A (en) * 1997-04-10 2000-05-09 Henkel Corporation Cleaning compositions having enhanced enzyme activity
BR0112778A (en) 2000-07-28 2003-07-01 Henkel Kommanditgellschaft Auf Amylolytically Bacillus sp. 7-7 (dsm 12368) as well as detergent and cleaning agent with this amylolytically enzyme
US20050187130A1 (en) * 2004-02-23 2005-08-25 Brooker Alan T. Granular laundry detergent composition comprising an anionic detersive surfactant, and low levels of, or no, zeolite builders and phosphate builders
US7863237B2 (en) * 2004-03-08 2011-01-04 Ecolab Inc. Solid cleaning products
BR102015019623A2 (en) * 2015-08-14 2017-02-21 Oxiteno S A Indústria E Comércio good enzymatic stability and high performance detergent composition for washing fabrics and surfaces
EP3805349A1 (en) * 2019-10-11 2021-04-14 The Procter & Gamble Company A method of laundering fabric

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4686063A (en) * 1986-09-12 1987-08-11 The Procter & Gamble Company Fatty peroxyacids or salts thereof having amide moieties in the fatty chain and low levels of exotherm control agents

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4770815A (en) * 1986-10-24 1988-09-13 The Procter & Gamble Company Detergent plus softener with imidazoline ingredient
EP0651794B1 (en) * 1992-07-23 2009-09-30 Novozymes A/S MUTANT $g(a)-AMYLASE, DETERGENT AND DISH WASHING AGENT
DK0867504T4 (en) * 1993-02-11 2011-08-29 Genencor Int Oxidatively stable alpha-amylase
BR9407767A (en) * 1993-10-08 1997-03-18 Novo Nordisk As Enzyme & -amylase variant use the same DNA vector expression construct the recombinant cell processes to produce a hybrid & -amylase hybrid and to prepare a variant of a detergent & -amylase additive and detergent compositions
GB2297978A (en) * 1995-02-15 1996-08-21 Procter & Gamble Detergent compositions containing amylase

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4686063A (en) * 1986-09-12 1987-08-11 The Procter & Gamble Company Fatty peroxyacids or salts thereof having amide moieties in the fatty chain and low levels of exotherm control agents

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6725490B2 (en) 2001-11-06 2004-04-27 The Procter & Gamble Company Complex motion toothbrush

Also Published As

Publication number Publication date
HUP9901584A3 (en) 2000-09-28
BR9609721A (en) 1999-02-23
JP2001519831A (en) 2001-10-23
EP0842254B1 (en) 2002-01-09
CA2227752C (en) 2003-12-30
DE69618465D1 (en) 2002-02-14
MX9800746A (en) 1998-04-30
CZ19698A3 (en) 1998-06-17
HUP9901584A2 (en) 1999-08-30
CA2227752A1 (en) 1997-02-06
DE69618465T2 (en) 2002-09-19
WO1997004067A1 (en) 1997-02-06
EP0842254A1 (en) 1998-05-20
CN1197478A (en) 1998-10-28

Similar Documents

Publication Publication Date Title
CN1172498A (en) Detergent compositions containing lipase and protease
CN1192084C (en) Detergent compositions of components
CN1094516C (en) Detergent compositions containing specific lipolytic enzymes
CN1042646C (en) Built dye transfer inhibiting compositions
CN1292062C (en) Bleaching detergent compositions
CN1067264A (en) The liquid detergents with aromatic borate of arrestin lytic enzyme
CN1170429A (en) Cleaning compositions comprising xylanases
CN1278862A (en) Cleaning compositions
CN1387559A (en) Laundry detergent compositions with fabric care
CN1738899A (en) Detergent composition
CN1148868A (en) Detergent composition comprising lipoxidase enzymes
CN1217742A (en) Detergent compositions comprising improved amylases
CN1309694A (en) Detergent tablet
CN1140665C (en) Method for treating polyester fabrics
CN1278297A (en) Detergent compositions
CN1352677A (en) Fabric softening component
CN1309693A (en) Detergent tablet
CN1231689A (en) Detergent composition comprising two cellulose components, with and without a cellulose-binding domain
CN1261400A (en) Laundry and cleaning compositions containing xyloglucanase enzymes
CN1091803C (en) Detergent compositions
CN1105173C (en) Dingy fabric clean-up with amylase enzyme in detergent compsns.
CN1113953C (en) Detergent particle
CN1216575A (en) Cleaning compositions comprising endo-dextranase
CN1238801A (en) Detergent composition or component
CN1113952C (en) Detergent compositions

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee