CN1384866A

CN1384866A - Controlled availability of formulation components, and laundry methods employing same

Info

Publication number: CN1384866A
Application number: CN00814991A
Authority: CN
Inventors: R·R·戴克施特拉; G·S·米拉克勒
Original assignee: Procter and Gamble Ltd
Current assignee: Procter and Gamble Ltd; Procter and Gamble Co
Priority date: 1999-08-27
Filing date: 2000-08-25
Publication date: 2002-12-11
Anticipated expiration: 2020-08-25
Also published as: EP1206513A2; CN100383230C; CA2382280A1; JP2003508581A; BR0013608A; MXPA02002122A; AU6935800A; WO2001016263A2; CZ2002723A3; TR200201062T2; MA25603A1; WO2001016263A3; AR028162A1

Abstract

The present invention relates to a method for the controlled availability of formulation components, such as organic catalysts, into a wash solution. More particularly, the present invention relates to products and bleaching compositions containing such formulation components and laundry methods employing such formulation components.

Description

The composition and the clothes washing method of this component are used in the may command utilization of formulation components

Invention field

The present invention relates to utilize the method for formulation components such as organic catalyzer to washing soln control.More specifically say, the present invention relates to contain the product and the bleaching composition of this formulation components and the clothes washing method that uses this formulation components.

Background of invention

For spot and dirt are removed easily, oxygen-bearing bleaching agent becomes more and more common in family and personal care product recently.SYNTHETIC OPTICAL WHITNER since its have decontamination, clean the fabric of making dirty, brighten with disinfectant properties and dye transfer rejection and receive an acclaim especially.It is found that in laundry product such as washing composition, automatic dishwashing usefulness product and hard surface cleaner, oxygen-bearing bleaching agent gets the nod especially.Yet how many effects of oxygen-bearing bleaching agent has limitation.Some defectives that often run into comprise that they damage the color of fabric and to the damage of laundry utensil.In addition, oxygen-bearing bleaching agent often extremely depends on rate of temperature change.Therefore, use their solution temperature low more, bleaching effect is poor more.For making the oxygen-bearing bleaching agent in the solution effective, generally need temperature to surpass 60 ℃.

For solving said temperature velocity of variation dependency problem, develop the compound that a class is known as " bleach-activating agent ".Bleach-activating agent is generally the acyl compounds of the crossed hydrolysis with leavings group, and as the oxygen benzene sulfonate, they and active oxy group (generally being hydrogen peroxide or its negatively charged ion) form more effective peroxy acid oxygenant.Then, this peracetic acid compound substrate oxidation that will stain or that make dirty.Yet bleach-activating agent also is temperature dependent.Bleach-activating agent is more effective in about 40 ℃-Yue 60 ℃ warm water.In being lower than about 40 ℃ water temperature, peracetic acid compound then part is lost its bleaching effectiveness.

People have done trial, and for example the US patent 5,360,568,5,360,569 and 5,370, disclosed in 826 (being Madison etc.), wherein researched and developed a kind of under low water temperature condition effective bleach system.Yet, disclosed dihydro-isoquinoline bleach boosters in these reference, when uniting with peralcohol, the decomposition that can take place not expect is particularly when when the washing soln component exists.

US patent 5,576,282 and 5,817,614 (being Miracle etc.) disclose another kind of trial, have have wherein researched and developed a kind of bleach system that contains organic catalyzer, and said organic catalyst is effectively and not to damage color under low water temperature condition.

Yet prior art does not have instruction or discloses delay (control) interpolation of formulation components such as organic catalyzer involved in the present invention.

In view of aforementioned, the researchist is devoted to slow down the method that (or control) organic catalyst decomposes, particularly with before oxidable spot contacts.

Therefore, still need a kind of effective transmission organic catalyst and the method for compositions that contains organic catalyzer, even thereby under low water temperature, also can provide effective bleaching, improved stability is provided and makes peracid performance just being brought into play to greatest extent in early days at the decomposition of the organic catalyst of not expecting in the cycles of washing process.

Summary of the invention

The present invention has satisfied this demand; a kind of method of transmitting organic catalyst wherein is provided, and said organic catalyst is bleaching potentiating compounds, bleaching class material, modified amine, modified oxidized amine, sulfimide, phosphono imines, N-acyl group imines and/or thiadiazoles dioxide (thiodiazole dioxide) specifically.

The non-limiting example of the benefit that method provided of transmission organic catalyst of the present invention comprises: remarkable bleaching is renderd a service, even under low water temperature; Avoided needing the usually decomposition of the organic catalyst of appearance in clean textile (that is the fabric of contamination) the pre-mixing process before in interpolation; Before transmitting organic catalyst, allow peracid that the staining fabric of need cleaning is carried out bleaching, so that make the concentration maximization of peracid to the spot on the fabric; And pass through bleaching and reduced acid concentration, reduce the speed of decomposing thus because of the organic catalyst that exists excessive peracid to cause in the washing soln.

One aspect of the present invention provides a kind of washing methods that needs clean textile, comprise may command utilization (validity) method (controlled availability method) that defines among testing program I, II by following discloses and/or the III, transmit organic catalyst to the washing soln that contains fabric, the associating or do not unite peroxygen source, preferably unite peroxygen source.

Another aspect of the present invention provides a kind of bleaching composition, wherein contain organic catalyst, unite or do not unite peroxygen source, preferred associating peroxygen source, wherein said organic catalyst can be by following discloses testing program I, II and/or III in the may command that defines utilize method (method of may command validity) to become can to utilize (effectively) (can to utilize by chemistry, interact with other compound), be used for carrying out bleaching when passing to washing soln with box lunch.

Another aspect of the present invention provides a kind of product, wherein contain organic catalyst, unite or do not unite peroxygen source, preferred associating peroxygen source, wherein said organic catalyst can be by following discloses testing program I, II and/or III in the may command that defines utilize method to become can to utilize (effectively) (can to utilize by chemistry, interact with other compound), be used for carrying out the bleaching that dye transfer suppresses form when passing to washing soln with box lunch.

Another aspect of the present invention provides a kind of product, wherein contain organic catalyst, unite or do not unite peroxygen source, preferred associating peroxygen source, wherein said organic catalyst can be by the testing program I of following discloses, the may command that defines among II and/or the III is utilized method and is become and can utilize and (can utilize by chemistry, interact with other compound), be used for carrying out bleaching when passing to washing soln with box lunch, this product also contains the specification sheets that is used for instructing use organic catalyst cleaning need clean textile, these working instructions may further comprise the steps: transmit a certain amount of product that contains organic catalyzer for the washing soln that contains fabric, associating or do not unite peroxygen source is so that be passed in the washing soln the most said organic catalyst of determining at least by transfer mode after fabric being added in the washing soln.

Unexpectedly find: containing peroxygen source and needing in the washing soln of clean textile, the organic catalyst that the may command that defines among testing program I, II that can be by following discloses and/or the III utilizes method to utilize, (can utilize by chemistry than in washing soln, utilizing immediately, interact with other compound) organic catalyst, the enhanced bleachability can be provided.

The may command that defines among testing program I, II by following discloses and/or the III is utilized method, control the utilizability of organic catalyst of the present invention in the washing soln that contains peroxygen source and fabric, can so that the cycles of washing process of peroxygen source/peracid when its concentration is the highest bleach in early days, and can avoid organic catalyst to contact with the peroxygen source/peracid of maximum concentration at this moment thus, thereby reduce the decomposition of organic catalyst.Then, the may command that defines among testing program I, II that organic catalyst can be by following discloses and/or the III utilizes method to become can to utilize (can chemistry be used for other compound be that peracid interacts).When in washing soln, become available after, organic catalyst can with the remaining available acid-respons of crossing, the oxygen-transfer agent (bleaching class material) that formation can the oxidation spot.Result optimizing the beneficial effect of peroxygen source/peracid and organic catalyst addition.

Do not fettered by theoretical, organic catalyst is particularly bleached potentiating compounds, can react with peroxygen source (preferred peracid) to form oxygen-transfer agent (bleaching class material).Various decomposition approach can cause bleaching potentiating compounds or oxygen-transfer agent and decompose, thus obtain also can with the degradation production of peroxygen source/mistake acid-respons.

Therefore, the utilizability of control organic catalyst, and control the time that contacts between all peroxygen source/peracid in organic catalyst and the washing soln thus, can be so that the peroxygen source/peracid that exists in the washing soln with before organic catalyst contacts, just can be carried out the bleaching of maximum effect to the selected spot on the fabric.

Under typical wash conditions,, thereby when being everlasting the cycles of washing end of processing, also have the available oxygen of peracid form because peracid is slower than oxygen-transfer agent with the reaction of spot.Available oxygen during the cycles of washing end of processing is in low concentration, and it is lower to cause bleaching speed, and after washing is finished, causes the waste of residue peracid.In fact, along with the cycles of washing process is carried out, because of peracid bleach spot and dirt, its concentration (after hydrolytic action is finished excessively) begins to descend.The bleaching that peracid carries out relatively slow (driven mechanics viewpoint is particularly under lower washing bath temperature), and have to increase washing time and cross acid concentration and just can make peracid remove spot to greatest extent.Important and necessary is to allow to exceed acid concentration to some oxidable spot effect, and then allow organic catalyst that the oxidable spot of stubbornness is carried out supplementary function.Known peracid and organic catalyst be fast response very, forms bleaching class material, bleaches the very fast and oxidable spot reaction of class material then.

Therefore, an object of the present invention is to provide: utilize normal direction to contain the method for the washing soln transmission organic catalyst of need clean textile by the may command that defines among testing program I, II and/or the III, this method shows to have improved performance, even in the solution of lesser temps, and can slow down decomposition that (or control) do not expect and bring into play the peracid performance in early days to greatest extent in the cycles of washing process; Washing needs the method for clean textile, transmits organic catalyst by the washing soln that utilizes normal direction to contain fabric with the may command that defines among following disclosed testing program I, II and/or the III; The bleaching composition that contains organic catalyzer, wherein said organic catalyst can be by following discloses testing program I, II and/or III in the may command that defines utilize method to become can to utilize/effectively (available); And the product that contains organic catalyzer, the may command that defines among testing program I, II that wherein said organic catalyst can be by following discloses and/or the III utilizes method to become and can utilize/effectively.By following specification sheets and appending claims, these and other objects of the present invention, characteristics and advantage will be approved by those skilled in the art.

Herein, unless other explanation is arranged, all percentage ratio, ratio and ratio are all in weight unit.All mentioned documents of this paper all are incorporated herein by reference.Detailed Description Of The Invention

The invention discloses the may command that defines among testing program I, II by following discloses and/or the III and utilize method, need clean textile (promptly to containing, stain/fabric made dirty) washing soln transmit the new and high-efficiency method of organic catalysis immunomodulator compounds, said organic catalysis immunomodulator compounds is also referred to as organic catalyst (" bleaching potentiating compounds ", " bleaching class material ", " modified amine ", " modified oxidized amine ", sulfimide, phosphinimine, thiadiazoles dioxide and composition thereof).

The may command that is used to transmit organic catalyst of the present invention utilizes method can provide the bleaching of increase to render a service, and, can slow down the decomposition that (or control) is not expected simultaneously even in the lesser temps field.As a result, organic catalyst of the present invention and using method thereof can obviously be slowed down the decomposition of not expecting, thereby increase catalytic efficiency, cause increasing bleaching effect, and strengthen the property thus.In addition, organic catalyst of the present invention and using method thereof can the cycles of washing process bring into play the peracid performance in early days to greatest extent, thereby improved overall performance.The may command that defines among the testing program I of following discloses, II and/or the III is utilized method, allow organic catalyst to become and to utilize by chemistry with the form (disposable the becoming of organic catalyst that is less than total amount can be utilized) of slowly-releasing, interact with other compound in the washing soln, rather than with the form (all disposable the becoming of organic catalyst of total amounts can be utilized) of summation.Definition

Herein, " become and can utilize (becoming effective) " refers to become and can utilize (chemistry effectively) by chemistry, so that can interact with other compound.

Herein, " peroxygen source " refers to produce the material of peralcohol, can comprise peralcohol itself.The example includes but not limited to bleach-activating agent, peracid, percarbonate, perborate, hydrogen peroxide, bleaching potentiating compounds and/or bleaching class material (for example ， Evil ethylene imine (oxaziridiniums)).

Herein, " peralcohol " comprises peracid and superoxide, for example, and hydrogen peroxide, alkyl hydroperoxide etc.

Herein, " peracid " refers to peroxy acid such as peroxycarboxylic acid and/or peroxide one sulfuric acid (trade name OXONE) and salt thereof.

The method of transmission organic catalyst of the present invention associating or do not unite conventional peroxide bleaching source, preferably unite conventional peroxide bleaching source and implement is so that provide the bleaching of above-mentioned increase to render a service and remarkable slow down the decomposition of not expecting.The organic catalysis immunomodulator compounds

The non-limiting example of organic catalysis immunomodulator compounds is as bleaching potentiating compounds and bleaching class materialization compound, in US patent 5,041,232,5,045,223,5,047,163,5,310,925,5,413,733,5,360,568,5,482,515,5,550,256,5,360,569,5,478,357,5,370,826,5,442,066,5,576,282,5,760,222,5,753,599,5,652,207 and 5,817,614, PCT openly applies for WO98/23602, WO95/13352, WO95/13353, WO95/13351, describe to some extent among WO97/06147 and WO98/23717 and the EP728182.

The organic catalysis immunomodulator compounds of the present invention that is particularly suitable for using in the methods of the invention with the bleaching composition (product) that contains this organic catalysis immunomodulator compounds is, satisfy organic catalysis immunomodulator compounds of being offered among testing program I, II and/or the III and the composition that contains it, said testing program I, II and/or III will be in following discloses.

Preferably, organic catalysis immunomodulator compounds of the present invention, imido grpup more preferably of the present invention (iminium-based) organic catalysis immunomodulator compounds, include but not limited to bleach potentiating compounds, modified amine, modified oxidized amine, sulfimide, phosphinimine, thiadiazoles dioxide and composition thereof.I. bleach potentiating compounds-bleaching potentiating compounds of the present invention, preferred imido grpup bleaching potentiating compounds, include, but is not limited to the aryl imine positively charged ion, net charge for approximately+3 to-3 aryl imine polyion and net charge approximately for approximately+3 to-3 aryl imine zwitter-ion approximately.

The present invention's organic catalyst preferred and that be preferred for bleaching composition of the present invention is, be selected from the bleaching potentiating compounds of Qi Evil ethylene imine bleaching class material of aryl imine zwitter-ion Huo, because it is different with/Huo Evil ethylene imine positively charged ion with the aryl imine positively charged ion, zwitter-ion can provide effective bleaching, the damage that can not produce unacceptable degree to the color of fabric simultaneously.

A. aryl imine (Aryliminium) positively charged ion and polyion-aryl imine positively charged ion and net charge are represented by following formula [I] for pact+3 to about-3 aryl imine polyion:

R wherein ²And R ³Be independently selected from replace or do not replace, saturated or unsaturated group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ¹And R ⁴Be selected from replace or do not replace, saturated or unsaturated group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, ketone group and carbalkoxy; And X ^-Be the charge balance counter ion that suit, the preferably counter ion of bleach-compatible; And v is the integer of 1-3.

Preferably, aryl imine positively charged ion and net charge are represented by following formula [XI] for pact+3 to about-3 aryl imine polyion:

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; Each R ²⁰Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ²⁰Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ¹⁸Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ¹⁹Be to be selected from replacement or unsubstituted, saturated or undersaturated, H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl and heterocyclic group; G is selected from: (1)-O-; (2)-N (R ²³)-and (3)-N (R ²³R ²⁴)-; R ²¹-R ²⁴Be to replace or unsubstituted group, said group is independently selected from H, oxygen, straight or branched C ₁-C ₁₂Alkyl, alkylidene group, alkoxyl group, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle; Precondition is R ¹⁸, R ¹⁹, R ²⁰, R ²¹-R ²⁴Any one can with R ¹⁸, R ¹⁹, R ²⁰, R ²¹-R ²⁴Other any one be joined together to form the part of public ring; Any together with R ²¹-R ²²Can be in conjunction with forming carbonyl; Any ortho position R ²¹-R ²⁴Can be connected to form unsaturated group; And substituent R wherein ²¹-R ²⁴In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part; X ^-Be the charge balance counter ion that suit, the counter ion of preferred bleach-compatible; V is the integer of 1-3.

More preferably, be to make an appointment with+3 suc as formula aryl imine positively charged ion shown in [XI] and net charge to the aryl imine polyion of making an appointment with-3, comprise wherein R ¹⁸Be H or methyl and R ¹⁹Be H or replacement or do not replace, saturated or unsaturated C ₁-C ₁₄The formula of alkyl or cycloalkyl [XI].B. aryl imine zwitter-ion-net charge is represented by following formula [II] for pact+3 to about-3 aryl imine zwitter-ion: R wherein ⁵-R ⁷Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Also exist in this formula by the group shown in the following formula:

Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from replace or do not replace, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle.

Preferably, net charge is represented by following formula [XII] for pact+3 to about-3 aryl imine zwitter-ion:

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; Each R ²⁶Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ²⁶Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ²⁵Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Also exist in this formula by the group shown in the following formula: Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from:

Wherein q is the integer of 1-8; R ²⁹Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from: (1)-O-; (2)-N (R ³⁰)-and (3)-N (R ³⁰R ³¹)-; R ²⁷, R ²⁸, R ³⁰And R ³¹Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ³⁰And R ³¹In any one can with R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ³⁰And R ³¹In other any one be joined together to form the part of public ring; Any together with R ²⁷-R ²⁸Can be in conjunction with forming carbonyl; Any ortho position R ²⁷-R ³¹Can be connected to form unsaturated group; And substituent R wherein ²⁷-R ³¹In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part.

More preferably, for making an appointment with+3, comprise wherein R of formula [XII] by the net charge shown in the formula [XII] to the aryl imine zwitter-ion of making an appointment with-3 ²⁵Be H or methyl, and to formula:

Shown group, Z _p ^-Be-CO ₂ ^-,-SO ₃ ^-Or-OSO ₃ ^-, and p is 1 or 2; More preferably Z _p ^-Be-SO ₃ ^-Or-OSO ₃ ^-, and p is 1.II. modified amine/oxidative amination compound-modified amine of the present invention and/or oxidative amination compound include, but is not limited to modified amine and net charge for approximately+3 to-3 modified oxidized amine approximately.A. modified amine-modified amine is represented by following formula [V] and [VI]: R wherein ⁹-R ¹⁰Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ⁸And R ¹¹, when existing, be to be selected to replace or not replacement saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, ketone group and carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ¹²Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 37＞pKa＞-2; Precondition is any R ⁸-R ¹², when existing, can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; And also exist in this formula by the group shown in the following formula:

Preferably, modified amine is represented by following formula [XV] and [XVI]:

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; R ³⁴Be to be selected to replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical (perhydroxy), alkoxyl group is crossed alkoxyl group (peralkoxy), and carboxyl is crossed carboxyl (percarboxylic), and sulfonate radical closes the group that closes with the persulfonic acid root; Each R ³⁵Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ³⁵Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ³²Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ³³Can be to replace or do not replace, saturated or undersaturated group, said group is selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, and also exist in this formula by the group shown in the following formula:

Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from:

Wherein q is the integer of 1-8; R ³⁸Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from: (1)-O-; (2)-N (R ³⁹)-and (3) N-(R ³⁹R ⁴⁰)-; R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one can with R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In other any one be joined together to form the part of public ring; Any together with R ³⁶-R ³⁷Can be in conjunction with forming carbonyl; Any ortho position R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Can be connected to form unsaturated group; And substituent R wherein ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part.

The example of this modified amine includes, but is not limited to R ³⁴Group is selected from and replaces or not replacements, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group, cross alkoxyl group, carboxyl, carboxyl, sulfonate radical closes, the persulfonic acid root closes modified amine excessively.

Preferably, R ³⁴Be selected from replacement or not replacement, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group and cross alkoxyl group.Following example has exemplified this modified amine of the present invention, but is not to be used for limiting or defining in addition scope of the present invention.

More preferably, concerning the modified amine shown in formula [XV] and [XVI], R ³⁴Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 30＞pKa＞0; More preferably 23＞pKa＞3; More preferably 21＞pKa＞9; 17＞pKa＞11 most preferably.

Preferably, concerning the modified amine shown in formula [XV] and [XVI], R ¹²Be selected from replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group and cross alkoxy base.More preferably, concerning the modified amine shown in formula [XV] and [XVI], wherein said R ¹²Be selected from hydroxyl or perhydroxyl radical.

More preferably modified amine shown in [XV] and [XVI], comprises that net charge is about+1 to about-1 modified amine, wherein R ³²Be H or Me; R ³⁴It is the group that is selected from hydroxyl and perhydroxyl radical; R ³⁵Be independently selected from H, alkyl, nitro, halogen, sulfonate radical closes, alkoxyl group, carboxyl and carbalkoxy and/or Z _p ^-Be-CO ₂ ^-,-SO ₃ ^-Or-OSO ₃ ^-

Concerning modified amine, R ¹²Be leavings group (LG), the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 37＞pKa＞-2; Preferred 30＞pKa＞0; More preferably 23＞pKa＞3; More preferably 17＞pKa＞11; R most preferably ¹²By replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group and cross the leavings group that alkoxyl group is formed, and any R ⁸-R ¹²Can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles.B. modified oxidized amine-modified oxidized amine of the present invention is represented by following formula [VII]-[X]:

R wherein ⁸-R ¹⁰Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ¹¹Be to be selected to replace or not replacement saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ¹²Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 37＞pKa＞-2; Precondition is any R ⁸-R ¹², when existing, can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; And also exist in this formula by the group shown in the following formula:

Preferably, concerning the modified oxidized amine shown in formula [VII]-[X], R ¹²Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 30＞pKa＞0; More preferably 23＞pKa＞3; More preferably 21＞pKa＞9; 17＞pKa＞11 most preferably.

Preferably, concerning the modified oxidized amine shown in formula [VII]-[X], R ¹²Be selected from and replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group and mistake alkoxyl group.More preferably, concerning the modified oxidized amine shown in formula [VII]-[X], R ¹²Be selected from hydroxyl or perhydroxyl radical.

Also preferred, modified oxidized amine is represented by following formula [XVII]-[XX]: Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; R ³⁴Be to be selected to replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group is crossed alkoxyl group, and carboxyl is crossed carboxyl, and sulfonate radical closes, the group that the persulfonic acid root closes; Each R ³⁵Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ³⁵Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ³²Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ³³Can be to replace or do not replace, saturated or undersaturated group, said group is selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, and also exist in this formula by the group shown in the following formula:

Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from: Wherein q is the integer of 1-8; R ³⁸Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from (1)-O-; (2)-N (R ³⁹)-and (3) N-(R ³⁹R ⁴⁰); R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one can with R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, E ³⁹And R ⁴⁰In other any one be joined together to form the part of public ring; Any together with E ³⁶-R ³⁷Can be in conjunction with forming carbonyl; Any ortho position R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Can be connected to form unsaturated group; And substituent R wherein ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part;

The example of this modified oxidized amine includes, but is not limited to R ³⁴Group is selected from and replaces or do not replace, saturated or unsaturated hydroxyl, and perhydroxyl radical, alkoxyl group is crossed alkoxyl group, and carboxyl is crossed carboxyl, and sulfonate radical closes the modified oxidized amine that closes with the persulfonic acid root.

Preferably, R ³⁴Be selected from and replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group and mistake alkoxyl group.

More preferably, concerning the modified oxidized amine shown in formula [XVII] and [XX], R ³⁴Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 30＞pKa＞0; More preferably 23＞pKa＞3; More preferably 21＞pKa＞9; First-selected 17＞pKa＞11.

Preferably, concerning the modified oxidized amine shown in formula [XVII]-[XX], R ³⁴Be selected from and replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group and mistake alkoxyl group.More preferably, concerning the modified oxidized amine shown in formula [XVII]-[XX], R ³⁴Be selected from hydroxyl or perhydroxyl radical.

More preferably, modified oxidized amine shown in [XVII] and [XX], comprises that net charge is about+1 to about-1 modified oxidized amine, wherein R ³²Be H or Me; R ³⁴It is the group that is selected from hydroxyl and perhydroxyl radical; R ³⁵Be independently selected from H, alkyl, nitro, halogen, sulfonate radical closes, alkoxyl group, carboxyl and carbalkoxy and/or Z _p ^-Be-CO ₂ ^-,-SO ₃ ^-Or-OSO ₃ ^-

Concerning modified oxidized amine, R ¹²Be leavings group (LG), the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 37＞pKa＞-2; Preferred 30＞pKa＞0; More preferably 23＞pKa＞3; More preferably 17＞pKa＞11; R most preferably ¹²By replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group and cross the leavings group that alkoxyl group is formed, and any R ⁸-R ¹²Can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles.

The non-limiting example of suitable modified amine compound (modified amine and/or modified oxidized amine) of the present invention (and R ¹²The pKa (H of protonated form ₂The O contrast) value) include but not limited to:

With modified amine compound of the present invention and peroxygen source Joint Implementation, can provide more effective bleach system.Peroxygen source be well known in the art and the present invention in used peroxygen source can comprise any of these known sources, comprise peralcohol and the compound that under the condition that the human consumer uses, can produce the significant quantity peroxide on the spot.Peroxygen source can comprise hydrogen peroxide cource, and the reaction by hydrogen peroxide cource and bleach-activating agent can form acid anion, the mixture of ready-formed peracid compound or suitable peroxygen source on the spot.Certainly, one skilled in the art will appreciate that the peroxygen source that can be used other under the prerequisite of the scope of the invention deviating from.Preferably, peroxygen source is organic and/or inorganic peracid.IV. sulfimide, phosphono imines, N-acyl group imines, thiadiazoles dioxide-sulfimide of the present invention, phosphono imines, N-acyl group imines and thiadiazoles dioxide be respectively by following formula [XXIa], and [XXIb], [XXII] and [XXIII] expression:

R wherein ⁴¹-R ⁴⁴, when existing, be independently selected from replacement or not replacement, saturated or undersaturated group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Precondition is R ⁴¹-R ⁴⁴In any one can with R ⁴¹-R ⁴⁴In other any one can be joined together to form the part of public ring, comprise fused-aryl, fused iso or annelated heterocycles.II. bleach class material-bleaching class material (Evil ethylene imine ， Evil ethylene imine) also can directly use in the present invention.Bleaching class material of the present invention includes but not limited to Evil ethylene imine positively charged ion, net charge is for making an appointment with+3 to about-3 De Evil ethylene imine polyions, net charge is to make an appointment with+3 to about-3 De Evil ethylene imine zwitter-ion Evil ethylene imine sulfimide Evil ethylene imine phosphono imines ， Evil ethylene imine thiadiazoles dioxide, and composition thereof.

Organic catalyst of the present invention, particularly aryl imine positively charged ion, aryl imine polyion, aryl imine zwitter-ion, sulfimide, phosphono imines, thiadiazoles dioxide and peroxygen source (when existing) associating can increase bleaching and render a service.Be not bound by theory, it is believed that the reaction of organic catalyst and peroxygen source forms and have more active bleaching class material, season Evil ethylene imine and/or Evil ethylene imine compound, for example represent by the reaction shown in descending:

The Evil ethylene imine is with/Huo Evil ethylene imine compound has increase or preferred active than peralcohol at a lower temperature.A. Evil ethylene imine positively charged ion and polyion-Evil ethylene imine positively charged ions and net charge are represented by following formula [III] for pact+3 to about-3 polyion:

R wherein ^{2 '}-R ^{3 '}Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ^{1 '}And R ^{4 '}Be to be selected to replace or do not replace, saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, the group of ketone group and carbalkoxy; And X ^-Be the charge balance counter ion that suit, the counter ion of preferred bleach-compatible; And v is the integer of 1-3.

Preferred ， Evil ethylene imine positively charged ion and net charge are for+3 being represented by following formula [XIII] to-3 polyion approximately approximately:

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; Each R ^{20 '}Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ^{20 '}Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ^{18 '}Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ^{19 '}Can be to replace or do not replace, saturated or undersaturated group, said group is selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl and heterocycle.G is selected from: (1)-O-; (2)-N (R ^{23 '})-and (3)-N (R ^{23 '}R ^{24 '})-; R ^{21 '}-R ^{24 '}Be to replace or unsubstituted group, said group is independently selected from H, oxygen, straight or branched C ₁-C ₁₂Alkyl, alkylidene group, alkoxyl group, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle; Precondition is R ^{18 '}, R ^{19 '}, R ^{21 '}-R ^{24 '}In any one can with R ^{18 '}, R ^{19 '}, R ^{21 '}-R ^{24 '}In other any one can be joined together to form the part of public ring; Any together with R ^{21 '}-R ^{22 '}Can be in conjunction with forming carbonyl; Any ortho position R ^{21 '}-R ^{24 '}Can be connected to form unsaturated group; And substituent R wherein ^{21 '}-R ^{24 '}In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part; And substituent R wherein ^{21 '}-R ^{24 '}In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part; X ^-Be the charge balance counter ion that suit, the counter ion of preferred bleach-compatible; And v is the integer of 1-3.

More preferably, by formula [XIII] expression De Evil ethylene imine positively charged ion and net charge for approximately+3 to-3 De Evil ethylene imine polyions approximately, comprise R in the formula [XIII] ^{18 '}Be H or methyl and R ^{19 '}Be H or replacement or do not replace, saturated or unsaturated C ₁-C ₁₄Those of alkyl or cycloalkyl.B. Evil ethylene imine zwitter-ion-net charge is for making an appointment with+3 to making an appointment with-3 De Evil ethylene imine zwitter-ions to be represented by following formula [IV]:

R wherein ^{5 '}-R ^{7 '}Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Also exist in this formula by the group shown in the following formula: Z ' wherein _p ^-With T ' _oCovalently bound, and Z ' _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T ' _oBe selected from replace or do not replace, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle.

Preferably, net charge is for making an appointment with+3 to making an appointment with-3 De Evil ethylene imine zwitter-ions to be represented by following formula [XIV]:

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; Each R ^{26 '}Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ^{26 '}Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ^{25 '}Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; And also exist in this formula by the group shown in the following formula: Z ' wherein _p ^-With T ' _oCovalently bound, and Z ' _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-And a is 1 or 2; T _oBe selected from:

Wherein q is the integer of 1-8; R ^{29 '}Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from (1)-O-; (2)-N (R ^{30 '})-and (3)-N (R ^{30 '}R ^{31 '})-; R ^{27 '}, R ^{28 '}, R ^{30 '}And R ^{31 '}Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ^{25 '}, R ^{26 '}, R ^{27 '}, R ^{28 '}, R ^{30 '}And R ^{31 '}Can with R ^{25 '}, R ^{26 '}, R ^{27 '}, R ^{28 '}, R ^{30 '}And R ^{31 '}In other any one be joined together to form the part of public ring; Any together with R ^{27 '}-R ^{28 '}Can be in conjunction with forming carbonyl; Any ortho position R ^{27 '}-R ^{31 '}Can be connected to form unsaturated group; And substituent R wherein ^{27 '}-R ^{31 '}In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part.

More preferably, by the net charge of formula [XIV] expression for approximately+3 to-3 aryl imine zwitter-ion approximately, comprise R in the formula [XIV] ^{25 '}Be H or methyl, and to formula:

Shown group, Z ' _p ^-Be-CO ₂ ^-,-SO ₃ ^-Or-OSO ₃ ^-, and p is 1 or 2 ion.C) Evil ethylene imine sulfimide, the thiadiazoles dioxide, N-acyl group imines-Evil ethylene imine sulfimides [XXIVa], phosphono imines [XXIVb], N-acyl group imines [XXV] and thiadiazoles dioxide [XXVI] and [XXVII] following expression:

R wherein ^{41 '}-R ^{44 '}, when existing, being independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, and ketone group, carboxyl, carbalkoxy, precondition is R ^{41 '}-R ^{44 '}In any one can with R ^{41 '}-R ^{44 '}In other any one can be joined together to form the part of public ring, comprise fused-aryl, fused iso or annelated heterocycles.

X ^-The suitable example of (anionic counter-ion) includes, but is not limited to: BF ₄ ^-, OTS ^-With WO97/06147, WO95/13352, WO95/13353, WO95/13351, WO98/23717, US patent 5,360,568,5,360569,5,482,515,5,550,256,5,478,357,5,370,826,5,442,066, disclosed other anionic counter-ion among EP728182B1 and the UK1215656.Preferably, anionic counter-ion is a bleach-compatible.

For any structure that does not carry net charge, there is not counter ion compound association therewith.

For any structure that carries net negative charge, X ⁺The suitable example of (cation counterbalancing ion) includes but not limited to Na ⁺, K ⁺, H ⁺

For any structure that carries many net charges, the suitable example of negatively charged ion and cation counterbalancing ion includes but not limited to above-mentioned those.Other organic catalysis immunomodulator compounds-except that above-mentioned bleaching potentiating compounds, bleaching class material and modified amine and amine oxide, the organic catalysis immunomodulator compounds can also be any compound that can form oxygen-transfer agent (SYNTHETIC OPTICAL WHITNER) with the mistake acid-respons known in the art.Organic catalyst compound concentrations-organic catalysis immunomodulator compounds of the present invention can be about 0.00001% (0.0001ppm)-Yue 10% (100ppm) of composition weight to the addition of washing soln, about 0.0001% (0.001ppm) of preferred composition weight-Yue 2% (20ppm), more preferably from about 0.005% (0.05ppm)-Yue 0.5% (5ppm), more preferably from about 0.01% (0.1ppm)-Yue 0.2% (2ppm).0.02% (0.2ppm)-Yue 0.1% (1ppm) most preferably from about.

Preferably, the bleaching of bleaching composition of the present invention can make with the amount of the organic catalysis immunomodulator compounds that contains in the composition that bleaching potentiating compounds concentration reaches the about 5ppm of about 0.001ppm-in the washing soln.

In addition, contain a certain amount of peralcohol (when existing) and a certain amount of organic catalysis immunomodulator compounds in the preferred bleaching composition of the present invention, so that the mol ratio of said peralcohol and organic catalysis immunomodulator compounds is preferably more than 1: 1 in the washing soln, more preferably greater than 10: 1, more preferably greater than 50: 1.The preferred molar ratio range of peralcohol and cationic organic catalyst immunomodulator compounds is about 30,000: about 10: 1 of 1-, more preferably from about 10,000: about 50: 1 of 1-, more preferably from about 5,000: about 100: 1 of 1-, more preferably from about 3,500: about 150: 1 of 1-.

Being the example purpose, is 1000ppm in the product working concentration, and scaled value (in ppm) is provided.The 1000ppm washing soln that portion contains the product of 0.2wt% organic catalysis immunomodulator compounds can provide the organic catalyst compound concentration of 2ppm.Equally, the portion 3500ppm washing soln that contains the product of 0.2wt% organic catalysis immunomodulator compounds can provide the organic catalyst compound concentration of 6.5ppm.

The method that is particularly suitable for the transmission organic catalysis immunomodulator compounds of the present invention of the inventive method with the method for transmitting the bleaching composition (product) that contains this organic catalysis immunomodulator compounds is, the organic catalysis immunomodulator compounds can be competent at the preferred method of bleaching dirty substrate in the water-bearing media that contains peroxygen source and organic catalysis immunomodulator compounds with the composition that contains it, the structure of wherein said organic catalysis immunomodulator compounds defines in the present invention, and contains active oxygen and the about 5ppm of 0.001ppm-from peralcohol that the about 250ppm/ of the 0.05-that has an appointment rises medium in the wherein said medium, the preferred about 3ppm of about 0.01ppm-, the about 2ppm of 0.1ppm-more preferably from about, the said organic catalysis immunomodulator compounds of the about 1ppm of 0.2ppm-most preferably from about.

This preferred method of bleaching dirty substrate in the water-bearing media that contains peroxygen source and organic catalysis immunomodulator compounds be to have very much value concerning those are concerned about the purposes that needs the dirty substrate colors protection of cleaning.In these purposes, preferred embodiment (for example, the about 3ppm of 0.01ppm-) is to realizing that can accept the fabric color protection is particularly important.Not too be concerned about the purposes that needs the dirty substrate colors protection of cleaning for other, can preferred higher working concentration.The decomposition of organic catalyst

Organic catalyst of the present invention is particularly bleached potentiating compounds, decomposes by various decomposition approach easily, includes but not limited to the aromizing approach.It is well known in the art that the aromizing (decompositions) of 6 yuan of ring bleach boosters is reacted, for example not bound by theory, and at Hanquet etc., Tetrahedron 1993,49, example to some extent in the 423-438 page or leaf, and as follows:

The alternate manner that decomposes includes, but is not limited to, attack bleaching potentiating compounds and/or bleaching class material by nucleophilic reagent, include but not limited to oxyhydroxide negatively charged ion, other nucleophilic reagent of crossing oxyhydroxide negatively charged ion, carboxylate anion, percarboxylic acids root negatively charged ion and under wash conditions, existing.For example, and do not wish to be subjected to theory, the decomposition reaction of 6 Yuan Huan Evil ethylene imines, this process that can cause bleaching efficiency to descend, as follows as example: The may command of organic catalyst is utilized method

Unexpectedly find, in containing the washing soln of fabric, the organic catalyst that the may command that defines among testing program I, II that can be by following discloses and/or the III utilizes method to utilize, the uncontrollable organic catalyst that is utilized in the method that utilizes than defining in testing program I, the II of following discloses and/or III can provide the enhanced bleachability.In addition, the organic catalyst that discovery utilizes method to utilize in the may command that contains peracid and need to define among testing program I, II in the washing soln of clean textile, can be by following discloses and/or the III, than the uncontrollable organic catalyst that is utilized in the method that utilizes in containing the washing soln that needs clean textile, that can in testing program I, the II of following discloses and/or III, define, can provide the enhanced bleachability.

Among the present invention, can use any suitable mode and/or method, transmit of the present invention can be by following discloses testing program I, II and/or III in define utilize the organic catalyst of method by may command.

The non-limiting example that belongs to the transfer mode of the scope of the invention and/or method is as follows.Transfer mode-transfer mode of the present invention can be any way that can control organic catalyst utilizability of the present invention, so that make the may command that defines among testing program I, II that organic catalyst can be by following discloses in washing soln and/or the III utilize method and can utilize (effectively).

Suitable transfer mode includes, but is not limited to add the sustained release material that contains organic catalyst of the present invention, sustained release material as capsule or agglomerate or other type, the utilizability of sustained release control of material organic catalyst wherein is so that make the may command that defines among testing program I, II that organic catalyst can be by following discloses in washing soln and/or the III utilize the method utilization.Preferably, the utilizability of sustained release control of material organic catalyst is after peroxygen source (if any) is released and preferred peroxygen source is bleached if having time and/or after adding to fabric in the washing soln.The organic catalyst of interpolation encapsulate-as mentioned above, the another kind of suitable transfer mode of the present invention is before or after peroxygen source (if any) is added in the washing soln and/or needs to add the organic catalyst that contains or do not contain the encapsulate of detergent component to washing soln before or after clean textile is added in the washing soln.The organic catalyst of encapsulate includes, but is not limited to contain the bleaching composition of organic catalyst of the present invention, wherein bleaching composition prevents that the organic catalysts of most amounts are discharged in the washing soln, and until peroxygen source (if any) is released after and preferably peroxygen source is bleached and/or if having time after adding to the need clean textile in the washing soln.For example, if before adding the need clean textile to washing soln, the organic catalyst of encapsulate is added in the washing soln, then the organic catalyst of encapsulate prevents that organic catalyst is discharged in the washing soln, after adding to fabric in the washing soln.In general, this time bar is about 2 minutes, more preferably 1 minute, and more preferably 1 second-Yue 10 minutes, preferred 7 minutes, more preferably 5 minutes.Yet, seldom under the occasion this moment between the time limit can reach 24 hours or more.

On the other hand, if the organic catalyst of encapsulate is added in the washing soln that contains the need clean textile, then the organic catalyst of encapsulate preferably prevents the release of organic catalyst, and all peracid that exist in washing soln are finished after the fabric bleaching.In general, interval this moment, be limited to about 2 minutes, and more preferably 1 minute, more preferably 1 second-Yue 10 minutes, preferred 7 minutes, more preferably 5 minutes.

Can use any suitable encapsulate material well known by persons skilled in the art.This being applicable to includes but not limited to the example of the encapsulate in the organic catalyst encapsulate of the present invention with material, the microsphere of plastic production, said plastics such as thermoplastics, vinyl cyanide, methacrylonitrile, polyacrylonitrile, polymethacrylonitrile and composition thereof; And/or siliceous material, as glass.The microsphere of commercially available acquisition can be by the Expancel (Akzo Nobel company) of trade name EXPANCEL  available from Sweden; By trade name PM6545, PM6550, PM7220, PM7228, EXTENDOSPHERES ^, LUXSIL ^, Q-CEL ^, SPHERICEL ^Available from Pq Corp.; And press trade name ALBUMEX  available from Malinckrodt.

Other suitable encapsulate comprises that with material biological polymer such as starch and US patent 5,703,034 (authorize Offshack etc., The Procter ﹠amp; Gamble company has) described in polyoxyethylene glycol and paraffin.

Can contain one or more organic catalysts of the present invention in the organic catalyst of encapsulate, and can not necessarily contain one or more following detergent components: filling salt, tensio-active agent, other SYNTHETIC OPTICAL WHITNER, enzyme (preferred bleaching-stable enzyme), sequestrant, washing assistant, dye transfer inhibitor, spices, fabric softener, dirt release agent (soil releaseagent) and whitening agent.

The non-limiting example of a suitable form of the organic catalyst of encapsulate is gel capsules (gel cap).Contain the agglomerate of organic catalyzer-as mentioned above, the another kind of suitable transfer mode of the present invention is before or after peroxygen source (if any) is added in the washing soln and/or needs to add the agglomerate that contains organic catalyst of the present invention that contains or do not contain detergent component to washing soln before or after clean textile is added in the washing soln.Agglomerant organic catalyst includes, but is not limited to contain the bleaching composition of organic catalyst of the present invention, wherein bleaching composition prevents that the organic catalysts of most amounts are discharged in the washing soln, and until peroxygen source (if any) is released after and preferably peroxygen source is bleached and/or if having time after adding to fabric in the washing soln.

For example, if before adding the need clean textile to washing soln, the agglomerate that contains a certain amount of organic catalyst is added in the washing soln, then agglomerate prevents that organic catalyst is discharged in the washing soln, after adding to fabric in the washing soln.In general, this time bar is about 2 minutes, more preferably 1 minute, and more preferably 1 second-Yue 10 minutes, preferred 7 minutes, more preferably 5 minutes.Yet, seldom under the occasion this moment between the time limit can reach 24 hours or more.

On the other hand, if the agglomerate that contains a certain amount of organic catalyst is added in the washing soln that contains the need clean textile, then agglomerate preferably prevents the release of organic catalyst, and all peracid that exist in washing soln are finished after the fabric bleaching.In general, interval this moment, be limited to about 2 minutes, and more preferably 1 minute, more preferably 1 second-Yue 10 minutes, preferred 7 minutes, more preferably 5 minutes.

Can use any suitable agglomeration material well known by persons skilled in the art.This being applicable to includes, but is not limited to solid, water-soluble ionizable material with the agglomerant agglomeration of organic catalyst of the present invention with the example of material, as organic acid, organic and inorganic acid salt and composition thereof.This agglomeration visible US patent 5,540,855 of example (Baillely etc.) and 5,482,642 (Agar etc.) of material, these two pieces are The Procter ﹠amp; Gamble company has.

Contain in the agglomerate of organic catalyzer and can contain one or more organic catalysts of the present invention, and can not necessarily contain one or more following detergent components: filling salt, tensio-active agent, other SYNTHETIC OPTICAL WHITNER, enzyme (preferred bleaching-stable enzyme), sequestrant, washing assistant, dye transfer inhibitor, spices, fabric softener, dirt release agent and whitening agent.The bleaching composition that contains organic catalyzer

Except that above-mentioned encapsulate and agglomeration, the peroxygen source coupling in organic catalyst of the present invention and other bleaching composition can also not considered their form.For example, can in the laundry additive product, use the organic catalysis immunomodulator compounds.

In bleaching composition, can with bleaching potentiating compounds of the present invention with or not with the peroxygen source coupling, preferably with the peroxygen source coupling.In bleaching composition of the present invention, the amount of peroxygen source can be about 0.1% (1ppm)-Yue 60% (600ppm) of composition weight, about 1% (10ppm) of preferred composition weight-Yue 40% (400ppm), and the amount of organic catalysis immunomodulator compounds can be about 0.00001% (0.0001ppm)-Yue 10% (100ppm) of composition weight, and about 0.0001% (0.001ppm) of preferred composition weight-Yue 2% (20ppm), more preferably from about 0.005% (0.05ppm)-Yue 0.5% (5ppm), more preferably from about 0.01% (0.1ppm)-Yue 0.2% (2ppm).0.02% (0.2ppm)-Yue 0.1% (1ppm) most preferably from about.

Preferred bleaching potentiating compounds concentration is the bleaching potentiating compounds of about 300 gram/moles in molecular weight, but for oligomeric or polymeric bleaching potentiating compounds, the molecular weight of bleaching potentiating compounds can be preferably 150-1000 gram/mole, even higher.For example, in bleaching composition of the present invention, when the bleaching potentiating compounds so that more preferably the amount of about 0.005% (0.05ppm)-Yue 0.5% (5ppm) exists, mole (M) concentration of bleaching potentiating compounds will be 1.7 * 10 ^-8M to 1.7 * 10 ^-5M.If use the organic catalysis immunomodulator compounds of higher molecular weight in bleaching composition of the present invention, then preferred volumetric molar concentration remains unchanged, and preferred weight concentration (in ppm) will increase.For example, molecular weight is that the bleaching potentiating compounds of about 600 gram/moles will exist with about 0.01% (0.1ppm) more preferably-Yue 1.0% (10ppm).Concerning oligomeric or polymeric bleaching potentiating compounds, preferred volumetric molar concentration will in the relevant monomeric unit of imines Huo Evil ethylene imine active sites.

This preferred method of bleaching dirty substrate in the water-bearing media that contains peroxygen source and organic catalysis immunomodulator compounds be to have very much value concerning those are concerned about the purposes that needs the dirty substrate colors protection of cleaning.In these purposes, preferred embodiment (for example, the about 3ppm of 0.01ppm-) is to realizing that can accept the fabric color protection is particularly important.Not too be concerned about the purposes that needs the dirty substrate colors protection of cleaning for other, can preferred higher working concentration.

The may command that is particularly suitable for defining among testing program I, II that the organic catalyst of the present invention that uses preferably can be by following discloses and/or the III in bleaching composition of the present invention utilizes method containing the available organic catalyst that becomes in the washing soln of bleaching composition, contains organic catalyzer in the wherein said bleaching composition.Organic catalyst can be itself just can be by following discloses testing program I, II and/or III in the may command that defines utilize method in containing the washing soln of organic catalyzer, to become can to utilize.Perhaps, the bleaching composition that contains organic catalyzer can be prepared into and make the may command that defines among testing program I, II that organic catalyst can be by following discloses and/or the III utilize method in containing the washing soln of bleaching composition, to become to utilize (effectively).

Bleaching composition of the present invention laundry purposes, hard-surface cleaning, automatic dishwashing purposes, relevant with wood pulp and/or textiles brighten and/or bleach purposes, antibiotic and/or sterilization purposes and beautifying use as artificial tooth, tooth, hair and skin in application be favourable.Yet, because it has efficient and can distinguishedly slow down organic catalyst and not expect the distinct advantages of decomposing at lesser temps solution, organic catalyst of the present invention can be ideally suited and be used to the purposes of doing washing, and for example contains the washing composition of SYNTHETIC OPTICAL WHITNER by use or the laundry bleaching additive comes bleached woven fabric and/or bleaching dyestuff (as suppressing dye transfer).In addition, organic catalyst of the present invention can particle, the form utilization of powder, rod, paste, foam, gel and liquid composition.

Therefore, can contain other required in various laundry purposes detergent component in the bleaching composition of the present invention.These components include, but is not limited to the stain release type tensio-active agent; Other SYNTHETIC OPTICAL WHITNER comprises other bleaching catalyst; Washing assistant; Sequestrant; Enzyme; The aggretion type dirt release agent; Whitening agent and various other detergent component.The composition that contains these various additional detergent components preferably makes the pH of 1% solution of bleaching composition about 12 for about 6-, preferably about 8-about 10.5.

Preferably contain at least a stain release type tensio-active agent, at least a sequestrant, at least a stain release type enzyme in the bleaching composition, and the pH of 1% solution of preferred bleaching composition is about 12 for about 6-, more preferably from about 8-about 10.5.

It is desirable also containing peroxygen source in the bleaching composition, is described in detail below.Can also contain the powdery or the liquid composition of hydrogen peroxide cource or peroxygen source in the bleaching composition, elaborate below.

If contain hydrogen peroxide cource in the bleaching composition, it is desirable then also containing bleach-activating agent in the laundry additive product, is described in detail below.

In another embodiment of the invention, provide a kind of method that to wash fabric that is used to wash.This preferable methods comprises fabric is contacted with laundry solution.Fabric can comprise the most fabric that can wash in the normal consumer working conditions.Contain the bleaching composition that the present invention describes in detail in the laundry solution.Water temperature is preferably about 0 ℃-Yue 50 ℃ or higher.Water is preferably about 1 with the ratio of fabric: about 15: 1 of 1-.

Can also contain at least a other detergent component in the laundry solution, said component is selected from stain release type tensio-active agent, other SYNTHETIC OPTICAL WHITNER, sequestrant, stain release type enzyme and composition thereof.Preferably, the pH of laundry solution counts about 8-about 10.5 with 1% solution of bleaching composition.

Another aspect of the present invention provides a kind of laundry additive product.The organic catalyst of having described in detail above containing in this laundry additive product.This laundry additive product is ideally suited the washing process that is used to expect additional bleaching effect.This situation can include but not limited to the cryogenic fluid laundry applications.

The may command that is particularly suitable for defining among testing program I, II that the organic catalyst of the present invention that uses preferably can be by following discloses and/or the III in laundry additive product of the present invention utilizes method containing the available organic catalyst that becomes in the washing soln of laundry additive product, contains organic catalyzer in the wherein said laundry additive product.Organic catalyst can be itself just can be by following discloses testing program I, II and/or III in the may command that defines utilize method in containing the washing soln of organic catalyzer, to become can to utilize.Perhaps, the laundry additive product preparation that contains organic catalyzer can be become to make the may command that defines among testing program I, II that organic catalyst can be by following discloses and/or the III to utilize method in the washing soln that contains the laundry additive product, to become effective.

It is desirable also containing peroxygen source in the laundry additive product, is described in detail below.Can also contain the powdery or the liquid composition of hydrogen peroxide cource or peroxygen source in the laundry additive product, elaborate below.

In addition, if contain hydrogen peroxide cource in the laundry additive product, it is desirable then also containing bleach-activating agent in the laundry additive product, is described in detail below.

Preferably, with the packaged of laundry additive product, so that add the laundry processes of using peroxygen source and the high bleaching effect of expectation to the single dose formulation.This single dose formulation can comprise pill, tablet, gel capsules (gel cap) or other single dose units, as the powder or the liquid of predetermined amount.If desired, can contain the volume that filler or solid support material increase composition.Salt that suitable filler or solid support material can be selected from (but being not limited to) various vitriol, carbonate and silicate and talcum, clay or the like.The filler or the solid support material that are used for liquid composition can be water or low molecular weight primary or secondary alcohol, comprise polyvalent alcohol and glycol.The example comprises methyl alcohol, ethanol, propyl alcohol and Virahol.Also can use monohydroxy-alcohol.This material that can contain the 5%-that has an appointment about 90% in the composition.Can use acid filler to reduce pH.

A kind of preferred bleaching composition is the bleaching composition that contains following composition:

(a) contain the bleach system of peroxygen source; With

(b) organic catalyst; Wherein the may command that defines among testing program I, II that organic catalyst can be by following discloses and/or the III utilizes method to become effective in containing the washing soln of said bleaching composition.Bleach system-except that organic catalyst of the present invention, bleaching composition of the present invention also preferably contains bleach system.Generally contain peroxygen source in the bleach system.Peroxygen source be well known in the art and the present invention in used peroxygen source can comprise any of these known sources, comprise peralcohol and the compound that under the condition that the human consumer uses, can produce the significant quantity peroxide on the spot.Peroxygen source can comprise hydrogen peroxide cource, and the reaction by hydrogen peroxide cource and bleach-activating agent can form acid anion, the mixture of ready-formed peracid compound or suitable peroxygen source on the spot.Certainly, one skilled in the art will appreciate that the peroxygen source that under the prerequisite that does not deviate from the scope of the invention, can use other.Preferably, peroxygen source is selected from: (i) ready-formed peracid compound, be selected from percarboxylic acids and salt, percarbonic acid and salt are crossed imido acid and salt, peroxide one sulfuric acid and salt, and composition thereof, (ii) hydrogen peroxide cource is selected from perborate compound, percarbonate compound, superphosphate compound and composition thereof, and bleach-activating agent.

When existing, the amount of peroxygen source (peracid and/or hydrogen peroxide cource) is generally about 1% from composition weight, preferably from about 5% to about 30%, preferably to about 20%.If present, the amount of bleach-activating agent be generally the bleaching composition weight that contains SYNTHETIC OPTICAL WHITNER-Jia-bleach-activating agent from about 0.1%, preferably from about 0.5% to about 60%, preferably to about 40%.A. the prefabricated peracid compound of ready-formed peracid-the present invention's use is the compound of any routine, it is stable and can produces the acid anion of crossing of significant quantity under human consumer's working conditions, organic catalysis immunomodulator compounds of the present invention can with prefabricated peracid compound coupling, said prefabricated peracid compound is selected from percarboxylic acids and salt, and percarbonic acid and salt are crossed imido acid and salt, peroxide one sulfuric acid and salt with and composition thereof, the example is described in US patent 5,576,282 (Miracle etc.) to some extent.

The organic peroxy carboxylic acid that one class is suitable has following general formula:

Wherein R is alkylidene group or the alkylidene group of replacement or the phenylene of phenylene or replacement that contains about 22 carbon atoms of 1-, and Y is hydrogen, halogen, alkyl, aryl, C (O) OH or-C (O) OOH.

Be suitable for organic peroxide acid of the present invention and can contain one or two peroxy-radical, and can be aliphatic series or aromatics.When organic peroxycarboxylic acid was aliphatic series, unsubstituted peracid had following general formula: Wherein Y can be, for example, and H, CH ₃, CH ₂Cl, C (O) OH, or C (O) OOH; And n is the integer of 0-20.When organic peroxycarboxylic acid was aromatics, unsubstituted peracid had following general formula:

Wherein Y can be, for example, and hydrogen, alkyl, alkyl halide, halogen, C (O) OH or C (O) OOH.

Can be used for a typical peroxy acid of the present invention and comprise alkyl and aryl peroxy acids, as: (i) benzoyl hydroperoxide and cyclosubstituted benzoyl hydroperoxide, for example, peroxide-α-Nai Jiasuan, one peroxide phthalic acid (magnesium salts hexahydrate), and neighbour-carboxyl benzamido is crossed oxy hexanoic acid (sodium salt); (ii) aliphatic series, replace aliphatic series and arylalkyl one peroxy acid, for example, the peroxide lauric acid, the peroxide stearic acid, amino oxy hexanoic acid (NAPCA), the N of crossing of N-nonanoyl, amino oxy hexanoic acid (SAPA) and N, the N-O-phthalic amido peroxide caproic acid (PAP) crossed of N-(3-octyl group succinyl); (iii) the amido peroxy acid for example, is crossed a nonyl acid amides (NAPSA) of oxydisuccinic acid or a nonyl acid amides (NAPAA) of peroxide hexanodioic acid.

Can be used for typical diperoxy acid of the present invention and comprise alkyl diperoxy acid and the acid of aryl diperoxy, as: (iv) 1,12-diperoxy dodecanedioic acid; (v) 1, the 9-diperoxyazelaic acid; (vi) diperoxy undecane dicarboxylic acid; Diperoxy sebacic acid and diperoxy m-phthalic acid; (vii) 2-decyl diperoxy butane-1,4-diacid; (viii) 4,4 '-alkylsulfonyl diperoxy phenylformic acid.

This SYNTHETIC OPTICAL WHITNER is disclosed in US patent 4,483,781 (Hartman, 1984.11.20 authorizes), US patent 4,634,551 (Burns etc.), EP patent application 0,133,354 (Banks etc., 1985.2.20 open) and US patent 4,412,934 (Chung etc., 1983.11.1 authorizes).The peroxide acid source also comprises US patent 4,634,551, and 6-nonyl amino-6-oxo of describing in detail in (1987.1.6 authorizes Burns etc.) is crossed oxy hexanoic acid.Persulfate compound, for example (Wilmington, the DE) OXONE of Zhi Zaoing also can be as suitable peroxide one source of sulfuric acid for E.I.DuPont de Nemours.B. hydrogen peroxide cource-over hydrogenation hydrogen source can be any suitable hydrogen peroxide cource and the content existence to describe in detail in the US patent 5,576,282.For example, hydrogen peroxide cource can be selected from the perborate compound, percarbonate compound, superphosphate compound and composition thereof.

Hydrogen peroxide cource Kirk Othmer " encyclopedia of chemical technology " the 4th edition (1992, John Wiley ﹠amp; Sons), the 4th volume has detailed description in the 271-300 page or leaf " SYNTHETIC OPTICAL WHITNER (scanning) ", and introduces here as a reference, and comprises various forms of Sodium peroxoborate and SPC-D, comprises various coatings and modified form.

Can be used for preferred hydrogen peroxide cource of the present invention can be any conventional source, comprises hydrogen peroxide itself.For example, perborate, for example, can use Sodium peroxoborate (any hydrate, but preferred one or tetrahydrate), yellow soda ash peroxyhydrate or similar substance, percarbonate, trisodium phosphate peroxyhydrate, urea peroxyhydrate, or sodium peroxide.As persulphate SYNTHETIC OPTICAL WHITNER (for example, OXONE, DuPont manufacturing), also be the useful source of available oxygen.Preferred especially Sodium peroxoborate monohydrate and SPC-D.Also can use the mixture of any conventional hydrogen peroxide cource.

Preferred percarbonate bleach comprises that mean particle size is about 500 microns-Yue 1,000 micron dried particle, the said particle that is not more than about 10wt% less than about 200 microns and the said particle that is not more than about 10wt% greater than about 1,250 micron.Not necessarily, can give percarbonate silicon-coating hydrochlorate, borate or water soluble surfactant active.Percarbonate can derive from various commercial source, as FMC, and Solvay and Tokai Denka.

Can also contain chlorine type albic material in the composition of the present invention as SYNTHETIC OPTICAL WHITNER.This SYNTHETIC OPTICAL WHITNER is well known in the art, and comprises, for example, and dichloroisocyanuric acid sodium (" NaDCC ").Yet, chlorine type SYNTHETIC OPTICAL WHITNER be contain in the enzyme composition not too preferred.B. bleach-activating agent-preferred is formulated in peroxygen source and activator (peracid precursors) in the composition.The amount of activator be composition weight from about 0.01%, preferably from about 0.5%, more preferably from about 1% to about 15%, preferably to about 10%, more preferably to about 8%.The used bleach-activating agent of the present invention is any compound that can produce on the spot during with the hydrogen peroxide cource coupling corresponding to the peracid of bleach-activating agent.The various non-limiting examples of activator are specifically disclosed in US patent 5,576,282, US patent 4,915,854 and the US patent 4,412,934.Other can be used for typical SYNTHETIC OPTICAL WHITNER of the present invention and activator also can be referring to US4, and 634,551.

Preferred activator is selected from tetra acetyl ethylene diamine (TAED); benzoyl caprolactam (BzCL); 4-nitro benzoyl hexanolactam; 3-chlorobenzene formacyl hexanolactam; benzoyl oxygen base benzene sulfonate (BOBS); nonanoly acyloxy benzene sulfonate (NOBS), phenol benzoate (PhBz), the last of the ten Heavenly stems acyloxy benzene sulfonate (C ₁₀-OBS), benzoyl Valerolactim (BZVL), hot acyloxy benzene sulfonate (C ₈-OBS), can cross ester of hydrolysis and composition thereof, most preferably benzoyl caprolactam and benzoyl Valerolactim.PH is the activator with OBS or VL leavings group for the particularly preferred bleach-activating agent of about 8-about 9.5.

Preferred hydrophobic bleach activator includes but not limited to nonanoly acyloxy benzene sulfonate (NOBS); The amino hexylyloxy of 4-[N-(nonanoyl)]-Phenylsulfonic acid sodium salt (NACA-OBS), the visible US patent 5,523,434 of one of them example; Bay acyloxy benzene sulfonate (LOBS or C ₁₂-OBS); 10-undecylene acyloxy benzene sulfonate (has UDOBS or C that insatiable hunger is closed on 10 ₁₁-OBS) and caprinoyl aminobenzoic acid (DOBA).

The preferred visible US5 of bleach-activating agent, 698,504 (Christie etc., 1997.12.16 authorizes); US5,695,679 (Christie etc., 1997.12.9 authorizes); US5,686,401 (Willey etc., 1997.11.11 authorizes); US5,686,014 (Hartshorn etc., 1997.11.11 authorizes); US5,405,412 (Willey etc., 1995.4.19 authorizes); US5,405,413 (Willey etc., 1995.4.11 authorizes); US5,130,045 (Mitchel etc., 1992.7.14 authorizes) and US4,412,934 (Chung etc., 1983.11.1 authorizes) and our common patent application US series number 08/709,072,08/064,564 undetermined, all these all are incorporated herein by reference.

Among the present invention, peroxy bleaching compound (AvO) is generally at least 1: 1 with the mol ratio of bleach-activating agent, preferably from about 20: 1, more preferably from about 10: about 1: 1 of 1-, preferably to about 3: 1.

(Quaternary substituted) bleach-activating agent that also can comprise tetrasubstituted.This bleaching composition preferably includes the bleach-activating agent (QSBA) of tetrasubstituted or the peracid (QSP) of tetrasubstituted; More preferably the former.The structure of preferred QSBA is at US5,686,015 (Willey etc., 1997.11.11 authorizes); US5,654,421 (Taylor etc., 1997.8.5 authorizes); US5,460,747 (Gosselink etc., 1995.10.24 authorizes); US5,584,888 (Miracle etc., 1996.12.17 authorize) and US5,578,136 (Taylor etc. have further description in 1996.11.26); All these all are incorporated herein by reference.

Can be used for highly preferred bleach-activating agent of the present invention is above mentioned US5, the activator of acid amides-replacement of describing in 698,504, US5,695,679 and US5,686,014.The preferred embodiment of this bleach-activating agent comprises: (the amino caproyl of 6-decoyl) oxygen benzene sulfonate, (the amino caproyl of 6-nonanoyl) oxygen benzene sulfonate, (the amino caproyl of 6-caprinoyl) oxygen benzene sulfonate and composition thereof.

The activator that other is useful is disclosed in US5, and 698,504, US5,695,679, US5,686,014 (every piece is above-mentioned mentioned) and US4,966,723 (Hodge etc., 1990.10.30 authorize) in, comprise benzoxazine type activator, as on the 1st, 2, having condensed-C (O) OC (R ¹)=N-partial C ₆H ₄Ring.

According to activator and definite purposes, be that about 6-is about 13, preferably the bleach system of about 9.0-about 10.5 can obtain good bleaching effect by using pH.In general, for example, use activator to be used for nearly neutral or neutral following pH scope with electrophilic part.Can use alkali and buffer reagent to guarantee this pH scope.

The acyl lactam activator, as US5,698; 504, US5,695,679 and US5; described in 686,014 (every piece is above-mentioned mentioned), be highly suitable for the present invention; particularly acyl caprolactam (for example referring to WO94-28102A) and acyl group Valerolactim are (referring to US5; 503,639, Willey etc.; 1996.4.2 authorize, be incorporated herein by reference).D. organo-peroxide, particularly diacyl peroxide-except that above-mentioned SYNTHETIC OPTICAL WHITNER, can not necessarily contain organo-peroxide in the bleaching composition of the present invention.Organo-peroxide is at " encyclopedia of chemical technology " the 17th volume (JohnWiley﹠amp of Kirk Othmer; Sons) the 27-90 page or leaf particularly has deep illustrating in the 63-72 page or leaf nineteen eighty-two, and all are incorporated herein by reference.If the use diacyl peroxide, preferably it produces minimum disadvantageous effect to going spot/film forming.E. can also not necessarily contain metallic bleaching catalyst in metallic bleaching catalyst-bleaching composition, preferably contain the bleaching catalyst of manganese and cobalt.

One type metallic bleaching catalyst is a catalyst system, and this system contains and has active transition-metal cation of certain bleach catalyst such as copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese positively charged ion; Seldom or do not have an active assistant metal positively charged ion of bleach catalyst, as zinc or aluminium cations and (multivalence) sequestrant that catalytic and complementary metallic cation are had certain stability constant, ethylenediamine tetraacetic acid (EDTA) particularly, ethylenediamine tetraacetic (methylene phosphonic acid) and water-soluble salt thereof.These catalyzer are disclosed in US4, among 430,243 (Bragg, 1982.2.2 authorizes).I. manganese metal complex-if desired, can pass through manganic compound catalysis composition of the present invention.This compound and consumption thereof are well known in the art, and comprise, for example, US5,576,282 (Miracle etc., 1996.11.19 authorize), US5,246,621 (Favre etc., 1993.9.21 mandate), US5,244,594 (Favre etc., 1993.9.14 authorizes), US5,194,416 (Jureller etc., 1993.3.16 authorizes), US5,114,606 (vanVliet etc., 1992.5.19 authorize) and EP patent application 549,271A1,549,272A1,544,440A2 and 544, disclosed manganese type catalyzer among the 490A1; The preferred embodiment of these catalyzer comprises Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(PF ₆) ₂, Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄(ClO ₄) ₄, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₃, Mn ^IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH ₃) ₃(PF ₆) and composition thereof.Other metal mold bleaching catalyst comprises US4,430,243 (this piece is above-mentioned mentioning) and US5, disclosed catalyzer among 114,611 (the van Kralingen, 1992.5.19 authorizes).Also reported in the following patent and used manganese to strengthen bleaching action: US4,728,455 (Rerek, 1988.3.1 authorizes) with various complex compound ligands; US5,284,944 (Madison, 1994.2.8 authorizes); US5,246,612 (van Dijk etc., 1993.9.21 authorizes); US5,256,779 (Kerschner etc., 1993.10.26 authorizes); US5,280,117 (Kerschner etc., 1994.1.18 authorizes); US5,274,147 (Kerschner etc., 1993.12.28 authorizes); US5,153,161 (Kerschner etc., 1992.10.6 authorizes) and US5,227,084 (Martens etc., 1993.7.13 authorizes).Ii. cobalt metal complex-can be used for cobalt bleaching catalyst of the present invention is known, and, for example, US5,597,936 (Perkins etc., 1997.1.28 authorizes); US5,595,967 (Miracle etc., 1997.1.21 authorizes); US5,703,030 (Perkins etc., 1997.12.30 authorizes) and M.L.Tobe, " basic hydrolysis of transition-metal complex ", and Adv.Inorg.Bioinorg.Mech., (1983) are described in 2, the 1-94 pages or leaves to some extent.Can be used for most preferred cobalt catalyst of the present invention is formula [Co (NH ₃) ₅OAc] T _yFive shown amine acetate moietys close cobalt salt, wherein " OAc " expression acetate moiety part and " T _y" be negatively charged ion, five amine acetate cobalt chloride particularly, [Co (NH ₃) ₅OAc] Cl ₂And [Co (NH ₃) ₅OAc] (OAc) ₂[Co (NH ₃) ₅OAc] (PF ₆) ₂[Co (NH ₃) ₅OAc) (SO ₄); [Co (NH ₃) ₅OAc] (BF ₄) ₂[Co (NH ₃) ₅OAc] (NO ₃) ₂(being " PAC " herein).

These cobalt catalyst can prepare easily by already known processes, for example above-mentioned US5 that mentions, 597,936, US5,595,967, US5,703,030, article and reference and US patent 4,810, the 410 (Diakun etc. of the Tobe that mentions of this paper, 1989.3.7 authorize), J.Chem.Ed. (1989), 66 (12), 1043-45; " the synthetic and sign of mineral compound ", W.L.Jolly (Prentice-Hall; 1970), 461-3 page or leaf; " inorganic chemistry " (Inorg.Chem.), 18,1497-1502 (1979); " inorganic chemistry ", 21,2881-2885 (1982); " inorganic chemistry ", 18,2023-2025 (1979); Inorg.Synthesis, 173176 (1960); " physical chemistry magazine " (Journal ofPhysical Chemistry), 56, instruct among the 22-25 (1952).Iii. more big ring encircles and can also contain big ring aptly in the transition metal complex-composition of the present invention of rigidity ligand and encircle the transition metal complex of rigidity ligand as bleaching catalyst more.Sometimes write a Chinese character in simplified form " MRL " in term " the many rings of the big ring rigidity ligand " argumentation below.Its consumption is a catalytically effective amount, about 1ppb or suit more, for example mostly be most about 99.9%, be more typically about 0.001ppm or more, the preferred about 500ppm of about 0.05ppm-(wherein " ppb " represents per 1,000,000,000 (billion)/one weight, and " ppm " represents per 1,000,000/weight).

Below will be with suitable transition metal, for example Mn illustrates." big ring many ring " refer to MRL be big ring be again many rings." many rings " expression is dicyclo at least.Herein, term " rigidity " comprises " having superstructure " and " cross-bridge "." rigidity " is defined as flexible constraint regurgitation: referring to D.H.Busch., and chemistry comment (Chemical Reviews), (1993), and 93,847-860 is incorporated herein by reference.More specifically say, " rigidity " herein refer to MRL than other character all identical (size of ring and type are identical with atomicity on the main ring) but lack the big ring (" mother encircles greatly ") of the superstructure that exists among the MRL (particularly connection portion or, preferred cross-bridge part) must measure rigidity more.When mensuration had or do not have the relative rigidity of big ring of superstructure, what mensuration person used was the free form (not being the form of metal link) of big ring.Known rigidity is useful when bigger ring; Measure, measure or relatively during rigidity suitable method comprise computing method (referring to, for example, Zimmer, the chemistry comment, (1995), 95 (38), 2629-2648 or Hancock etc., Inorganica Chimica Acta, (1989), 164,73-84).

Preferred MRL of the present invention is the super-rigidity ligand of a special defects, and it is crosslinked." cross-bridge " has indefiniteness ground explanation in following 1.11.In 1.11, cross-bridge is-the CH2CH2-part.N in its bridging example structure ¹And N ⁸By relatively, " homonymy " bridge, for example, if with it in 1.11 in N ¹And N ¹²Between introduce, then can not be enough to constitute " cross-bridge ", and not be preferred therefore.

Suitable metal in the rigidity ligand complexe comprises Mn (II), Mn (III), Mn (IV), Mn (V), Fe (II), Fe (III), Fe (IV), Co (I), Co (II), Co (III), Ni (I), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II), Cr (III), Cr (IV), Cr (V), Cr (VI), V (III), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (II), Ru (II), Ru (III) and Ru (IV).Preferred transition-metal comprises manganese, iron and chromium in the transition metal bleach catalyzer of the present invention.

More generally, MRL of the present invention (and corresponding transition-metal catalyst) comprises aptly: (a) at least a main ring contains four or more a plurality of heteroatomic big ring; (b) can increase the covalently bound nonmetal superstructure of big ring stiffness, be preferably selected from: (i) bridging superstructure, as the connection portion; (ii) crosslinked (bridge) superstructure is as crosslinked (bridge) connection portion; (iii) its combination

Herein, term " superstructure " is definition to some extent in the document of Busch etc., for example referring to the article of Busch in " chemistry comment ".

Preferred herein superstructure not only strengthens the rigidity of female big ring, and helps to make big ring folding, so that the metal-complexing in it and the crack.Suitable superstructure can be simple in the extreme, for example can use down any of example among Fig. 1 and Fig. 2:

Fig. 1 wherein n is an integer, as 2-8, preferably less than 6, is generally 2-4, or

Fig. 2 wherein m and n is the integer of about 1-8, more preferably 1-3; Z is N or CH; And T is compatible substituting group, H for example, alkyl, trialkyl ammonium, halogen, nitro, sulfonate etc.1.10 in aromatic ring can be replaced by saturated rings, wherein with the Z that is connected of ring in atom can contain N, O, S or C.

Following compound further indefiniteness illustrates suitable MRL:

Fig. 3

It is the highly preferred MRL of the present invention, and it is the derivative crosslinked (bridge), methyl-replacements (all nitrogen-atoms uncles for) that ring draws amine.In form, with this ligand called after 5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] n-Hexadecane uses the vonBaeyer system that prolongs.Referring to " the IUPAC nomenclature guide of organic compound: recommend version 1993 ", R.Panico, W.H.Powell and J-CRicher (Eds.), BlackwellScientificPublications, BosTon, 1993; Particularly save referring to R-2.4.2.1.

Transition-the metal bleach catalyst that is suitable for the big ring rigidity ligand of the present composition generally speaking can comprise the known compound that meets this paper definition, more preferably, any in a large amount of new compounds that specially design for the present invention laundry or cleaning purposes, and anyly illustrate as indefiniteness by following:

Two chloro-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II)

Two hydrations-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] n-Hexadecane phosphofluoric acid manganese (II)

Hydration-hydroxyl-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] n-Hexadecane phosphofluoric acid manganese (III)

Two hydrations-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] n-Hexadecane Tetrafluoroboric acid manganese (II)

Two chloro-5,12-dimethyl-1,5,8,12-four azabicyclos [6.6.2] n-Hexadecane phosphofluoric acid manganese (III)

Two chloro-5,12-di-n-butyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II)

Two chloro-5,12-dibenzyl-1,5,8,12-four azabicyclos [6.6.2] hexadecane manganeses (II)

Two chloro-5-normal-butyl-12-methyl isophthalic acids, 5,8,12-four aza-bicyclos [6.6.2] hexadecane manganeses (II)

Two chloro-5-n-octylcyclam 2-methyl isophthalic acids, 5,8,12-four aza-bicyclos [6.6.2] hexadecane manganeses (II)

Two chloro-5-normal-butyl-12-methyl isophthalic acids, 5,8,12-four aza-bicyclos [6.6.2] hexadecane manganeses (II).

In fact and not as restriction, composition of the present invention and cleaning course can be adjusted into the active bleaching catalyst that at least hundred million/a order of magnitude is provided in the aqueous cleaning medium, the about 25ppm of about 0.01ppm-, the more preferably from about about 10ppm of 0.05ppm-, the bleaching catalyst of the about 5ppm of 0.1ppm-most preferably from about preferably are provided in washings.Be in the washings of washing process automatically, to obtain this content, generally contain about 0.0005%-of cleaning compositions weight about 0.2%, more preferably from about bleaching catalyst, particularly manganese or the cobalt catalyst of 0.004%-about 0.08% in the composition of the present invention.

Preferably, peroxygen source is selected from hydrogen peroxide cource and bleach-activating agent, and wherein said hydrogen peroxide cource is selected from the perborate compound, percarbonate compound, superphosphate compound and composition thereof.Preferably, bleach-activating agent is selected from hydrophobic bleach activator disclosed herein.

The purpose of this bleaching composition is the decomposition that slows down undesirable organic catalyst, and the fabric such as the dirty fabric performance bleachability that allow the peracid in the washing soln earlier need to be cleaned before organic catalyst is utilized.Detergent component

Although it is necessary not reach the object of the invention, the many conventional assistant agent that below exemplifies all is suitable for bleaching composition of the present invention, and it is desirable being spiked in the preferred embodiments of the invention, for example, help or strengthen clean-up performance, (when the containing spices, tinting material, dyestuff etc.) attractive in appearance of handling substrate to be cleaned or improving bleaching composition.The definite character and the addition content thereof of these annexing ingredients will depend on the physical form of composition and the character of used clean operation.Unless other explanation is arranged, bleaching composition of the present invention is passable, for example, is mixed with the universal of particle or powder type or " heavy duty type " washing composition, particularly cloth-washing detergent; Liquid, the universal washing composition of gel or paste, particularly so-called heavy duty type kind of liquid; Liquid high-count fabric washing composition; Manual wash up is with washing composition or light-duty wash up washing composition, particularly high bubble type washing composition; The use in dishwasher washing composition comprises the various tablets of using to family expenses and public organizations, particle, liquid and rinse aid type; Liquid cleaning and sterilizing agent comprise the antibiotic type of washing one's hands, washing soap, mouth wash shua, denture cleanser, automobile or carpet washing lotion, bathroom detergent; Shampoo and hair conditioner; Spray glue and bubble are bathed and metal detergent; And the cleaning supplement is as bleaching additive and " stain bonding strip " or pre-treatment type.Tensio-active agent-preferred, contain tensio-active agent or surfactant system in the bleaching composition of the present invention, wherein tensio-active agent can be selected from nonionic and/or negatively charged ion and/or cats product and/or both sexes and/or zwitter-ion and/or semi-polar nonionic surfactants.

The amount of tensio-active agent be generally bleaching composition weight from about 0.1%, preferably from about 1%, more preferably from about 5% about 99.9% to bleaching composition weight, preferably to about 80%, more preferably to about 35%, most preferably from about 30%.

Tensio-active agent can be a nonionic, negatively charged ion, both sexes, zwitter-ion or cationic.Also can use these surfactant mixtures.Preferably, the mixture that contains anion surfactant or anion surfactant and other tensio-active agent, particularly nonionogenic tenside in the bleaching composition.

Preferably, allocate into composition in the tensio-active agent of the enzyme component compatibility that exists.In liquid or gelatinous composition, the tensio-active agent of most preferably allocating into can promote the stability of all enzymes in the composition, perhaps can not make the stability decreases of all enzymes at least.

Suitable nonionic, negatively charged ion, positively charged ion, both sexes, the non-limiting example of zwitter-ion and semi-polar nonionic surfactants is disclosed in US patent 5,707,950 and 5,576, in 282." emulsifying agent and washing composition " (Emulsifiers and Detergents) of the visible Mc Cutcheon of other example of suitable tensio-active agent, North America version, 1997, Mc CutcheonDivision, MC publishing company is in US patent 3,929, in 678 and 4,259,217; " tensio-active agent science " (Surfactant Science) series, Marcel Dekker company limited (New York and Basel); " tensio-active agent handbook " (Handbook of Surfactants), M.R.Porter, Chapman and Hall, the 2nd edition, 1994; " tensio-active agents in the consumer's goods " (Surfactants in Consumer Porducts), J.Falbe compiles, Springer-Verlag, 1987 and " tensio-active agent and washing composition " (SurfaceActive Agent and Detergents) (I and II volume, Schwartz, Perry and Berch).

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

R ²-C (O)-N (R ¹)-Z is R wherein ¹Be H, or R ¹Be C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or its mixture, R ²Be C _5-31Alkyl, and Z is polyhydroxy alkyl, and it has the straight-chain alkyl chain that directly is connected with at least 3 hydroxyls on the chain, or its alkoxy derivative.Preferably, R ¹Be methyl, R ²It is straight chain C _11-15Alkyl or C _16-18Alkyl or alkenyl chain such as cocounut oil alkyl or its mixture, and Z derives from the reducing sugar such as glucose, fructose, maltose, lactose, obtains by reductive amination process.

Highly preferred anion surfactant comprises, alkyl alkoxylated sulfate surfactant, and it is formula RO (A) _mSO ₃The water-soluble salt of M or acid, wherein R does not replace C ₁₀-C ₂₄Alkyl or have C ₁₀-C ₂₄The hydroxyalkyl of moieties, preferred C ₁₂-C ₂₀Alkyl or hydroxyalkyl, more preferably C ₁₂-C ₁₈Alkyl or hydroxyalkyl, A are oxyethyl group or propoxy-unit, and m is greater than 0, and it is about 6 to be generally about 0.5-, and more preferably from about 0.5-is about 3, and M is H or positively charged ion, can be metallic cations (as sodium, potassium, lithium, calcium, magnesium etc.) for example; Ammonium or replacement ammonium cation.Alkyl ethoxylated sulfate and alkyl propoxylated sulphates are also included within here.

When existing, generally contain in the bleaching composition of the present invention, particularly laundry detergent composition from about 1%, preferably from this anion surfactant of about 3% weight to about 40%, preferably to this anion surfactant of about 20% weight.

Present composition camber preferred cationic surfactants is the water-soluble quaternary ammonium compound with following formula:

R ₁R ₂R ₃R ₄N ⁺X ^-R wherein ₁Be C ₈-C ₁₆Alkyl, each R ₂, R ₃And R ₄Be C independently ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, benzyl and-(C ₂H ₄₀) _xH, wherein the value of x is that 2-5 and X are negatively charged ion.R ₂, R ₃Or R ₄In to be no more than one should be benzyl.

When comprising, generally contain in the bleaching composition of the present invention from about 0.2%, more preferably from this cats product of about 1% weight to about 25%, more preferably to this cats product of about 8% weight.

When comprising, generally contain in the bleaching composition of the present invention from about 0.2%, more preferably from the amphoterics of about 1% weight to about 15%, more preferably to the amphoterics of about 10% weight.

When comprising, bleaching composition of the present invention generally contains from about 0.2%, and more preferably from about the zwitterionics of 1% weight is to about 15%, more preferably from about the zwitterionics of 10% weight.

When comprising, generally contain in the bleaching composition of the present invention from about 0.2%, more preferably from the semi-polar nonionic surfactants of about 1% weight to about 15%, more preferably to the semi-polar nonionic surfactants of about 10% weight.

One or more (preferred two or more mixtures) mid-chain branched tensio-active agents that also contain the 0.001%-that has an appointment about 100% in the bleaching composition of the present invention preferably have the mid-chain branched alkyl alkoxy alcohol of following formula: Mid-chain branched alkyl-sulphate with following formula: And mid-chain branched alkyl alkoxy sulfate with following formula: Wherein the total carbon atom number in the branched primary alkyl moiety of these formulas part (comprises R, R ¹And R ²Branch, but do not comprise the carbon atom that contains any EO/PO alkoxyl group part) be 14-20, and furtherly, concerning this surfactant mixture, the average total carbon atom number in the branched primary alkyl moiety of the following formula part is to about 17.5 (preferably about 15-about 17) greater than 14.5; R, R ¹And R ²Be selected from hydrogen independently of one another, C ₁-C ₃Alkyl and composition thereof, preferable methyl; Precondition is R, R ¹And R ²Not hydrogen entirely, and when z is 1, R or R at least ¹Not hydrogen.M is water-soluble cationic and the positively charged ion that can comprise more than one types, for example, and the mixture of sodium and potassium.Subscript w is the integer of 0-13; X is the integer of 0-13; Y is the integer of 0-13; Z is to be 1 integer at least; Condition is that w+x+y+z is 8-14.EO and PO represent to have the inferior ethoxyl unit and the inferior propoxy-unit of following formula respectively:

Or Yet, other oxyalkyl units, particularly 1, the inferior propoxy-of 3-, butoxy and composition thereof also are suitable as the oxyalkyl units of mid-chain branched moieties side chain.

The mid-chain branched tensio-active agent is mixture preferably, constitutes surfactant system by it.Therefore, when containing oxyalkylated tensio-active agent in the surfactant system, the average extent of alkoxylation in the subscript m presentation surface active agent intermixture.At this point, it is about 0.01 that subscript m is at least, preferably from about 0.1, more preferably from about 0.5, most preferably from about 1 to about 30, preferably to about 10, more preferably to about 5.When considering only to contain the mid-chain branched surfactant system of alkoxy-based surface-active agent, the value representation of subscript m is corresponding to the distribution of the average extent of alkoxylation of m, perhaps it can be a specific oxyalkylated chain (for example, ethoxylation and/or propoxylation), its unit number just in time equals m.

The of the present invention preferred mid-chain branched tensio-active agent that is adapted at using in the surfactant system of the present invention has following formula: Or formula:

A wherein, b, d and e are integers, so that a+b is that 10-16 and d+e are 8-14; M is selected from sodium, potassium, magnesium, ammonium and replace ammonium with and composition thereof.

Preferably, the surfactant system that contains the mid-chain branched tensio-active agent of the present invention is prepared by two embodiments.First embodiment preferred contains from containing 25% or the mid-chain branched tensio-active agent that still less forms the raw material of mid-chain branched alkyl unit.Therefore with any other conventional surfactants blending before, contain 25% or the surfactant molecule that belongs to non-straight chain tensio-active agent still less in the mid-chain branched surface active agent composition.

Second preferred embodiment contains the mid-chain branched tensio-active agent that forms from the raw material that contains the about 70% mid-chain branched alkyl unit of about 25%-.Therefore, with any other conventional surfactants blending before, contain the surfactant molecule that belongs to non-straight chain tensio-active agent of the 25%-that has an appointment about 70% in the mid-chain branched surface active agent composition.

Also contain in the surfactant system of bleaching composition of the present invention from about 0.001% of surfactant system weight, preferably from about 1%, more preferably from about 5%, most preferably from about 10% to about 100%, preferably to about 60%, more preferably to one or more (the preferably mixture of two or more) mid-chain branched alkylaryl sulfonate surfactants of about 30%, the wherein aryl unit that preferably has following formula is the tensio-active agent of phenyl ring: Wherein L is the acyclic hydrocarbon group part that contains 6-18 carbon atom; R ¹, R ²And R ³Be hydrogen or C independently of one another ₁-C ₃Alkyl, precondition are R ¹And R ²Be free of attachment to the unitary end of L; M is the water-soluble cationic of electrically charged q, and wherein a and b combine and satisfy neutral charge.Other detergent component

Be other detergent component (assistant agent) that can use in bleaching composition of the present invention, particularly laundry detergent composition below, said assistant agent comprises washing assistant, optical whitening agent, soil release polymers, dye-transfer, dispersion agent, enzyme, suds suppressor, dyestuff, spices, tinting material, filling salt, hydrotropic agent, light activating agent, fluorescent agent, fabric conditioner, hydrolyzable tensio-active agent, sanitas, antioxidant, sequestrant, stablizer, anti-shrinking medium, anti-creasing agent, sterilant, mycocide, anticorrosive agent and composition thereof.Preferably contain one or more detergent builder compounds or builder system in washing assistant-bleaching composition of the present invention.When existing, generally contain washing assistant in the composition, preferably from about 5%, more preferably from about 10% to about 80%, preferably to about 50%, more preferably to the detergent builder compound of about 30% weight at least about 1%.

The content of washing assistant can be very different with its required physical form according to the end-use of composition.When existing, generally contain washing assistant in the composition at least about 1%.It is about 50% generally to contain the 5%-that has an appointment in the preparation, the detergent builder compound of about 30% weight of more typical about 5%-.It is about 80% generally to contain the 10%-that has an appointment in the granular preparation, the detergent builder compound of about 50% weight of more typical about 15%-.Yet, and do not mean that the lower or washing assistant of a large amount more of eliminating.

Inorganic or contain the P detergent builder compound and include, but is not limited to following basic metal, ammonium and alkanol ammonium salt: polyphosphate (tri-polyphosphate for example, pyrophosphate salt and glassy polymeric metaphosphate), phosphonate, phytic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.Yet, need the washing assistant of nonphosphate in some areas.Importantly, even composition of the present invention so-called " weak " washing assistant (comparing) with phosphoric acid salt for example Citrate trianion in the presence of, perhaps under the situation that the what is called that takes place with zeolite or layered silicate washing assistant " helps and washes deficiency (under built) ", also can unexpectedly produce good action.

The example of silicate-like builder is an alkalimetal silicate, particularly SiO ₂: Na ₂The O ratio is 1.6: 1-3.2: 1 those alkalimetal silicates and lamina sodium silicate, and as the layered silicate of describing in the US patent 4,664,839 (Rieck, 1987.5.12 authorizes).NaSKS-6 is the trade(brand)name (writing a Chinese character in simplified form " SKS-6 " usually) of the commercially available crystalline layered silicate of Hoechst.Different with zeolite builders, the NaSKS-6 silicate-like builder does not contain aluminium.NaSKS-6 has δ-Na ₂SiO ₅The layered silicate of form.It can be by as DE-A-3, and 417,649 and DE-A-3, the method described in 742,043 prepares.SKS-6 is the highly preferred layered silicate of the present invention, but can use other layered silicate, as has general formula NaMSi _xO _2x+1YH ₂The layered silicate of O, wherein M is sodium or hydrogen, x is the number of 1.9-4, preferably 2, y is the number of 0-20, preferably 0.Other commercially available layered silicate of Hoechst comprises NaSKS-5, NaSKS-7 and NaSKS-11, and it is α, β and γ form.As mentioned above, δ-Na ₂SiO ₅(NaSKS-6 form) is that the present invention most preferably uses.Other silicate also is available, and Magnesium Silicate q-agent for example can be as crisp dose in granular preparation, as the stablizer of oxygen-bearing bleaching agent with as the component of foam control system.

The example of carbonate builders is a German patent application 2,321, alkaline-earth metal and alkaline carbonate in 001 (1973.11.15 is open).

The silico-aluminate washing assistant is useful in the present invention.The silico-aluminate washing assistant is very important in the at present commercially available heavy duty type granular detergent composition of great majority, and can be the important washing assistant composition of liquid detergent preparation.The empirical formula of silico-aluminate washing assistant is:

[M _z(zAlO ₂) _y] xH ₂O wherein z and y is at least 6 integer, and the mol ratio of z and y is that 1.0-is about 0.5, and x is the integer of about 15-about 264.

Useful aluminosilicate ion exchange material is commercially available acquisition.The structure of these aluminosilicate ion exchange materials can be crystallization or unbodied, and can be naturally occurring silico-aluminate or synthetic the acquisition.Produce the visible US3 of a kind of method of this aluminosilicate ion exchange material, 985,669 (Krummel etc., 1976.10.12 authorizes).Preferred synthetic crystallization aluminosilicate ion exchange material can title zeolite A, zeolite P (B), zeolite MAP and X zeolite obtain.In an especially preferred embodiment, the crystal aluminosilicate ion-exchange material has following formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] xH ₂O wherein x is about 20-about 30, particularly about 27.This material is known as zeolite A.The present invention also can use dehydration zeolite (x=0-10).Preferably, grain graininess is the silico-aluminate of 0.1-10 micron diameter.

The organic detergent builder compound that is fit to the object of the invention includes but is not limited to various multi-carboxylate's compounds.Herein, " multi-carboxylate " refer to have a plurality of carboxylate groups, the compound of preferred at least 3 carboxylate groups.The multi-carboxy acid salt washing agent usually can acid form add in the composition, but form that also can neutralized salt is added.But when using with the form of salt, preferred as alkali salt is as sodium, potassium and lithium salts or alkanol ammonium salt.

Include various types of useful materials among the multi-carboxy acid salt washing agent.The important multi-carboxy acid salt washing agent of one class comprises the ether multi-carboxylate, comprises oxygen di-succinate, as US3, and 128,287 (Berg, 1964.4.7 authorize), US3,635,830 (Lamberti etc., 1972.1.18 authorize) and US3, disclosed among 936,448 (Lamberti, 1976.2.3 authorizes).Also referring to US4, " TMS/TDS " washing assistant among 663,071 (Bush etc., 1987.5.5 authorizes).Suitable ether multi-carboxylate also comprises ring compound, particularly alicyclic compound, as US3, and 923,679 (Rapko, 1975.12.2 authorizes); US4,158,635 (Crutchfield etc., 1979.6.19 authorizes); US4,120,874 (Crutchfield etc., 1978.10.17 authorizes) and US4, the compound of describing among 102,903 (Crutchfield etc., 1978.7.25 authorizes).

Other useful decontamination lotion promoter comprises ether hydroxypolycarboxylic acid salt, the multipolymer of maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyl oxygen connection succsinic acid, the basic metal of various polyacetic acids such as ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA), ammonium and substituted ammonium salt, and multi-carboxylate such as mellitic acid, succsinic acid, oxygen di-succsinic acid, More Malay acid, benzene 1,3,5-tricarboxylic acid, carboxyl methyl oxygen connection succsinic acid and soluble salt thereof.

The Citrate trianion washing assistant, for example citric acid and soluble salt thereof (particularly sodium salt) are the multi-carboxy acid salt washing agents of particularly important to the heavy duty liquid detergent preparation, because they can be biodegradable by renewable resource acquisition and they.Citrate trianion also can be used for particulate composition, particularly with zeolite and/or the coupling of layered silicate washing assistant.In described composition and coupling, oxygen di-succinate also is useful especially.

What be adapted at using in the bleaching composition of the present invention also has US4, disclosed 3 among 566,984 (Bush, 1986.1.28 authorizes), 3-dicarboxyl-4-oxa--1,6-adipate and relevant compound.Useful succsinic acid washing assistant comprises C ₅-C ₂₀Alkyl and alkenyl succinic and salt thereof.The particularly preferred compound of this type is the dodecenyl succinic succsinic acid.The specific examples of succinate washing assistant comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-15 carbene base succinates etc.The lauryl succinate is a preferred washing assistant and be described in EP patent application 86200690.5/0,200,263 (1986.11.5 is open) in this group.

Other suitable multi-carboxylate is disclosed in US4, and 144,226 (Crutchfield etc., 1979.3.13 authorizes) and US3 are among 308,067 (Diehl, 1967.3.7 authorizes).Also referring to the US patent 3,723,322 of Diehl.

Lipid acid, for example, C ₁₂-C ₁₈Monocarboxylic acid also can be spiked in the composition separately, or with particularly Citrate trianion and/or the coupling of succinate washing assistant of aforesaid washing assistant, so that additional washing assistant activity to be provided.This use of lipid acid can cause foam to reduce usually, and the makers-up should consider this point.

In the situation that can use phosphorus type washing assistant, particularly, can use various alkali metal phosphates, as is well known tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate at the soap bar preparation that is used for hand-washing operation.Also can use phosphonate washing assistant such as ethane-1-hydroxyl-1,1-diphosphonate and other known phosphonate (referring to, for example, US patent 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137).Can not necessarily contain one or more iron and/or manganese sequestrant in sequestrant-bleaching composition of the present invention.This sequestrant can be selected from aminocarboxylate, amino phosphonates do, and aromatic chelating agent of multifunctional-replacement and composition thereof, all will be described below.Do not wish to be subjected to theory, the benefit that it is believed that these materials partly is to remove the iron in the washing soln and the special performance of mn ion because they have by forming solvable inner complex.

The example and the visible US patent 5,576,282 and 5,728,671 of consumption thereof of suitable sequestrant.

Be used for preferred biodegradable cheating agent of the present invention and be ethylenediamine disuccinate (" EDDS '), particularly [S, S] isomer, of US patent 4,704,233 (1987.11.3 authorizes Hartman and Perkins).

Also can contain water-soluble methylglycine diacetic acid (MGDA) salt (or acid form) in the composition of the present invention, as sequestrant or can be used as and for example insoluble washing assistant such as zeolite, the shared complementary washing assistant of layered silicate.

If you are using, it is about 15% that these sequestrants account for about 0.1%-of bleaching composition weight of the present invention usually, more preferably to about 3.0%.Can also contain one or more in dye transfer inhibitor-bleaching composition of the present invention is used for being suppressed at fabric washing and includes dissolving that conditioning operation processes of yarn dyed fabric run into and the dyestuff of suspension is transferred to the compound of the dye transfer of another part fabric, dye transfer inhibitor from a fabric.

Suitable polymeric dye transfer inhibitor includes, but is not limited to, polyvinylpyrrolidonepolymers polymers, polyamine N-oxide pllymers, the multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole, polyvinyl oxazolidine ketone and polyvinyl imidazol or its mixture.The example of this dye transfer inhibitor is in US patent 5,707,950 and 5,707, and is open in 951.

Other suitable dye transfer inhibitor includes, but is not limited to cross-linked polymer.Cross-linked polymer is that its main chain is interconnected to polymkeric substance to a certain degree; These connections can be chemical property or physical properties, may be connected with active group on the main chain or the active group on the side chain; Cross-linked polymer is described in " polymer science magazine " the 22nd volume 1035-1039 page or leaf to some extent.

In one embodiment, cross-linked polymer is made in the mode that they have formed three-dimensional rigid structure, thereby dyestuff can be captured in the formed hole of three-dimensional structure.

In another embodiment, cross-linked polymer is caught dyestuff by swelling.

Suitable cross-linked polymer is described in our patent application 94870213.9 common undetermined.

Add this polymkeric substance and can also strengthen the performance of the enzyme in the bleaching composition of the present invention.

Dye transfer inhibitor has the ability of the fugitive dye that washes out in before dyestuff has an opportunity to adhere to other object that is in the suds complexing or the absorption DYED FABRICS.

In the time of in being present in bleaching composition of the present invention, the amount of dye transfer inhibitor be bleaching composition weight from about 0.0001%, more preferably from about 0.01%, most preferably from about 0.05% to about 10% of bleaching composition weight, more preferably to about 2%, most preferably to about 1%.Can also contain dispersion agent in dispersion agent-bleaching composition of the present invention.Suitable water-soluble organic salt is acid or its salt of homopolymerization or copolymerization, and wherein poly carboxylic acid contains at least two quilts and is no more than the carboxyl that two carbon atoms are separated from each other.

Such polymkeric substance is disclosed in GB-A-1, and 596,756.The example of this salt be MW2000-5000 polyacrylate and with the multipolymer of maleic anhydride, the molecular weight of this multipolymer is 1,000-100,000.

Specifically, the molecular weight that can add the 0.5-20% of composition weight in detergent composition of the present invention is 4000 acrylate and the multipolymer of methacrylate, for example 480N.

Can contain calcium soap peptizing agent compound in the composition of the present invention, it is no more than 8, preferably is no more than 7, is most preferably not exceeding 6 as the dispersion of calcium soap (LSDP) of giving a definition.The amount of this calcium soap peptizing agent compound is preferably 0-20% weight.

The numerical evaluation that the calcium soap peptizing agent is renderd a service defines by dispersion of calcium soap (LSDP), said LSDP measures by distributed test, and said distributed test is described in the article J.Am.Oil.Chem.Soc. of H.C.Borghetty and C.A.Bergman, the 27th volume, pp88-90, (1950).This calcium soap disperses testing method to be extensive use of by this area user and to be mentioned in following article: W.N.Linfield, tensio-active agent science series, the 7th volume, pp3; W.N.Linfleld, Tensidesurf.det., the 27th volume, pp159-183, (1990) and M.K.Nagarajan, W.FMasler " makeup and toilet articles " the 104th volume, pp71-73, (1989).LSDP is dispersion agent and the weight ratio of disperseing the needed sodium oleate % of calcium soap precipitates, and wherein said calcium soap precipitates is to be equivalent to 333ppmCaCO by the 0.025g sodium oleate at 30ml ₃(Ca: Mg=3: 2) form in the water of hardness.

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

Being used for LSDP of the present invention is no more than 8 exemplary surfactants and comprises C ₁₆-C ₁₈Dimethyl oxidation amine; Average degree of ethoxylation is the C of 1-5 ₁₂-C ₁₈Alkyl ethoxy sulfate, particularly degree of ethoxylation are the C of 3 (LSDP=4) ₁₂-C ₁₅Alkyl ethoxy sulfate surfactant; And average degree of ethoxylation is the C of 12 (LSDP=6) or 30 ₁₄-C ₁₅Ethoxylated alcohol, it is commercially available with trade(brand)name LutensolA012 and LutensolA030 respectively by BASFGmbH.

The polymerization calcium soap peptizing agent that is fit to the present invention's use is at M.K.Nagarajan, and W.F.Masler states in the article of describing in the 71-73 page or leaf (1989) in " makeup and toilet articles " (Cosmetics and Toiletres) the 104th volume.

The hydrophobic bleach agent is as the amino caproyl of 4-[N-capryloyl-6-] benzene sulfonate, the amino caproyl of 4-[N-nonanoyl-6-] benzene sulfonate, the amino caproyl of 4-[N-decanoyl-6-] benzene sulfonate and composition thereof; And nonanoly acyloxy benzene sulfonate also can be used as the use of calcium soap peptizing agent compound together with the hydrophilic/hydrophobic bleaching preparations.Except that amylase, can also contain the stain release type enzyme that one or more provide clean-up performance and/or fabric nursing benefit in enzyme-bleaching composition of the present invention.These enzymes can comprise proteolytic enzyme, amylase, cellulase and lipase.They can suspension, the form of " ball " or " bead " is spiked in the non-aqueous liquid detergent compositions of the present invention.The enzyme of another suitable type comprises the enzyme of the slurries form that is present in the nonionogenic tenside, and the trade(brand)name that the trade(brand)name of producing as Novo Nordish is produced for the enzyme or the Novo Nordish of " SL " is the enzyme in the microcapsule of wrapping into of " LDP ".Suitable enzyme and the visible US patent 5,576,282 of consumption thereof.

In the present invention, especially preferably adding enzyme in the present composition to is form with conventional enzyme bead.The size range of this bead is generally about 100-1, and 000 micron, more preferably from about 200-800 micron, and the on-aqueous liquid phase that can suspend and spread all over whole composition.It is found that bead is compared with other enzyme form in the present composition, show desirable especially enzyme stability aspect the enzymic activity keeping in time.Thus, use and to contain the conventional enzyme stabilizers that often must use when enzyme is spiked into aqueous liquid detergent in the composition of this kind of enzyme bead again.

The example of suitable enzyme includes, but is not limited to hemicellulase, peroxidase, proteolytic enzyme, cellulase, zytase, lipase, Phospholipid hydrolase, esterase, at, polygalacturonase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, lignoenzyme, Starch debranching enzyme, tannase, pentosanase, malic enzyme (malanase), beta-glucanase, arabinofuranosidase/xylosidase, Unidasa, chondroitinase, laccase and known amylase or its mixture.Preferred combination is the bleaching composition that contains the mixture of enzyme commonly used such as proteolytic enzyme, amylase, lipase, at and/or cellulase and amylase of the present invention associating.

The example of this suitable enzyme is disclosed in US patent 5,576,282,5,728, in 671 and 5,707,950.

Suitable proteolytic enzyme is subtilysin, and it derives from subtilis (B.subtilis) and Bacillus licheniformis (B.licheniformis) (subtilysin BPN and BPN ').A kind of suitable proteolytic enzyme derives from bacillus, has maximum activity in pH8-12, by Novo IndustriesA/S (after this being called " the Novo ") cultivation of Denmark and with ESPERASE ^Commercially available.The preparation of this kind of enzyme and enzyme of the same race is described in 243,784 (the authorizing Novo) to some extent at GB1.Other suitable proteolytic enzyme comprises the ALCALASE that Novo produces ^, DURAZYM ^And SAVINASE ^And the MAXATASE of Gist-Brocades product ^, MAXACAL ^, PROPERASE ^With MAXAPEM  (protein engineering Maxacal).Proteolytic ferment also comprises the bacterial serine proteolytic enzyme through modification, for example describe in the european patent application serial number 87303761.8 (1987.4.28 applies for (the 17th, 24 and 98 page specifically)), and this paper is referred to as " proteolytic enzyme B "; And describe in the european patent application 199,404 (Venegas, 1986.10.29 is open), it is that this paper is called it " protease A " through the bacterial serine proteolytic ferment of modifying.Alleged " the proteolytic enzyme C " of this paper more preferably, it is a kind of variant that derives from the alkaline serine protease of bacillus, wherein replaced arginine at the 27th Methionin, replaced Xie Ansuan at the 104th tyrosine, replaced l-asparagine and replaced Threonine at the 274th L-Ala at the 123rd Serine.Proteolytic enzyme C is described among the EP90915958:4 (corresponding to WO91/06637,1991.5.16 is open).The variant of genetic modification, particularly the variant of proteolytic enzyme C is also included among the present invention.Also referring to describe among the WO93/18140A (Novo) by the high pH proteolytic enzyme that obtains among the Bacillus NCIMB40338.A kind of enzyme type washing composition that contains proteolytic enzyme, one or more other enzymes and reversible protease inhibitors has been described among the WO92/03529A (Novo).When needs, can utilize WO95/07791 (Procter ﹠amp; That describes Gamble) has low absorbability and high water-disintegrable proteolytic enzyme.Being fit to detergent use recombinant trypsin proteinoid enzyme of the present invention describes in WO94/25583 (Novo) to some extent.

Say in detail, the proteolytic enzyme that is called as " proteolytic enzyme D " is the carbonylic hydrolase variant, its have natural in non-existent aminoacid sequence, this sequence derives from the precursor carbonylic hydrolase, by in carbonylic hydrolase, being equivalent to replace a plurality of amino-acid residues with different aminoacids on the+76 positions, also preferred combination replaces and to be equivalent to one or more following amino acid residue positions that are selected from: according to the numbering of bacillus amyloliquefaciens (Bacillus amyloliquefaciens) subtilysin+99, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206, + 210, + 216, + 217, + 218, + 222, + 260, + 265, and/or+274 of WO95/10615 (1995.4.20 is open, Genencor International).The proteolytic enzyme BLAP  that describes among proteolytic enzyme of describing among suitable patent application EP251446 in addition of the present invention and the WO91/06637 and the WO91/02792.The addition content of proteolytic ferment in bleaching composition of the present invention is the 0.0001%-2% of composition weight, preferred 0.001%-0.2%, the more preferably pure enzyme of 0.005%-0.1%.

Useful proteolytic enzyme also is described in the PCT application: (1995.11.9 is open, The Procter ﹠amp for WO95/30010; Gamble company); (1995.11.9 is open, TheProcter ﹠amp for WO95/30011; Gamble company); (1995.11.9 is open, The Procter﹠amp for WO95/29979; Gamble company).

Other particularly preferred proteolytic enzyme is the ease variants of multiple replacement, these ease variants comprise with another kind of naturally occurring amino-acid residue substituted amino acid residue, the amino acid residue position that replaces is equivalent to 103 of bacillus amyloliquefaciens subtilysin, and the combination that is equivalent to following amino-acid residue the position of substitution: the 1st of bacillus amyloliquefaciens subtilysin, 3,4,8,9,10,12,13,16,17,18,19,20,21,22,24,27,33,37,38,42,43,48,55,57,58,61,62,68,72,75,76,77,78,79,86,87,89,97,98,99,101,102,104,106,107,109,111,114,116,117,119,121,123,126,128,130,131,133,134,137,140,141,142,146,147,158,159,160,166,167,170,173,174,177,181,182,183,184,185,188,192,194,198,203,204,205,206,209,210,211,212,213,214,215,216,217,218,222,224,227,228,230,232,236,237,238,240,242,243,244,245,246,247,248,249,251,252,253,254,255,256,257,258,259,260,261,262,263,265,268,269,270,271,272,274 and 275 positions; Wherein when said ease variants is included in the amino-acid residue replacement that is equivalent to 103 and 76, be equivalent to bacillus amyloliquefaciens subtilysin 27,99,101,104,107,109,123,128,166,204,206,210,216,217,218,222,260, the replacement that also has amino-acid residue on one or more amino acid residue positions except the 265 or 274 amino-acid residue positions, and/or with the ease variants of another kind of naturally occurring amino-acid residue multiple replacement of substituted amino acid residue on one or more amino acid residue positions, wherein said substituted amino acid residue position is equivalent to 62 of bacillus amyloliquefaciens subtilysin, 212,230,232,252 and 257, as PCT application WO 99/20727, PCT 99/20726 and PCT 99/20723 (are TheProcter ﹠amp; Gamble company has).More preferably, comprise (amino acid) replacement group that is selected from following group in the ease variants:

12/76/103/104/130/222/245/261；

62/103/104/159/232/236/245/248/252；

62/103/104/159/213/232/236/245/248/252；

62/101/103/104/159/212/213/232/236/245/248/252；

68/103/104/159/232/236/245；

68/103/104/159/230/232/236/245；

68/103/104/159/209/232/236/245；

68/103/104/159/232/236/245/257；

68/76/103/104/159/213/232/236/245/260；

68/103/104/159/213/232/236/245/248/252；

68/103/104/159/183/232/236/245/248/252；

68/103/104/159/185/232/236/245/248/252；

68/103/104/159/185/210/232/236/245/248/252；

68/103/104/159/210/232/236/245/248/252；

68/103/104/159/213/232/236/245；

98/103/104/159/232/236/245/248/252；

98/102/103/104/159/212/232/236/245/248/252；

101/103/104/159/232/236/245/248/252；

102/103/104/159/232/236/245/248/252；

103/104/159/230/236/245；

103/104/159/232/236/245/248/252；

103/104/159/217/232/236/245/248/252；

103/104/130/159/232/236/245/248/252；

103/104/131/159/232/236/245/248/252；

103/104/159/213/232/236/245/248/252; With

103/104/159/232/236/245. more preferably, comprise the replacement group that is selected from following group in the ease variants:

12R/76D/103A/104T/130T/222S/245R/261D；

62D/103A/104I/159D/232V/236H/245R/248D/252K；

62D/103A/104I/159D/213R/232V/236H/245R/248D/252K；

68A/103A/104I/159D/209W/232V/236H/245R；

68A/76D/103A/104I/159D/213R/232V/236H/245R/260A；

68A/103A/104I/159D/213E/232V/236H/245R/248D/252K；

68A/103A/104I/159D/183D/232V/236H/245R/248D/252K；

68A/103A/104I/159D/232V/236H/245R；

68A/103A/104I/159D/230V/232V/236H/245R；

68A/103A/104I/159D/232V/236H/245R/257V；

68A/103A/104I/159D/213G/232V/236H/245R/248D/252K；

68A/103A/104I/159D/185D/232V/236H/245R/248D/252K；

68A/103A/104I/159D/185D/210L/232V/236H/245R/248D/252K；

68A/103A/104I/159D/210L/232V/236H/245R/248D/252K；

68A/103A/104I/159D/213G/232V/236H/245R；

98L/103A/104I/159D/232V/236H/245R/248D/252K；

98L/102A/103A/104I/159D/212G/232V/236H/245R/248D/252K；

101G/103A/104I/159D/232V/236H/245R/248D/252K；

102A/103A/104I/159D/232V/236H/245R/248D/252K；

103A/104I/159D/230V/236H/245R；

103A/104I/159D/232V/236H/245R/248D/252K；

103A/104I/159D/217E/232V/236H/245R/248D/252K；

103A/104I/130G/159D/232V/236H/245R/248D/252K；

103A/104I/131V/159D/232V/236H/245R/248D/252K；

103A/104I/159D/213R/232V/236H/245R/248D/252K; With

103A/104I/159D/232V/236H/245R.

Most preferably, ease variants comprises replacement group 101/103/104/159/232/236/245/248/252, preferred 101G/103A/104I/159D/232V/236H/245R/248D/252K.

The cellulase that can use in the present invention comprises two kinds of bacterium or fungal cellulases.Preferably, their best pH is 5-9.5.Suitable cellulase is disclosed in US patent 4,435,307 (Barbesgoard etc.), and it discloses the fungal cellulase of being produced by Humicola insolens.Suitable cellulase also is disclosed in GB-A-2.075.028; Among GB-A-2.095.275 and the DE-OS-2.247.832.

The example of this cellulase is the cellulase of being produced by Humicola Insolens (grey humicola lanuginosa mutation thermoidea) bacterial strain, particularly humicola lanuginosa strain DSM 1800.

To be the molecular weight that comes from the Insolens humicola lanuginosa be 5.5 and contain 415 amino acid whose cellulases for about 50KDa, iso-electric point other suitable cellulase; And the endoglucanase that derives from the 43kD that shows cellulase activity of Humicola Insolens DSM1800; Preferred endoglucanase component has disclosed aminoacid sequence among the PCT patent application WO91/17243.Suitable cellulase also has from the mould EG III cellulase of longibrachiatum wood, and it is described among the WO94/21801 (Genencor, 1994.9.29 is open).Shi Yi cellulase is to have the cellulase that protects chromatic effect especially.The example of this cellulase is the cellulase that is described in the european patent application 91202879.2 (1991.11.6 applies for (Novo)).Carezyme and Celluzyme (Novo Nordisk A/S) are particularly suitables.Also referring to WO91/17243.

Peroxidase is known in the art, and for example comprises horseradish peroxidase, lignoenzyme or halo peroxidase such as chloro-and bromo-peroxidase.The bleaching composition that contains peroxidase is in for example US patent 5,576,282,5,728,671 and 5,707,950, PCT International Application No. WO 89/099813, WO89/09813 and in European patent application EP 91202882.6 (1991.11.6 application) and EP96870013.8 (1996.2.20 application), have disclosed.Suitable laccase in addition.

The thiodiphenylamine that preferred toughener is replacement and phenoxazine, lysivane propionic acid (PPT), 10-ethyl thiodiphenylamine-4-carboxylic acid (EPC), 10-phenoxazine propionic acid (POP) and 10-first base phenoxazine (being described in WO94/12621) and the cloves acid esters (C3-C5 substituted alkyl cloves acid esters) and the phenol that replace.SPC-D or perborate are preferred hydrogen peroxide cources.

The incorporation of said peroxidase in bleaching composition is generally the pure enzyme of 0.0001-2% of bleaching composition weight.

Other preferred enzyme that can be included in the bleaching composition of the present invention comprises lipase.The lipase that is fit to the washing composition use comprises as English Patent 1,372,034 disclosed enzyme by the Rhodopseudomonas microorganisms producing, for example enzyme of producing by Situ Ci Shi pseudomonas (Pseudomonasstutzeri) ATCC19.154.Suitable lipase comprises the lipase that shows positive immunological cross-reaction with lipase antibody, and this enzyme is produced by microorganism Pseudomonas fluorescens (Pseudomonasfluorescent) IAM 1057.This lipase can trade(brand)name lipase P " Amano " available from Amano Pharm Pur GmbH (Japan Nagoya), after this it is called " Amano-P ".Other suitable commercially available lipase comprises Amano-CES; The thickness look bacillus lipase (chromobacter viscosum) of Toyo Jozo company (Tagata, Japan) is as the lipase of thickness look bacillus mutation lipolyticum NRRLB 3673 productions; The lipase that the thickness look bacillus lipase of U.S. Biochemics Inc. (U.S.A.) and Disoynth company (Holland) and gladiolus pseudomonas (Pseudomonas gladioli) produce.Shi Yi lipase is such as M1LIPASE especially ^And LIPOMAX ^(Gist-Brocades) and LIPOLASE ^And LIPOLASEULTRA ^(NOVO) lipase it is found that when with composition coupling of the present invention very effective.

Suitable at [EC3.1.1.50] in addition, it can think a special lipoidase, does not promptly need the lipase of interface activation.For example, in WO 88/09357 (Genencor), described to bleaching composition interpolation at.

Lipase and/or the at addition content in bleaching composition is generally the pure enzyme of 0.0001-2% of bleaching composition weight.

Can contain known amylase (α and/or β) and remove the carbohydrate type stain.Among the WO94/02597 (Novo Nordisk A/S, 1994.2.3 is open) cleaning compositions that is mixed with mutant amylase has been described.Be also shown in WO94/18314 (Genencor, 1994.8.18 is open) and WO95/10603 (Novo Nordisk A/S, 1995.4.20 is open).Known other amylase that can use in bleaching composition comprises α-and beta-amylase.α-Dian Fenmei is known in the art, and comprises US patent 5,003,257; EP252,666; WO91/00353; FR2,676,456; EP285,123; EP525,610; EP368,341 and UK Patent Application 1,296,839 (Novo) in disclosed amylase.Other suitable amylase is stable enhanced amylase, comprise PURAFACT OX AM  and the NovoNordisk A/S disclosed amylase variant in WO95/10603 (95.4) described among WO94/18314 (1994.8.18 is open) and the WO96/05295 (Genencor, 1996.2.22 is open).

The example of commercially available α-Dian Fenmei product is the TERMAMYL that Denmark Novo Nordisk A/S produces ^, BAN ^, FUNGAMYL ^And DURAMYL ^WO95/26397 has described other suitable amylase: α-Dian Fenmei, it is characterized in that its specific activity, 25-55 ℃ and at pH8-10 by the test of Phadebas  alpha-amylase activity, compare TERMARNYL ^Specific activity height at least 25%.Other amylolytic enzyme that level of activity and thermostability all are improved and have the greater activity degree has been described among the WO95/35382.

Can also contain mannase in the composition of the present invention.Preferably, mannase is selected from: three kinds of mannosans degrading enzyme: EC3.2.1.25: beta-Mannosidase, EC3.2.1.78: interior-1, the 4-beta-Mannosidase, hereinafter be called " mannase " and EC3.2.1.100:1, the biological Glycosylase of 4-β-sweet dew and composition thereof (IUPAC classification-enzyme nomenclature, 1992ISBN0-12-227165-2 Academic Press).

More preferably, when having mannase, contain the β-1 that is known as mannase in the composition for treating of the present invention, 4-mannosidase (EC3.2.1.78).Term " mannase " or " polygalactomannan enzyme " expression are according to the mannase of prior art with the official definition, its name is called mannosans interior-1,4-beta-Mannosidase and another name are called 'beta '-mannase and interior-1, the 4-mannase, and in catalysis mannosans, polygalactomannan, glucomannan and the galactoglucomannan 1, the reaction of the random hydrolysis of 4-β-D-seminose glycosidic bond.

Specifically, mannase (EC3.2.1.78) has constituted one group of polysaccharidase, its degraded mannosans and expression can be ruptured and be contained the enzyme of the unitary polysaccharide chain of seminose, promptly can break at the enzyme of the glycosidic link in mannosans, polygalactomannan, glucomannan and the galactoglucomannan.Mannase is to contain by β-1, the polysaccharide of the main chain that the seminose that 4-connects is formed; Glucomannan is to contain more or less rule change β-1, the polysaccharide of the seminose that 4-connects and the main chain of glucose; Polygalactomannan and galactoglucomannan are to have α-1, the mannosans and the glucomannan of the galactose side that 6-connects.These compounds can be acetylation.

By removing galactose side wholly or in part, can promote the degraded of polygalactomannan enzyme and galactoglucomannan enzyme.In addition, the degraded of acetylizad mannosans, glucomannan, polygalactomannan, galactoglucomannan can become easy by deacetylated wholly or in part.Ethanoyl can remove by alkali or by the mannosans acetylase.Can further degrade from the oligopolymer that mannase or the combination by mannase and alpha-galactosidase and/or mannosans acetylase discharge, from beta-Mannosidase and/or beta-glucosidase enzyme, discharge free maltose.

Mannase is discerned in the biology of many Bacilluss.For example, Talbot etc., Appl.Environ.Microbiol., Vol.56, No.11, pp.3505-3510 (1990) has described a kind of 'beta '-mannase by the dipolymer form that obtains in the bacillus stearothermophilus (Bacillus stearothermophilus), and its molecular weight is that 162kDa and best pH are 5.5-7.5.Mendoza etc., World J.Microbiol.Biotech., 10 volumes, 5 phases, 551-555 page or leaf (1994) has been described a kind of 'beta '-mannase that derives from Bacillus subtillis, its molecular weight is 38kDa, optimum activity pH5.0 and 55 ℃ down and pI be 4.8.JP-03047076 discloses a kind of 'beta '-mannase that derives from Bacillus, and its molecular weight is determined as 373kDa by gel-filtration, and best pH is that 8-10 and pI are 5.3-5.4.Production alkaline, heat-staple 'beta '-mannase that JP-63056289 has described, this enzymic hydrolysis is the β of mannosans-1 for example, 4-D-mannopyranose glycosidic bond, and produce manna oligosaccharide.JP-63036774 relates to bacillus microorganism belonging to genus FERMP-8856, and it produces 'beta '-mannase and beta-Mannosidase under alkaline pH.JP-08051975 discloses the alkaline ' beta '-mannase that obtains by among basophilia Bacillus (the alkalophilic Bacillus sp.) AM-001.Mannase of a kind of purifying that can be used for bleached pulp and paper from bacillus amyloliquefaciens and preparation method thereof is disclosed among the WO97/11164.WO91/18974 has described a kind of active hemicellulase that has under limit pH and temperature, as dextranase, and zytase or mannase.WO94/25576 discloses a kind of microorganism Aspergillus aculeatus (Aspergillusaculeatus) that derives from, CBS101.43, the active enzyme of demonstration mannase, this enzyme can be used for degraded and modified plant or alga cells wall material.WO93/24622 disclose a kind of from Trichoderma reseei isolating mannase, this enzyme can be used for the bleaching lignin cellulose slurry.Described among the WO91/18974 among a kind of hemicellulase of the hemicellulose that contains mannosans of can degrading and the WO97/11164 and described a kind of mannase that derives from the purifying of bacillus amyloliquefaciens.

Preferably, mannase is with undefined alkali mannanase, more preferably, derives from the mannase of bacterial origin.Specifically, contain in the laundry detergent composition of the present invention and be selected from following alkali mannanase: the mannase that derives from bacterial strain Bacillus agaradhaerensNICMB 40482; Derive from Bacillus subtillis bacterial strain 168, the mannase of gene yght; Derive from the mannase of Bacillus I633 and/or derive from the mannase of Bacillus AAI 12.The mannase that most preferably comprises in the detergent composition of the present invention is the mannase that derives from Bacillus I 633 described in we common autre action pendante Danish Patent Application PA 1,998 01340.

The enzymic activity that term " alkali mannanase " refers to be included in the appointment pH scope of 7-12, preferred 7.5-10.5 is at least 10% of its maximum activity, preferably at least 25%, and more preferably at least 40% enzyme.

The alkali mannanase that derives from Bacillus agaradhaerens NICMB 40482 is described in our the common autre action pendante US patent application series number 09/111,256.Say that more specifically this mannase is: i) by Bacillus agaradhaerens, the polypeptide that NCIMB 40482 produces; Or ii) contain the polypeptide of aminoacid sequence shown in the position 32-343 of SEQ ID NO:2 shown in the US patent application series number 09/111,256; Or iii) i) analogue of the polypeptide of definition or ii), its at least 70% with said homologous peptide, perhaps obtain by said polypeptide, perhaps be immune response with the polyclonal antibody that the said polypeptide of relative pure form produces by displacement, disappearance or additional one or more amino acid.Also comprise and have the active corresponding isolated polypeptide of mannase, be selected from: (a) polynucleotide molecule, its coding has the active polypeptide of mannase and contains shown in the US patent application series number 09/111,256 among the SEQ ID NO:1 nucleotide sequence shown in 1029 from Nucleotide 97 to Nucleotide; (b) species homologue (a); (c) polynucleotide molecule, coding have mannase active, at least 70% and US patent application series number 09/111,256 shown among the SEQ ID NO:2 from amino-acid residue 32 to amino-acid residue the identical polypeptide of the aminoacid sequence shown in 343; (d) with (a) and (b) or (c) complementary molecule; (e) (a) and (b), (c) or degeneracy (d) (degentrate) nucleotide sequence.The plasmid pSJ1678 that contains the polynucleotide molecule (dna sequence dna) of the said mannase of encoding has been converted to dust Xi Shi intestinal bacteria (E.coli) bacterial strain, it by the present inventor according to budapest treaty according to International Recognition of the Deposit ofMicroorganisms for the Purposes of Patent Procedure at theDeutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg lb, D-38124 Braunschweig, Germany (FederalRepublic of Germany), in preservation on May 19 in 1998, preserving number DSM12180.

Second kind of preferred enzyme is the mannase of describing in our the common autre action pendante US patent application series number 09/095,163 that derives from Bacillus subtillis bacterial strain 168.Say that more specifically this mannase is: i) encoding part of the analogue by dna sequence dna shown in the SED ID No.5 shown in the US patent application series number 09/095,163 or said sequence is coded; And/or ii) contain the polypeptide of aminoacid sequence shown in the SEQ ID NO:6 shown in the US patent application series number 09/095,163; Or the analogue of the polypeptide that iii) ii) defines, its at least 70% with said homologous peptide, perhaps obtain by said polypeptide, perhaps be immune response with the polyclonal antibody that the said polypeptide of relative pure form produces by displacement, disappearance or additional one or more amino acid.

Also comprise and have the active corresponding isolated polypeptide of mannase, be selected from: (a) polynucleotide molecule, its coding active polypeptide of tool mannase and contain the nucleotide sequence shown in the SEQ ID NO:5 shown in the US patent application series number 09/095,163; (b) species homologue (a); (c) polynucleotide molecule, coding have mannase active, at least 70% and US patent application series number 09/095,163 shown in the identical polypeptide of aminoacid sequence shown in the SEQ ID NO:6; (d) with (a) and (b) or (c) complementary molecule; (e) (a) and (b), (c) or degenerate core nucleotide sequence (d).

The third preferred mannase is described among we the common autre action pendante Danish Patent Application PA 1,998 01340.Say that more specifically this mannase is: the i) polypeptide that produces by Bacillus I633; The polypeptide that ii) contains aminoacid sequence shown in the position 33-340 of SEQ ID NO:2 shown in the Danish Patent Application PA 1,998 01340; Or iii) i) analogue of the polypeptide of definition or ii), its at least 65% with said homologous peptide, obtain by said polypeptide by displacement, disappearance or additional one or more amino acid, perhaps be immune response with the polyclonal antibody that the said polypeptide of relative pure form produces.

Also comprise and have the active corresponding isolated polypeptide of mannase, be selected from: (a) polynucleotide molecule, its coding active polypeptide of tool mannase and contain shown in the Danish Patent Application PA 1,998 01340 among the SEQ ID NO:1 nucleotide sequence shown in 1243 from Nucleotide 317 to Nucleotide; (b) species homologue (a); (c) polynucleotide molecule, the coding have mannase active, at least 65% with SEQ ID NO:2 shown in the Danish Patent Application PA 1,998 01340 in from amino-acid residue 33 to amino-acid residue the identical polypeptide of the aminoacid sequence shown in 340; (d) with (a) and (b) or (c) complementary molecule; (e) (a) and (b), (c) or degenerate core nucleotide sequence (d).

The plasmid pBX3 that contains the polynucleotide molecule (dna sequence dna) of the said mannase of encoding has been converted to coli strain, it by the present inventor according to budapest treaty according to International Recognition of the Deposit of Microorganismsfor the Purposes of Patent Procedure at the Deutsche Sammlungvon Mikroorganismen und Zellkulturen GmbH, Mascheroder Weglb, D-38124 Braunschweig, Federal Republic of Germany, in preservation on May 29 in 1998, preserving number DSM12197.

The 4th kind of preferred mannase is described in our common autre action pendante Danish Patent Application PA 1,998 01341.Say that more specifically this mannase is: the i) polypeptide that produces by Bacillus AAI12; The polypeptide that ii) contains aminoacid sequence shown in the position 25-362 of SEQ ID NO:2 shown in the Danish Patent Application PA 1,998 01341; Or iii) i) analogue of the polypeptide of definition or ii), its at least 65% with said homologous peptide, obtain by said polypeptide by displacement, disappearance or additional one or more amino acid, perhaps be immune response with the polyclonal antibody that the said polypeptide of relative pure form produces.Also comprise and have the active corresponding isolated polypeptide of mannase, be selected from: (a) polynucleotide molecule, its coding have the active polypeptide of mannase and contain shown in the Danish Patent Application PA 1,998 01341 among the SEQ ID NO:1 nucleotide sequence shown in 1236 from Nucleotide 225 to Nucleotide; (b) species homologue (a); (c) polynucleotide molecule, the coding have mannase active, at least 65% with SEQ ID NO:2 shown in the Danish Patent Application PA 1,998 01341 in from amino-acid residue 25 to amino-acid residue the identical polypeptide of the aminoacid sequence shown in 362; (d) with (a) and (b) or (c) complementary molecule; (e) (a) and (b), (c) or degenerate nucleotide sequence (d).

The plasmid pBX1 that contains the polynucleotide molecule (dna sequence dna) of the said mannase of encoding has been converted to dust Xi Shi coli strain, it by the present inventor according to budapest treaty according to International Recognition of the Deposit of Microorganismsfor the Purposes of Patent Procedure at the Deutsche Sammlungvon Mikroorganismen und Zellkulturen GmbH, Mascheroder Weglb, D-38124 Braunschweig, Germany (Federal Repubc ofGermany), in preservation on October 7 in 1998, preserving number DSM12433.

When existing, the incorporation of mannase in composition for treating of the present invention is the 0.0001%-2% of composition weight, more preferably 0.0005%-0.1%, the most preferably pure enzyme of 0.001%-0.02%.

Can also contain xyloglucanase enzymes in the composition of the present invention.The xyloglucanase enzymes that is suitable for the object of the invention is the enzyme that xyloglucan is shown special endoglucanase activity, and preferred content is that about 0.001%-of composition weight is about 1%, and more preferably from about 0.01%-about 0.5%.Herein, term " endoglucanase activity " refers to that enzymic hydrolysis is present in any cellulosic materials material such as Mierocrystalline cellulose, derivatived cellulose, lichenstarch, 1 in callose or the xyloglucan, the ability of 4-β-D-glycosidic link.Endoglucanase activity can be measured according to methods known in the art, the example in WO94/14953 and below describe to some extent.The endoglucanase activity of one unit (for example, CMCU, AVIU, XGU or BGU) be defined as from dextran substrate produce 1 μ mol reducing sugar/minute, dextran substrate is, for example, CMC (CMCU), the Avicell of acid-swellable (AVIU), xyloglucan (XGU) or cereal beta-glucan (BGU).The visible WO94/14953 of the mensuration of reducing sugar and below.Endo-dextranase is to the specific activity unit of the being defined as/milligram protein of substrate.

Suitable is shows the enzyme of high reactivity XGU endoglucanase activity (following be " special to xyloglucan "), this enzyme: i) coded by the dna sequence dna that contains or comprise following at least one local sequence:

(a)ATTCATTTGT?GGACAGTGGA?C(SEQ?ID?No：1)

(b)GTTGATCGCA?CATTGAACCA?(SEQ?ID?NO：2)

(c)ACCCCAGCCG?ACCGATTGTC?(SEQ?ID?NO：3)

(d)CTTCCTTACC?TCACCATCAT?(SEQ?ID?NO：4)

(e)TTAACATCTT?TTCACCATGA?(SEQ?ID?NO：5)

(f)AGCTTTCCCT?TCTCTCCCTT?(SEQ?ID?NO：6)

(g)GCCACCCTGG?CTTCCGCTGC?CAGCCTCC?(SEQ?ID?NO：7)

(h)GACAGTAGCA?ATCCAGCATT?(SEQ?ID?NO：8)

(i)AGCATCAGCC?GCTTTGTACA?(SEQ?ID?NO：9)

(j)CCATGAAGTT?CACCGTATTG?(SEQ?ID?NO：10)

(k)GCACTGCTTC?TCTCCCAGGT?(SEQ?ID?NO：11)

(l)GTGGGCGGCC?CCTCAGGCAA?(SEQ?ID?NO：12)

(m)ACGCTCCTCC?AATTTTCTCT?(SEQ?ID?NO：13)

(n)GGCTGGTAG?TAATGAGTCT?(SEQ?ID?NO：14)

(o)GGCGCAGAGT?TTGGCCAGGC?(SEQ?ID?NO：15)

(p)CAACATCCCC?GGTGTTCTGG?G(SEQ?ID?NO：16)

(q)AAAGATTCAT?TTGTGGACAG?TGGACGTTGA?TCGCACATTG

AACCAACCCC?AGCCGACCGA

TTGTCCTTCC?TTACCTCACC?ATCATTTAAC?ATCTTTTCAC?CATGAAGCTT

TCCCTTCTCT

CCCTTGCCAC?CCTGGCTTCC?GCTGCCAGCC?TCCAGCGCCG?CACACTTCTG

CGGTCAGTGG

GATACCGCCA?CCGCCGGTGA?CTTCACCCTG?TACAACGACC?TTTGGGGCGA

GACGGCCGGC ACCGGCTCCC AGTGCACTGG AGTCGACTCC TACAGCGGCG ACACCATCGC TTGTCACACC AGCAGGTCCT GGTCGGAGTA GCAGCAGCGT CAAGAGCTAT GCCAACG (SEQ ID NO:17) or (r) CAGCATCTCC ATTGAGTAAT CACGTTGGTG TTCGGTGGCC CGCCGTGTTG CGTGGCGGAG GCTGCCGGGA GACGGGTGGG GATGGTGGTG GGAGAGAATG TAGGGCGCCG TGTTTCAGTC CCTAGGCAGG ATACCGGAAA ACCGTGTGGT AGGAGGTTTA TAGGTTTCCA GGAGACGCTG TATAGGGGAT AAATGAGATT GAATGGTGGC CACACTCAAA CCAACCAGGT CCTGTACATA CAAGCATAT ACCAATTATA CCTACCAAAA AAAAAAAAAA AAAAAAAAAA AAAA (SEQ ID NO:18) or with its homologous sequence, this sequence encoding is to the specific polypeptide of the xyloglucan of tool endoglucanase activity, ii) with the relative i of passing through) antibody that produces of the high purifying endo-dextranase of the dna sequence encoding of definition is immune response, and derive from microorganism Aspergillus aculeatus, CBS101.43, and special to xyloglucan.

More specifically say, herein, term " special to xyloglucan " refers to that endo-dextranase shows the highest endoglucanase activity to the xyloglucan substrate, and the substrate of other cellulose such as carboxymethyl cellulose, Mierocrystalline cellulose or other dextran are shown preferably activity less than 75%, be more preferably less than 50% activity, most preferably less than about 25% activity.

Preferably, endo-dextranase is further defined as relative reactivity to the specificity of xyloglucan, and this relative reactivity is determined as the release by the reducing sugar under top condition of cultivating xyloglucan and other substrate acquisition to be measured with enzyme respectively.For example, specificity can be defined as xyloglucan to beta-glucan activity (XGU/BGU), and xyloglucan is to carboxymethyl cellulose activity (XGU/CMCU), or xyloglucan is to acid-swellable Avicell activity (XGU/AVIU), it is preferably greater than about 50, as 75,90 or 100.

Herein, term " derives from " and not only refers to the endo-dextranase that produces by bacterial strain CBS101.43, also refers to by separated DNA sequence encoding among the bacterial strain CBS101.43 and the endo-dextranase that produces in the host living beings with said dna sequence dna transformation.Herein, term " homologue " refers to the polypeptide by dna encoding, said DNA is hybridized in the same probe, as under given conditions (as pre-soaking in 5 * SSC and in the solution of 5 * SSC, 5 * Denhardt solution and 50 μ g sex change supersound process calf thymus DNAs-40 ℃ of following prehybridizations 1 hour,-40 ℃ of down hybridization 18 hours in the same solution of having replenished 50 μ Ci32-P-dCTP label probes subsequently, and 40 ℃ of washings in following 30 minutes three times in 2 * SSC, 0.2%SDS) coding is to the DNA of the special endo-dextranase of xyloglucan.Say that more specifically this term is intended to refer to dna sequence dna, its at least 70% with above-mentioned shown in coding to any sequence homology of the special endo-dextranase of xyloglucan, comprise at least 75%, at least 80%, at least 85%, at least 90%, in addition at least 95% and above-mentioned shown in any sequence homology.This term is intended to comprise the modification to any DNS sequence shown in above-mentioned, as nucleotide subsitution, this displacement does not produce the another kind of amino acid sequence of polypeptide of sequence encoding thus, but the codon that is equivalent to host living beings is chosen and introduced the DNA construct that contains any dna sequence dna; Perhaps nucleotide subsitution, this displacement does not produce different aminoacid sequences, and therefore do not produce possible different aminoacids sequence and so issuable different protein structure, this aminoacid sequence can cause producing the endo-dextranase mutant different with the natural enzyme performance with protein structure.Other suitable modification is to insert one or more Nucleotide to sequence, at the additional one or more Nucleotide of arbitrary end of sequence, perhaps lacks one or more Nucleotide at arbitrary end of sequence or in sequence.

Can use in the present invention to the special endo-dextranase of xyloglucan XGU/BGU preferably, XGU/CMU and/or XGU/AVIU are than (as above definition) enzyme greater than 50, as 75,90 or 100.

In addition, the special endo-dextranase of xyloglucan is not preferably had activity basically to beta-glucan and/or when the activity to xyloglucan is 100%, carboxymethyl cellulose and/or Avicell are shown 25% as maximum 10% or about 5% activity at the most.In addition, of the present invention preferably do not have transferase active (a kind of activity of finding) basically to the special endo-dextranase of xyloglucan in the major part of the plant origin endo-dextranase special to xyloglucan.

The endo-dextranase special to xyloglucan can obtain from the fungi microorganism Aspergillus aculeatus, described in WO94/14953.The microorganism endo-dextranase special to xyloglucan also described among the WO94/14953.Therefore derive from plant the special endo-dextranase of xyloglucan is described, but these enzymes have transferase active, whenever the thorough degraded of xyloglucan when being required, must think that it is less than the microorganism endo-dextranase special to xyloglucan.Another advantage of microbial enzyme is, on the whole, compares the enzyme in other source, and output is higher in microorganism host.

Xyloglucanase enzymes, when existing, the incorporation in composition for treating of the present invention is preferably the 0.0001%-2% of composition weight, more preferably 0.0005%-0.1%, the most preferably pure enzyme of 0.001%-0.02%.

Above-mentioned enzyme can derive from any suitable source, for example plant, animal, bacterium, fungi and yeast source.Can use the purifying of these enzymes or purified form not.The mutant that also comprises natural enzyme in the definition.Mutant can obtain by albumen and/or genetically engineered, chemistry and/or the physical modification as natural enzyme.Commonly used expresses enzyme in addition by host living beings, wherein clone the gene raw material that can be used for producing enzyme.

Under the normal circumstances, the incorporation of said enzyme in bleaching composition is the 0.0001-2% organized enzyme of bleaching composition weight.Enzyme can be used as independent batching to be added (bead, the particle that contain a kind of enzyme, stable liquid etc.) respectively or adds (as particle altogether) as the mixture of two or more enzyme.

Other suitable detergent ingredients that can add is the oxydasis scavenging agent.The example of this scavenging agent is ethoxylation four ethylidene polyamine.

WO93/07263 and WO93/07260 (Genencor International), WO89/08694 (Novo) and US3 also disclose a lot of proenzyme material among 553,139 (1971.1.5, the McCarty etc.) and they are incorporated into the mode of synthesizing in the bleaching composition.Enzyme also is disclosed in US4,101,457 (Place etc., 1978.1.18) and US4,507,219 (Hughes, 1985.3.26) in.Enzyme that suitable liquid detergent preparation is used and the method that is incorporated in this preparation thereof are disclosed in US4,261,868 (Hora etc., 1981.4.14).The enzyme that uses in enzyme stabilizers-washing composition can be by various consistent.The enzyme stabilization technology is at US3,600,319 (1971.8.17 Gedge etc.), EP199, and 405 and EP200,586 (1986.10.29 has disclosed and example in Venegas).The enzyme stabilization system also is described in for example US3, in 519,570.A kind of bacillus AC13 that produces proteolytic enzyme, zytase and cellulase has been described among the WO9401532 (Novo).The used enzyme of the present invention can be stablized by the water-soluble sources that has calcium and/or magnesium ion in final product composition having, and the water-soluble sources of wherein said calcium and/or magnesium ion provides these ions to enzyme.Suitable enzyme stabilizers and consumption thereof are described in US patent 5,576,282 to some extent.Can also not necessarily contain following one or more compositions in other detergent ingredients-bleaching composition of the present invention: polymeric dispersant, earth stain remover/anti-redeposition agent, whitening agent, suds suppressor, dyestuff, spices, the structure softening agent, fabric softener, carrier, hydrotropic agent, processing aid and/or pigment.The visible US patent 5,576,282 of the suitable example of these other detergent ingredients and consumption thereof.The method of laundering of textile fabrics

Organic catalyst of the present invention can be used for any washing or cleaning method basically with the composition that contains this organic catalyst, comprises the method for immersion process, pretreatment process and band rinse step, can add the rinse aid composition separately in this method.

The method of laundering of textile fabrics of the present invention preferably includes fabric is contacted with washing soln, contains by the may command that defines among testing program I, II and/or the III in the wherein said solution and utilizes method and become available (effectively) organic catalyst in washing soln.Not necessarily, but preferred, contain peroxygen source in the washing soln.

Method of the present invention can be implemented in cleaning course easily.Cleaning method preferably carries out under 5-95 ℃, particularly carries out under 10-60 ℃.The pH of washing soln is 7-11 preferably.The organic catalyst product

Use in the various products that organic catalyst of the present invention and/or bleaching composition can be used in laundry processes.

In a preferred embodiment, the invention provides a kind of product, wherein contain organic catalyst of the present invention and/or contain the composition of organic catalyzer, wherein organic catalyst by following discloses testing program I, II and/or III in the may command that defines utilize method and in washing soln, become and can utilize.This product also contains and is used for instruct using the specification sheets that organic catalyst and/or bleaching composition clean needs clean textiles (preferred dirty fabric).These working instructions may further comprise the steps: transmit a certain amount of product that contains organic catalyzer and/or bleaching composition for the washing soln that contains fabric, associating or do not unite peroxygen source, so as organic catalyst by following discloses testing program I, II and/or III in the may command that defines utilize method and in washing soln, become and can utilize (effectively).The mensuration of organic catalyst may command usability

Whether belong to scope of the present invention for ease of the product of determining organic catalyst of the present invention or bleaching composition or containing organic catalyst of the present invention or bleaching composition, below provide three testing programs, testing program I, II and III.

Have only as the situation I that satisfies scheme I ₁, scheme II situation II ₁Situation III with scheme III ₁, the product (OCCP) that contains organic catalyzer does not just belong to scope of the present invention.OCCP testing program I

General provisions/parameter: all solution remain 25 ℃.Use suitable yellow soda ash or sulfuric acid to regulate pH on demand.With all solution continuously stirring under 250rpm, except that a small amount of (1-5mL) dye bleach solution (DBS) aliquots containig work of taking-up mensuration absorbancy is used.At λ _MaxMeasure the absorbance of contrast dye solution (RDS) down.

Carry out test operation to determine parameter d _BleachOr w _OCCPWhether need reset by its default value.

d _BleachBe describe that dye bleach solution (DBS) forms and data obtain between parameter in the final testing program of elapsed time.This parameter d _BleachDefault value be 1 minute, but can be defined as according to following situation I the longer time.

w _OCCPIt is the parameter of describing in the final testing program of the product that contains organic catalyzer (OCCP) weight of the solution (OCCPS) be used to form the product that contains organic catalyzer.The default value of this parameter is 1.00g, but can be defined as less amount or weight according to following situation II.

CDS is dense dye solution, is defined as (Aldrich) the 300ppm solution in deionized water of amaranth dyestuff (Amaranth dye), and its pH is 10.

OCCP is the product of preparing fully that contains organic catalyzer (as above definition), and wherein organic catalyst can exist with various auxiliary materials.

OCCPS is the solution that contains the product of organic catalyzer, is dissolved in 25 ℃ of deionized waters of 1.0L by the product (OCCP) that 1.00g is contained organic catalyzer to make, and it is 9.9-10.1 that its pH is adjusted to the pH that makes final solution in advance.

DBS is that the OCCPS with the 100mL aliquots containig adds the dye bleach solution that forms among the 10mL CDS to.

A _MaxMensuration: the deionized water of 100mLpH10 is added among the 10mLCDS.By the UV visible spectrum at λ _Max(approximately 518nm) measures the absorbancy of the even contrast dye solution (RDS) of gained down, and it is A _Max

Get the time of aliquots containig: the time of getting aliquots containig from OCCPS comprises set time (t _f) and specified time in time limit (t _Dd).t _fValue be 0.5,1.5,2.5 and 3.5 minute.t _DdValue be 0.25D, 0.50D and 0.75D, wherein D be the washing recommended period.Do not get t _DdTime limit regulation aliquots containig less than 5 minutes.In this test, D can be not less than 5 minutes and be not more than 16 hours.If the producer of OCCP does not recommend to wash the time limit, then D is set for 20 minutes.For example, if be 60 minutes wash(ing)cycle, then remove t _fOuter required t _DdIt is 15,30 and 45 minutes.For 12 minutes wash(ing)cycle, required data point is relevant with the aliquots containig of getting 0.5,1.5,2.5,3.5,6 and 9 minute the time.

Use d _BleachAnd W _OCCPDefault value carry out following the test.From all fixing and time limit regulation aliquots containigs, determine one and produce the minimum absorbance A of measuring _MinAliquots containig Q.Time (t during with this Q of taking-up _fOr t _Dd) be defined as t _QNotice that this same point is represented maximum δ A (A just _Max-A _Min).According to A _MinValue, have three kinds of situations.

Situation I: if A _Min＞0.9A _Max, the recast test is so that reset d _BleachValue.In new test, with t _QThe time aliquots containig such as the pre-treatment of getting, difference is to stir with other 1 minute increment, until absorbance A _Min≤ 0.9A _MaxTime.With satisfy the required DBS of absorbancy condition stir the minimum time (minute) the new d of definition _Bleach, so that carry out final testing program.Yet d if desired _BlanchGreater than 30 minutes [promptly, if in 30 minutes, even when δ A is maximum the time point of (when organic catalyzer exists with maximum concentration), can not reach 10% bleaching], then OCCP can not be proved by the scheme I that belongs to the scope of the invention, but can find that OCCP belongs to scope of the present invention by scheme II and/or III.

Situation 2: if A _Min＜0.25A _Max, the recast test is so that reset W _OCCPValue.Prepare OCCPS with 50% of OCCP default volume.Repeating this process (that is, reduces to 0.5g with OCCP from 1.0g, reduces to 0.25g etc. then if desired from 0.5g) till satisfying situation 3 described absorbancy conditions.

Situation 3: if 0.25A _Max≤ A _Min≤ 0.9A _Max, this test operation is just as final testing program program.Under these conditions, need not to change used d _BleachAnd W _OCCPDefault value.

Testing program I: the first step is by described preparation OCCPS.The time set that OCCP is added in the deionized water when forming OCCPS is t=0.(t when at every turn getting aliquots containig _fOr t _Dd), take out the OCCPS of 100mL aliquots containig, immediately at t=(t _fOr t _Dd) to t=(t _fOr t _Dd+ 0.25 minute) during in filter, removing undissolved OCCP, and with filtrate at t=(t _fOr t _Dd+ 0.50 minute) time disposable adding among the 10.0mLCDS.Being about to carry out absorbance measurement (data are obtained) before, from the DBS of gained, get 1-5mL aliquots containig (C).Work as d _BleachDuring end, at λ _MaxMeasure the absorbancy of C down.

Timing definition in the time of will measuring aliquots containig C absorbancy (data are obtained) is t _CTherefore, require t _C=(t _fOr t _Dd)+0.50 minute+d _BleachWith t _CThe time absorbance measured be defined as A _{T (C)}Symbol δ A _{T (C)}Be defined as A _Max-A _{T (C)}For example, if be 12 minutes wash(ing)cycle, d then _BleachValue be 1 minute, and the time of getting aliquots containig be 0.5,1.5,2.5,3.5,6 and 9 minute, data acquisition time (t _C) be 2,3,4,5,7.5 and 10.5 minutes.

Value Be any data acquisition time, t _C, its what its data acquisition time in office Obtain before.Therefore, The time absorbancy be The time absorbancy be According to

With

Value, have two kinds of situations.

Situation I ₁If: any ＜any , and according to definition

The may command usability that then contains the product (OCCP) of organic catalyzer is shown, and this may command utilizes the product that contains organic catalyzer of (validity) to belong to scope of the present invention.

The situation I of 20 minutes cycles of washing process ₁Example:

??t	??t _C	??A _max	??A _t(C)	?δA _t(C)	The % dyestuff
??t	??t _C	??A _max	??A _t(C)	?δA _t(C)	The % dyestuff	??0	??0	??1.20			??100
??0.5	??2	??1.20	??1.00	??0.20	??83	??0	??0	??1.20			??100
??0.5	??2	??1.20	??1.00	??0.20	??83	??1.5	??3	??1.20	??0.84	??0.36	??71
??2.5	??4	??1.20	??0.70	??0.50	??58	??1.5	??3	??1.20	??0.84	??0.36	??71
??2.5	??4	??1.20	??0.70	??0.50	??58	??3.5	??5	??1.20	??0.67	??0.53	??56
??5	??6.5	??1.20	??0.72	??0.48	??60	??3.5	??5	??1.20	??0.67	??0.53	??56
??5	??6.5	??1.20	??0.72	??0.48	??60	??10	??11.5	??1.20	??0.78	??0.42	??65
??15	??16.5	??1.20	??0.83	??0.37	??69	??10	??11.5	??1.20	??0.78	??0.42	??65

Situation I ₂If: each

〉=each

, and according to definition The may command usability of product (OCCP) that then contains organic catalyzer is not indicated by scheme I, yet, can find that OCCP belong to scope of the present invention by testing program II and/or testing program III.Illustrate, this situation may occur concerning the product that contains organic catalyzer (OCCP) of uncontrollable utilization, wherein at first t _fOCCP just is dissolved among the OCCPS fully before, so that the A of back _{T (C)}It is constant that value will keep.The decomposition of organic catalyst in the whole time among the OCCPS (cause the consumption of dyestuff in DBS less in the whole time) causes each

〉=each

The situation I of 20 minutes cycles of washing process ₂Example:

Testing program II

General provisions/parameter/scheme: identical with testing program I definition has following additional content.

OCSP is the product that contains independent organic catalyst, by making the OCCP that does not contain organic catalyzer again, organic catalyst is added to again make in the product then, so that whole whole compositions of OCSP are identical with OCCP.

OCSPS is the solution that contains the product of independent organic catalyst, is dissolved in 25 ℃ of deionized waters of 1.0L by the product (OCSP) that 1.00g is contained independent organic catalyst to make, and it is 9.9-10.1 that its pH is adjusted to the pH that makes final solution in advance.

W _OCSPIt is the parameter of describing in the final testing program of the product that contains independent organic catalyst (OCSP) weight of the solution (OCSPS) be used to form the product that contains independent organic catalyst.The default value of this parameter is 1.00g, but can be defined as less amount or weight according to following situation II.

DBS2 is that the OCSPS with the 100mL aliquots containig adds the dye bleach solution that forms among the 10mL CDS to.

The time of getting aliquots containig from OCSPS is with aforesaid the same from OCCPS.

Testing program II: the first step is to finish by described scheme I.Use identical d with scheme I definition _Bleach, repeat identical process (remove and replace OCCP) with OCSP.The time set that OCSP is added in the deionized water when forming OCSPS is t=0.(t when at every turn getting aliquots containig _fOr t _Dd), take out the OCSPS of 100mL aliquots containig, immediately at t=(t _fOr t _Dd) to t=(t _fOr t _Dd+ 0.25 minute) during in filter, removing undissolved OCSP, and with filtrate at t=(t _fOr t _Dd+ 0.50 minute) time disposable adding among the 10.0mLCDS.Being about to carry out absorbance measurement (data are obtained) before, from the DBS2 of gained, get 1-5mL aliquots containig (S).Work as d _BleachDuring end, at λ _MaxMeasure the absorbancy of S down.

Timing definition in the time of will measuring aliquots containig S absorbancy (data are obtained) is t _STherefore, require t _S=(t _fOr t _Dd)+0.50 minute+d _Bleach=t _CWith t _SThe time absorbance measured be defined as A _{T (S)}Symbol δ A _{T (S)}Be defined as A _Max-A _{T (S)}For example, if be 12 minutes wash(ing)cycle, d then _BleachValue be 1 minute, and the time of getting aliquots containig be 0.5,1.5,2.5,3.5,6 and 9 minute, data acquisition time (t _S) be 2,3,4,5,7.5 and 10.5 minutes.

According to t _S=t _CThe time A _{T (C)}And A _{T (S)}Value, have two kinds of situations.

Situation II ₁If: at least one A _{T (S)}＜A _{T (C)}, and according to definition δ A _{T (S)}＞δ A _{T (C)}, the may command usability (validity) that then contains the product (OCCP) of organic catalyzer is shown, and the product that contains organic catalyzer of this may command utilization belongs to scope of the present invention.

The situation II of 20 minutes cycles of washing process ₁Example:

More preferably, concerning scheme II, even at least one situation, 1.2xA _{T (S)}＜A _{T (C)}, the may command usability that then contains the product (OCCP) of organic catalyzer is shown, and OCCP belongs to scope of the present invention.

Situation II ₂If: each A _{T (S)}〉=each A _{T (C)}, and according to definition δ A _{T (S)}≤ δ A _{T (C)}, the may command usability of product (OCCP) that contains organic catalyzer is not indicated by scheme II, yet, can find that OCCP belong to scope of the present invention by testing program I and/or testing program III.Testing program III

General provisions/parameter/scheme: identical with testing program I definition has following additional content.Can derive from the 32wt% solution of peracetic acid in acetic acid,diluted of Aldrich.

OCCPS ' among the scheme III is the solution that contains the product of organic catalyzer, be dissolved in 1.0L by the product (OCCP) that 1.00g is contained organic catalyzer and contain in 25 ℃ of deionized waters of 100mg peracetic acid (in 100% activity) and make, it is 9.9-10.1 that its pH is adjusted to the pH that makes final solution in advance.

Testing program III: institute is identical with scheme I in steps, and difference is with OCCPS ' replacement OCCPS.

Situation III ₁If: any ＜any , and according to definition The may command usability that then contains the product (OCCP) of organic catalyzer is shown, and the product that contains organic catalyzer of this may command utilization belongs to scope of the present invention.

Situation III ₂If: each 〉=each , and according to definition

The may command usability of product (OCCP) that then contains organic catalyzer is not indicated by scheme I, yet, can find that OCCP belong to scope of the present invention by testing program I and/or testing program II.

Composition of the present invention can select any technology to prepare aptly by the makers-up, and the non-limiting case description of said technology is at US5,691,297 (Nassano etc., 1997.11.11 authorizes); US5,574,005 (Welch etc., 1996.11.12 authorizes); US5,569,645 (Dinniwell etc., 1996.10.29 authorizes); US5,565,422 (Del Greco etc., 1996.10.15 authorizes); US5,516,448 (Capeci etc., 1996.5.14 authorizes); US5,489,392 (Capeci etc., 1996.2.6 authorizes); US5,486,303 (Capeci etc., 1996.1.23 authorizes), all these all are incorporated herein by reference.

Except that above-mentioned embodiment, organic catalyst of the present invention can also be mixed with any suitable laundry detergent composition, the visible US5 of its non-limiting example, 679,630 (Baeck etc., 1997.10.21 authorizes); US5,565,145 (Watson etc., 1996.10.15 authorizes); US5,478,489 (Fredj etc., 1995.10.26 authorizes); US5,470,507 (Fredj etc., 1995.11.28 authorizes); US5,466,802 (Panandiker etc., 1995.11.14 authorizes); US5,460,752 (Fredj etc., 1995.10.24 authorizes); US5,458,810 (Fredj etc., 1995.10.17 authorizes); US5,458,809 (Fredj etc., 1995.10.17 authorizes); US5,288,431 (Huber etc., 1994.2.22 authorizes), all these all are incorporated herein by reference.

By the present invention having been made detailed description, it will be apparent to those skilled in the art that under the prerequisite that does not deviate from scope of the present invention and can make various changes and improvements, and the present invention not will be understood that the description that is restricted to specification sheets above with reference to preferred embodiment.

Sequence table＜110〉The Procter ﹠amp; Gamble Company

Dykstra，Robert

Miracle, Gregory＜120〉the may command utilization of formulation components, the composition that uses this component and clothes washing method＜130〉7749x＜150〉60/151,002＜151〉1999-08-27＜150〉60/151,004＜151〉1999-08-27＜160〉18＜170〉PatentIn version 3.0＜210〉1＜211〉21＜212〉DNA＜213〉microorganism Aspergillus aculeatus (Aspergillus aculeatus)＜400〉1 attcatttgt ggacagtgga c

21＜210〉2＜211〉20＜212〉DNA＜213〉microorganism Aspergillus aculeatus＜400〉2 gttgatcgca cattgaacca

20＜210〉3＜211〉20＜212〉DNA＜213〉microorganism Aspergillus aculeatus＜400〉3 accccagccg accgattgtc

20＜210〉4＜211〉20＜212〉DNA＜213〉microorganism Aspergillus aculeatus＜400〉4 cttccttacc tcaccatcat

20＜210〉5＜211〉20＜212〉DNA＜213〉microorganism Aspergillus aculeatus＜400〉5 ttaacatctt ttcaccatga

20＜210〉6＜211〉20＜212〉DNA＜213〉microorganism Aspergillus aculeatus＜400〉6 agctttccct tctctccctt

20＜210〉7＜211〉28＜212〉DNA＜213〉microorganism Aspergillus aculeatus＜400〉7 gccaccctgg cttccgctgc cagcctcc

28＜210〉8＜211〉20＜212〉DNA＜213〉microorganism Aspergillus aculeatus

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gacagtagca?atccagcatt

20

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＜213〉microorganism Aspergillus aculeatus

<400>??9

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20

<210>??10

<211>??20

<212>??DNA

＜213〉microorganism Aspergillus aculeatus

<400>??10

ccatgaagtt?caccgtattg

20

<210>??11

<211>??20

<212>??DNA

＜213〉microorganism Aspergillus aculeatus

<400>??11

gcactgcttc?tctcccaggt

20

<210>??12

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＜213〉microorganism Aspergillus aculeatus

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＜212〉DNA＜213〉microorganism Aspergillus aculeatus＜400〉13 acgctcctcc aattttctct

20＜210〉14＜211〉19＜212〉DNA＜213〉microorganism Aspergillus aculeatus＜400〉14 ggctggtagt aatgagtct

19＜210〉15＜211〉20＜212〉DNA＜213〉microorganism Aspergillus aculeatus＜400〉15 ggcgcagagt ttggccaggc

20＜210〉16＜211〉21＜212〉DNA＜213〉microorganism Aspergillus aculeatus＜400〉16 caacatcccc ggtgttctgg g

21＜210〉 17＜211〉 347＜212〉 DNA＜213〉＜400〉 17aaagattcat ttgtggacag tggacgttga tcgcacattg aaccaacccc agccgaccga 60ttgtccttcc ttacctcacc atcatttaac atcttttcac catgaagctt tcccttctct 120cccttgccac cctggcttcc gctgccagcc tccagcgccg cacacttctg cggtcagtgg 180gataccgcca ccgccggtga cttcaccctg tacaacgacc tttggggcga gacggccggc 240 accggctccc agtgcactgg agtcgactcc tacagcggcg acaccatcgc ttgtcacacc 300 agcaggtcct ggtcggagta gcagcagcgt caagagctat gccaacg 347＜210〉 18＜211〉 294＜212〉 DNA＜213〉＜400〉 18cagcatctcc attgagtaat cacgttggtg ttcggtggcc cgccgtgttg cgtggcggag 60gctgccggga gacgggtggg gatggtggtg ggagagaatg tagggcgccg tgtttcagtc 120cctaggcagg ataccggaaa accgtgtggt aggaggttta taggtttcca ggagacgctg 180tataggggat aaatgagatt gaatggtggc cacactcaaa ccaaccaggt cctgtacata 240caatgcatat accaattata cctaccaaaa aaaaaaaaaa aaaaaaaaaa aaaa 294

Claims

1. a clothes washing method comprises that utilizing method to make by may command needs the fabric of cleaning to contact with organic catalyst.

2. according to the process of claim 1 wherein that said organic catalyst is selected from:

A) aryl imine positively charged ion and net charge are about+3 to about-3 aryl imine polyion, and it is represented by following formula [I]:

R wherein ²And R ³Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ¹And R ⁴Be selected from replacement or not replacement, saturated or unsaturated group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, ketone group and carbalkoxy; And X ^-Be the charge balance counter ion that suit; And v is the integer of 1-3;

B) net charge is about+3 to about-3 aryl imine zwitter-ion, and it is represented by following formula [II]:

R wherein ⁵-R ⁷Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Also exist in this formula by the group shown in the following formula:

Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from replace or do not replace, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle;

C) net charge is about-3 to about+3 modified amine, and it is represented by following formula [V] and [VI]: R wherein ⁹-R ¹⁰Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ⁸And R ¹¹, when existing, be to be selected to replace or not replacement saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, ketone group and carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ¹²Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 37＞pKa＞-2; Precondition is any R ⁸-R ¹², when existing, can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; And the group shown in the following formula: Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from replace or do not replace, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle;

D) net charge is about-3 to about+3 modified oxidized amine, and it is represented by following formula [VII]-[X]: R wherein ⁹-R ¹⁰Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ⁸And R ¹¹Be to be selected to replace or not replacement saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ¹²Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 37＞pKa＞-2; Precondition is any R ⁸-R ¹², when existing, can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; And also exist in this formula by the group shown in the following formula:

Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂-,-SO ₃-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from replace or do not replace, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle;

E) sulfimide, the phosphono imines, N-acyl group imines and thiadiazoles dioxide, it is respectively by following formula [XXIa], [XXIb], [XXII] and [XXIII] expression:

R wherein ⁴¹-R ⁴⁴, when existing, be independently selected from replacement or not replacement, saturated or unsaturated group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Precondition is R ⁴¹-R ⁴⁴In any one can with R ⁴¹-R ⁴⁴In other any one can be joined together to form the part of the public ring of a part of public ring, comprise fused-aryl, fused iso or annelated heterocycles;

F) Evil ethylene imine positively charged ion and net charge are about+3 to about-3 polyion, and it is represented by following formula [III]: R wherein ²'-R ³' being independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ¹' and R ⁴' be to be selected to replace or do not replace, saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, the group of ketone group and carbalkoxy; And X ^-Be the counter ion that the charge balance that suits is used, the counter ion of preferred bleach-compatible;

G) net charge is for making an appointment with+3 to about-3 De Evil ethylene imine zwitter-ions, and it is represented by following formula [IV]: R wherein ^{5 '}-R ^{7 '}Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Also exist in this formula by the group shown in the following formula: Z ' wherein _p ^-With T ' _oCovalently bound, and Z ' _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from replace or do not replace, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle;

H) Evil ethylene imine sulfimide [XXIVa], phosphono imines [XXIVb], N-acyl group imines [XXV] and thiadiazoles dioxide [XXVI] and [XXVII], it is expressed as follows: R wherein ^{41 '}-R ^{44 '}, when existing, being independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, and ketone group, carboxyl, carbalkoxy, precondition is R ^{41 '}-R ^{44 '}In any one can with R ^{41 '}-R ^{44 '}In other any one in conjunction with the part that forms public ring, comprise fused-aryl, fused iso or annelated heterocycles; And

I) its mixture.

3. according to the method for claim 2, wherein organic catalyst is selected from:

A) aryl imine positively charged ion and net charge are about+3 to about-3 aryl imine polyion, and it is represented by following formula [XI]:

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; Each R ²⁰Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ²⁰Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ¹⁸Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ¹⁹Be to be selected to replace or do not replace, saturated or unsaturated, H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl and heterocycle; G is selected from: (1)-O-; (2)-N (R ²³)-and (3)-N (R ²³R ²⁴)-; R ²¹-R ²⁴Be to replace or unsubstituted group, said group is independently selected from H, oxygen, straight or branched C ₁-C ₁₂Alkyl, alkylidene group, alkoxyl group, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle; Precondition is R ¹⁸, R ¹⁹, R ²⁰, R ²¹-R ²⁴In any one can with R ¹⁸, R ¹⁹, R ²⁰, R ²¹-R ²⁴In other any one be joined together to form the part of public ring; Any together with R ²¹-R ²²Can be in conjunction with forming carbonyl; Any ortho position R ²¹-R ²⁴Can be connected to form unsaturated group; And substituent R wherein ²¹-R ²⁴In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part; X ^-Be the charge balance counter ion that suit; And v is the integer of 1-3;

B) net charge is about+3 to about-3 aryl imine zwitter-ion, and it is represented by following formula [XII]: Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; Each R ²⁶Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ²⁶Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ²⁵Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Also exist in this formula by the group shown in the following formula:

Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from the group shown in the following formula: Wherein q is the integer of 1-8; R ²⁹Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from (1)-O-; (2)-N (R ³⁰)-and (3) N (R ³⁰R ³¹)-, R ²⁷, R ²⁸, R ³⁰And R ³¹Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ³⁰And R ³¹In any one can with R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ³⁰And R ³¹In other any one be joined together to form the part of public ring; Any together with R ²⁷-R ²⁸Can be in conjunction with forming carbonyl; Any ortho position R ²⁷-R ³¹Can be in conjunction with forming unsaturated group; And substituent R wherein ²⁷-R ³¹In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part;

C) modified amine, represent by following formula [XV] and [XVI]:

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; R ³⁴Be to be selected to replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group is crossed alkoxyl group, carboxyl, perhydroxyl radical, sulfonate radical close the group that closes with the persulfonic acid root, each R ³⁵Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ³⁵Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ³²Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ³³Can be to replace or do not replace, saturated or undersaturated group, said group is selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, and also exist in this formula by the group shown in the following formula: Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from the group shown in the following formula:

Wherein q is the integer of 1-8; R ³⁸Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from: (1)-O-; (2)-N (R ³⁹)-and (3)-N (R ³⁹R ⁴⁰)-; R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one can with R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In other any one be joined together to form the part of public ring; Any together with R ³⁶-R ³⁷Can be in conjunction with forming carbonyl; Any ortho position R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Can be in conjunction with forming unsaturated group; And substituent R wherein ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part;

D) modified oxidized amine, represent by following formula [XVII]-[XX]:

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; R ³⁴Be to be selected to replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group is crossed alkoxyl group, and carboxyl is crossed carboxyl, and sulfonate radical closes the group that closes with the persulfonic acid root; Each R ³⁵Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ³⁵Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ³²Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ³³Can be to replace or do not replace, saturated or undersaturated group, said group is selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, and also exist in this formula by the group shown in the following formula: Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from the group shown in the following formula: Wherein q is the integer of 1-8; R ³⁸Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from: (1)-O-; (2)-N (R ³⁹)-and (3) N (R ³⁹R ⁴⁰)-; R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one can with R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In other any one be joined together to form the part of public ring; Any together with R ³⁶-R ³⁷Can be in conjunction with forming carbonyl; Any ortho position R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Can be in conjunction with forming unsaturated group; And substituent R wherein ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part;

E) sulfimide [XXVIIIa], phosphono imines [XXVIIIb], N-acyl group imines [XXIX], following expression:

Each R wherein ⁴⁶Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two vicinal R ⁴⁶Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ⁴⁵Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; G when existing, is selected from: (1)-O-; (2)-N (R ⁴⁷)-and (3)-N (R ⁴⁷R ⁴⁸)-; R ⁴⁷-R ⁴⁸Be to replace or unsubstituted group, said group is independently selected from H, oxygen, straight or branched C ₁-C ₁₂Alkyl, alkylidene group, alkoxyl group, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle;

F) Evil ethylene imine positively charged ion and net charge are about+3 to about-3 polyion, and it is represented by following formula [XIII]: Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; Each R ^{20 '}Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ^{20 '}Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ^{18 '}Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ^{19 '}Can be to replace or do not replace, saturated or undersaturated group, said group is selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl and heterocycle .G are selected from: (1)-O-; (2)-N (R ^{23 '})-and (3)-N (R ^{23 '}R ^{24 '}); R ^{21 '}-R ^{24 '}Be to replace or unsubstituted group, said group is independently selected from H, oxygen, straight or branched C ₁-C ₁₂Alkyl, alkylidene group, alkoxyl group, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle; Precondition is R ^{18 '}, R ^{19 '}, R ^{21 '}-R ^{24 '}In any one can with R ^{18 '}, R ^{19 '}, R ^{21 '}-R ^{24 '}In other any one be joined together to form the part of public ring; Any together with R ^{21 '}-R ^{22 '}Can be in conjunction with forming carbonyl; Any ortho position R ^{21 '}-R ^{24 '}Can be in conjunction with forming unsaturated group; And substituent R wherein ^{21 '}-R ^{24 '}In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part; And substituent R wherein ^{21 '}-R ^{24 '}In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part; X ^-Be the charge balance counter ion that suit; And v is the integer of 1-3;

G) net charge is for making an appointment with+3 to about-3 De Evil ethylene imine zwitter-ions, and it is represented by following formula [XIV]: Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; Each R ^{26 '}Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ^{26 '}Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ^{25 '}Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Group shown in the following formula: Z ' wherein _p ^-With T ' _oCovalently bound, and Z ' _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1 or 2; T ' _oBe selected from the group shown in the following formula:

Wherein q is the integer of 1-8; R ^{29 '}Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from: (1)-O-(2)-N (R ³⁰)-and (3) N (R ^{30 '}R ^{31 '})-, R ^{27 '}, R ^{28 '}, R ^{30 '}And R ^{31 '}Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ^{25 '}, R ^{26 '}, R27 ', R ^{28 '}, R ^{30 '}And R ^{31 '}In any one can with R ^{25 '}, R ^{26 '}, R ^{27 '}, R ^{28 '}, R ^{30 '}And R ^{31 '}In other any one be joined together to form the part of public ring; Any together with R ^{27 '}-R ^{28 '}Can be in conjunction with forming carbonyl; Any ortho position R ^{27 '}-R ^{31 '}Can be connected to form unsaturated group; And substituent R wherein ^{27 '}-R ^{31 '}In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part;

H) Evil ethylene imine sulfimide [XXXIa], phosphono imines [XXXIb], N-acyl group imines [XXXII], following expression: Each R wherein ^{46 '}Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two vicinal R ^{46 '}Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ^{45 '}Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; G when existing, is selected from: (1)-O-; (2)-N (R ^{47 '})-and (3)-N (R ^{47 '}R ^{48 '})-; R ^{47 '}-R ^{48 '}Be to replace or unsubstituted group, said group is independently selected from H, oxygen, straight or branched C ₁-C ₁₂Alkyl, alkylidene group, alkoxyl group, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle; And

I) its mixture.

4. the process of claim 1 wherein and comprise spot in the said fabric.

5. bleaching composition, contain:

(a) peroxygen source; With

(b) organic catalyst; Wherein organic catalyst utilizes method to become in containing the washing soln of said bleaching composition by may command can to utilize.

6. according to the bleaching composition of claim 5, wherein said peroxygen source is selected from:

(i) ready-formed peracid compound is selected from percarboxylic acids and salt, and percarbonic acid and salt are crossed imido acid and salt, peroxide one sulfuric acid and salt, and composition thereof and

(ii) hydrogen peroxide cource is selected from the perborate compound, percarbonate compound, superphosphate compound and composition thereof, and bleach-activating agent.

7. according to the bleaching composition of claim 6, wherein said peroxygen source is selected from hydrogen peroxide cource, is selected from the perborate compound, percarbonate compound, superphosphate compound and composition thereof, and bleach-activating agent.

8. according to the bleaching composition of claim 7, wherein said bleach-activating agent is selected from hydrophobic bleach activator.

9. according to the bleaching composition of claim 7; wherein said bleach-activating agent is selected from tetra acetyl ethylene diamine (TAED); benzoyl caprolactam (BzCL); 4-nitro benzoyl hexanolactam; 3-chlorobenzene formacyl hexanolactam, benzoyl oxygen base benzene sulfonate (BOBS), nonanoly acyloxy benzene sulfonate (NOBS); phenol benzoate (PhBz), the last of the ten Heavenly stems acyloxy benzene sulfonate (C ₁₀-OBS), benzoyl Valerolactim (BZVL), hot acyloxy benzene sulfonate (C ₈-OBS), can cross the ester of hydrolysis, the amino hexylyloxy of 4-[N-(nonanoyl)]-Phenylsulfonic acid sodium salt (NACA-OBS), bay acyloxy benzene sulfonate (LOBS or C ₁₂-OBS), (the 10th has UDOBS or the C that insatiable hunger is closed to 10-undecylene acyloxy benzene sulfonate ₁₁-OBS), caprinoyl aminobenzoic acid (DOBA) and composition thereof.

10. according to the SYNTHETIC OPTICAL WHITNER of claim 5, wherein said organic catalyst is selected from:

R wherein ¹-R ²Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ¹And R ⁴Be selected from replacement or not replacement, saturated or unsaturated group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, ketone group and carbalkoxy; And X ^-Be the charge balance counter ion that suit; And v is the integer of 1-3;

B)+3 to-3 aryl imine zwitter-ions approximately, it is by following formula [II] for approximately for net charge: R wherein ⁵-R ⁷Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Also exist in this formula by the group shown in the following formula: Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from replace or do not replace, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle;

C) net charge is about-3 to about+3 modified amine, and it is represented by following formula [V] and [VI]: R wherein ⁹-R ¹⁰Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ⁸And R ¹¹, when existing, be to be selected to replace or not replacement saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ¹²Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 37＞pKa＞-2; Precondition is any R ⁸-R ¹², when existing, can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; And the group shown in the following formula: Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from replace or do not replace, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle;

D)-3 to+3 modified oxidized amine approximately, it is by following formula [VII]-[X] for approximately for net charge:

R wherein ⁹-R ¹⁰Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ⁸And R ¹¹Be to be selected to replace or do not replace, saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, ketone group and carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ¹²Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 37＞pKa＞-2; Precondition is any R ⁸-R ¹², when existing, can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; And also exist by the group shown in the following formula in this formula Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from replace or do not replace, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle;

R wherein ⁴¹-R ⁴⁴, when existing, be independently selected from replacement or not replacement, saturated or unsaturated group, said group is selected from H, alkyl, cycloalkyl; Aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Precondition is that precondition is R ⁴¹-R ⁴⁴In any one can with R ⁴¹-R ⁴⁴In other any one can be joined together to form the part of the public ring of a part of public ring, comprise fused-aryl, fused iso or annelated heterocycles;

F+3 to-3 polyions approximately, it is by following formula [III] for approximately for) Evil ethylene imine positively charged ion and net charge:

R wherein ^{2 '}-R ^{3 '}Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ^{1 '}And R ^{4 '}Be to be selected to replace or do not replace, saturated or unsaturated, H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, ketone group and carbalkoxy; And X ^-Be the counter ion that the charge balance that suits is used; And v is the integer of 1-3;

G) net charge is for making an appointment with+3 to about-3 De Evil ethylene imine zwitter-ions, and it is represented by following formula [IV]: R wherein ^{5 '}-R ^{7 '}Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Also exist in this formula by the group shown in the following formula:

Z ' wherein _p ^-With T ' _oCovalently bound, and Z ' _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from replace or do not replace, saturated or unsaturated alkyl, cycloalkyl, aryl, alkaryl, aralkyl and heterocycle;

H) Evil ethylene imine sulfimide [XXIVa], phosphono imines [XXIVb], N-acyl group imines [XXV] and thiadiazoles dioxide [XXVI] and [XXVII], following expression: R wherein ^{41 '}-R ^{44 '}, when existing, being independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, and ketone group, carboxyl, carbalkoxy, precondition is R ^{41 '}-R ^{44 '}In any one can with R ^{41 '}-R ^{44 '}In other any one be joined together to form the part of public ring, comprise fused-aryl, fused iso or annelated heterocycles;

I) its mixture.

11. according to the bleaching composition of claim 10, wherein organic catalyst is selected from:

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; Each R ²⁰Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ²⁰Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ¹⁸Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R19 is selected to replace or do not replace, and is saturated or unsaturated, H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl and heterocycle; G is selected from: (1)-O-; (2)-N (R ²³)-and (3)-N (R ²³R ²⁴)-; R ²¹-R ²⁴Be to replace or unsubstituted group, said group is independently selected from H, oxygen, straight or branched C ₁-C ₁₂Alkyl, alkylidene group, alkoxyl group, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle; Precondition is R ¹⁸, R ¹⁹, R ²⁰, R ²¹-R ²⁴In any one can with R ¹⁸, R ¹⁹, R ²⁰, R ²¹-R ²⁴In other any one be joined together to form the part of public ring; Any together with R ²¹-R ²²Can be in conjunction with forming carbonyl; Any ortho position R ²¹-R ²⁴Can be in conjunction with forming unsaturated group; And substituent R wherein ²¹-R ²⁴In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part; X ^-Be the counter ion that the charge balance that suits is used; And v is the integer of 1-3;

B) net charge is about+3 to about-3 aryl imine zwitter-ion, and it is represented by following formula [XII]

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; Each R ²⁶Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ²⁶Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ²⁵Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Also exist in this formula by the group shown in the following formula: Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from the group shown in the following formula:

Wherein q is the integer of 1-8; R ²⁹Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from (1)-O-; (2)-N (R ³⁰)-and (3) N (R ³⁰R ³¹)-, R ²⁷, R ²⁸, R ³⁰And R ³¹Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ³⁰And R ³¹In any one can with R ²⁵, R ²⁶, R ²⁷, R ²⁸, R ³⁰And R ³¹In other any one be joined together to form the part of public ring; Any together with R ²⁷-R ²⁸Can be in conjunction with forming carbonyl; Any ortho position R ²⁷-R ³¹Can be in conjunction with forming unsaturated group; And substituent R wherein ²⁷-R ³¹In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part;

C) modified amine, it is represented by following formula [XV] and [XVI]:

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; R ³⁴Be to be selected to replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group is crossed alkoxyl group, and carboxyl is crossed carboxyl, and sulfonate radical closes the group that closes with the persulfonic acid root; Each R ³⁵Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ³⁵Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ³²Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ³³Can be to replace or do not replace, saturated or undersaturated group, said group is selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, and also exist in this formula by the group shown in the following formula:

Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from the group shown in the following formula: Wherein q is the integer of 1-8; R ³⁸Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from: (1)-O-; (2)-N (R ³⁹)-and (3) N (R ³⁹R ⁴⁰)-; R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one can with R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In other any one be joined together to form the part of public ring; Any together with R ³⁶-R ³⁷Can be in conjunction with forming carbonyl; Any ortho position R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Can be in conjunction with forming unsaturated group; And substituent R wherein ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part;

D) modified oxidized amine, it is represented by following formula [XVII]-[XX]: Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; R ³⁴Be to be selected to replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group is crossed alkoxyl group, and carboxyl is crossed carboxyl, and sulfonate radical closes the group that closes with the persulfonic acid root; Each R ³⁵Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ³⁵Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ³²Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ³³Can be to replace or do not replace, saturated or undersaturated group, said group is selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, and also exist in this formula by the group shown in the following formula: Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from the group shown in the following formula:

Wherein q is the integer of 1-8; R ³⁸Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from: (1)-O-; (2)-N (R ³⁹)-and (3) N (R ³⁹R ⁴⁰)-; R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one can with R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In other any one be joined together to form the part of public ring; Any together with R ³⁶-R ³⁷Can be in conjunction with forming carbonyl; Any ortho position R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Can be in conjunction with forming unsaturated group; And substituent R wherein ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part;

Each R wherein ⁴⁶Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ⁴⁶Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ⁴⁵Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; G when existing, is selected from: (1)-O-; (2)-N (R ⁴⁷)-and (3)-N (R ⁴⁷R ⁴⁸)-; R ⁴⁷-R ⁴⁸Be to replace or unsubstituted group, said group is independently selected from H, oxygen, straight or branched C ₁-C ₁₂Alkyl, alkylidene group, alkoxyl group, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle; And n is the integer of 0-4;

F) Evil ethylene imine positively charged ion and net charge are about+3 to about-3 polyion, and it is represented by following formula [XIII]: Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; Each R ^{20 '}Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ^{20 '}Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ^{18 '}Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ^{19 '}Can be to replace or do not replace, saturated or undersaturated group, said group is selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl and heterocycle.G is selected from: (1)-O-; (2)-N (R ^{23 '})-and (3)-N (R ^{23 '}R ^{24 '})-; R ^{21 '}-R ^{24 '}Be to replace or unsubstituted group, said group is independently selected from H, oxygen, straight or branched C ₁-C ₁₂Alkyl, alkylidene group, alkoxyl group, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle; Precondition is R ^{18 '}, R ^{19 '}, R ^{21 '}-R ^{24 '}In any one can with R ^{18 '}, R ^{19 '}, R ^{21 '}-R ^{24 '}In other any one be joined together to form the part of public ring; Any together with R ^{21 '}-R ^{22 '}Can be in conjunction with forming carbonyl; Any ortho position R ^{21 '}-R ^{24 '}Can be in conjunction with forming unsaturated group; And substituent R wherein ^{21 '}-R ^{24 '}In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part; And substituent R wherein ^{21 '}-R ^{24 '}In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part; X ^-Be the counter ion that the charge balance that suits is used; And V is the integer of 1-3;

G) net charge is for making an appointment with+3 to about-3 De Evil ethylene imine zwitter-ions, and it is represented by following formula [XIV]:

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; Each R ²⁶Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ²⁶Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ²⁵Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; Group shown in the following formula: Z ' wherein _p ^-With T _oCovalently bound, and Z ' _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1 or 2; T _oBe selected from the group shown in the following formula: Wherein q is the integer of 1-8; R ^{29 '}Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from: (1)-O-; (2)-N (R ^{30 '})-and (3) N (R ^{30 '}R ^{31 '})-; R ^{27 '}, R ^{28 '}, R ^{30 '}And R ^{31 '}Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ^{25 '}, R ^{26 '}, R ^{27 '}, R ^{28 '}, R ^{30 '}And R ^{31 '}In any one can with R ^{25 '}, R ^{26 '}, R ^{27 '}, R ^{28 '}, R ^{30 '}And R ^{31 '}In other any one be joined together to form the part of public ring; Any together with R ^{27 '}-R ^{28 '}Can be in conjunction with forming carbonyl; Any ortho position R ^{27 '}-R ^{31 '}Can be in conjunction with forming unsaturated group; And substituent R wherein ^{27 '}-R ^{31 '}In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part;

H) Evil ethylene imine sulfimide [XXXIa], phosphono imines [XXXIb], N-acyl group imines [XXXII], following expression: Each R wherein ^{46 '}Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two vicinal R ^{46 '}Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ^{45 '}Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; G when existing, is selected from: (1)-O-; (2)-N (R ^{47 '})-and (3)-N (R ^{47 '}R ^{48 '})-; R ^{47 '}-R ^{48 '}Be to replace or unsubstituted group, said group is independently selected from H, oxygen, straight or branched C ₁-C ₁₂Alkyl, alkylidene group, alkoxyl group, aryl, alkaryl, aralkyl, cycloalkyl and heterocycle; And n is the integer of 0-4; And

I) its mixture.

12. according to the bleaching composition of claim 5, wherein said bleaching compounds also contains one or more and is selected from following detergent component: tensio-active agent, solvent, buffer reagent, enzyme, dirt release agent, clay stain remover, dispersion agent, whitening agent, suds suppressor, fabric softener, foaming organic catalyst, enzyme stabilizers, washing assistant, sequestrant, other SYNTHETIC OPTICAL WHITNER comprises metal catalyst, other organic catalyst, dyestuff, dye transfer inhibitor, spices and composition thereof.

13. product that contains organic catalyzer, this product also contains to be used for instructing and uses the specification sheets that said compound cleans needs clean textile, these working instructions comprise the step that described fabric is contacted with the washing soln that contains described product, wherein utilize method by may command, it is effective that organic catalyst becomes in described washing soln.

14. according to the product of claim 13, wherein said product is a cloth-washing detergent.

15. according to the product of claim 13, wherein said product is a laundry additive.

16. a modified amine compound is selected from by the modified oxidized amine shown in following general formula [VII]-[X]: R wherein ⁸-R ¹⁰Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, ketone group, carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ¹¹, when existing, be to be selected to replace or not replacement saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, ketone group, carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ¹²Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 37＞pKa＞-2; Precondition is any R ⁸-R ¹², when existing, can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles.

17. according to the modified amine compound of claim 16, wherein R ¹¹Be expressed from the next:

18. according to the modified amine compound of claim 18, wherein to R ¹², the pKa value is greater than 3 and less than 23.

19. according to the modified amine compound of claim 17, wherein to R ¹², the pKa value is greater than 9 and less than 21.

20. according to the modified amine compound of claim 18, wherein to R ¹², the pKa value is greater than 11 and less than 17.

21. according to the modified amine compound of claim 16, wherein R ¹²Be selected from and replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group and mistake alkoxyl group.

22. according to the modified amine compound of claim 21, wherein said R ¹²Be selected from hydroxyl or perhydroxyl radical.

23. according to the modified amine compound of claim 16, wherein said modified amine compound has following general formula [XVII]-[XX]:

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; R ³⁴Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 37＞pKa＞-2; Each R ³⁵Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, and cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ³⁵Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ³²Can be to replace or unsubstituted group, said group be selected from H, alkyl, and cycloalkyl, alkaryl, aryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy; R ³³Can be to replace or do not replace, saturated or undersaturated group, said group is selected from H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, heterocycle comprises the group that carries negatively charged ion and/or cationic charge.

24. according to the modified amine compound of claim 23, wherein R ³³Be expressed from the next:

Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from the group shown in the following formula:

Wherein q is the integer of 1-8; R ³⁸Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from: (1)-O-; (2)-N (R ³⁹)-and (3) N (R ³⁹R ⁴⁰)-; R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one can with R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In other any one be joined together to form the part of public ring; Any together with R ³⁶-R ³⁷Can be in conjunction with forming carbonyl; Any ortho position R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Can be in conjunction with forming unsaturated group; And substituent R wherein ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part.

25. according to the modified amine compound of claim 23, wherein to R ³⁴, the pKa value is greater than 3 and less than 23.

26. according to the modified amine compound of claim 25, wherein to R ³⁴, the pKa value is greater than 11 and less than 17.

27. according to the modified amine compound of claim 23, wherein R ³⁴Be selected from and replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group and mistake alkoxyl group.

28. according to the modified amine compound of claim 27, wherein R ³⁴Be selected from hydroxyl or perhydroxyl radical.

29. according to the modified amine compound of claim 16, wherein said modified amine compound has following general formula [XV]-[XVI]:

Wherein m is 1-3 when G exists, and m is 1-4 when G does not exist; And n is the integer of 0-4; R ³⁴Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 20＞pKa＞10; Each R ³⁵Be independently selected from H, alkyl, cycloalkyl, aryl, fused-aryl, heterocycle, annelated heterocycles, nitro, halogen, cyano group, sulfonate radical closes, alkoxyl group, ketone group, carboxyl and carbalkoxy, and any two ortho position R ³⁵Substituting group can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles; R ³²Be to be selected from H or Me; R ³³Be to replace or do not replace, saturated or undersaturated group, said group is selected from the C3-C18 alkyl, the group of C3-C18 cycloalkyl and band negatively charged ion and/or cationic charge.

30. according to the modified amine compound of claim 29, wherein R ³³Be expressed from the next: Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from the group shown in the following formula:

Wherein q is the integer of 1-8; R ³⁸Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from: (1)-O-; (2)-N (R ³⁹)-and (3) N (R ³⁹R ⁴⁰)-, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one can with R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In other any one be joined together to form the part of public ring; When G exists, any together with R ³⁶-R ³⁷Can be in conjunction with forming carbonyl; Any ortho position R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Can be in conjunction with forming unsaturated group; And substituent R wherein ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part.

31. according to the modified amine compound of claim 29, wherein R ³⁴Be selected from hydroxyl or perhydroxyl radical.

32. bleaching composition that contains modified amine compound and associating or do not unite peroxygen source, wherein said modified amine compound is selected from the modified oxidized amine shown in the modified amine shown in following general formula [V] and/or [VI], following general formula [VII]-[X], and composition thereof: R wherein ⁸-R ¹⁰Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, ketone group, carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ¹¹, when existing, be to be selected to replace or not replacement saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, ketone group, carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ¹²Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 37＞pKa＞-2; Precondition is any R ⁸-R ¹², when existing, can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles.

33. according to the bleaching composition of claim 32, wherein R ¹¹Be expressed from the next:

34. according to the bleaching composition of claim 32, wherein to R ¹², the pKa value is greater than 3 and less than 23.

35. according to the bleaching composition of claim 34, wherein to R ¹², the pKa value is greater than 9 and less than 21.

36. according to the bleaching composition of claim 35, wherein to R ¹², the pKa value is greater than about 11 and less than about 17.

37. according to the bleaching composition of claim 32, wherein R ¹²Be selected from and replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group and mistake alkoxyl group.

38. according to the bleaching composition of claim 37, wherein R ¹²Be selected from hydroxyl or perhydroxyl radical.

39. according to the bleaching composition of claim 32, wherein said modified amine compound accounts for about 10% weight of about 0.001%-of said composition weight, and said peroxygen source, when existing, accounts for about 60% weight of about 0.01%-of said composition weight.

40. according to the bleaching composition of claim 32, wherein said peroxygen source when existing, is selected from:

(a) ready-formed peracid compound is selected from percarboxylic acids and salt, and percarbonic acid and salt are crossed imido acid and salt, peroxide one sulfuric acid and salt, with and composition thereof;

(b) hydrogen peroxide cource is selected from the perborate compound, percarbonate compound, superphosphate compound and composition thereof; And bleach-activating agent.

41. a bleaching composition, wherein said modified amine compound has following general formula [XV]-[XX]:

42. according to the bleaching composition of claim 41, wherein R ³³Be expressed from the next:

Z wherein _p ^-With T _oCovalently bound, and Z _p ^-Be selected from-CO ₂ ^-,-SO ₃ ^-,-OSO ₃ ^-,-SO ₂ ^-With-OSO ₂ ^-, and p is 1,2 or 3; T _oBe selected from the group shown in the following formula: Wherein q is the integer of 1-8; R ³⁸Be independently selected from replacement or unsubstituted group, said group is selected from straight or branched H, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; G is selected from: (1)-O-; (2)-N (R ³⁹)-and (3) N (R ³⁹R ⁴⁰)-; R ³⁶, R ³⁷, R ³⁹And R ⁴⁰Be to replace or unsubstituted group, said group is independently selected from H, oxygen, alkyl, cycloalkyl, alkaryl, aryl, aralkyl, alkylidene group, heterocycle, alkoxyl group, aryl carbonyl, carboxyalkyl and amide group; R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one can with R ³², R ³³, R ³⁴, R ³⁵, R ³⁶, R ³⁷, R ³⁹And R ⁴⁰In other any one be joined together to form the part of public ring; Any together with R ³⁶-R ³⁷Can be in conjunction with forming carbonyl; Any ortho position R ³⁶, R ³⁷, R ³⁹And R ⁴⁰, can be in conjunction with forming unsaturated group; And substituent R wherein ³⁶, R ³⁷, R ³⁹And R ⁴⁰In any one group can be in conjunction with form to replace or unsubstitutedly condense unsaturated part.

43. according to the bleaching composition of claim 41, wherein to R ³⁴, the pKa value is greater than 3 and less than 23.

44. according to the bleaching composition of claim 43, wherein to R ³⁴, the pKa value is greater than 11 and less than 17.

45. according to the bleaching composition of claim 41, wherein R ³⁴Be selected from and replace or do not replace, saturated or unsaturated hydroxyl, perhydroxyl radical, alkoxyl group and mistake alkoxyl group.

46. according to the bleaching composition of claim 45, wherein R ³⁴Be selected from hydroxyl or perhydroxyl radical.

47. according to the bleaching composition of claim 32, wherein said bleaching composition also contains one or more and is selected from following detergent component: tensio-active agent, solvent, buffer reagent, enzyme, dirt release agent, clay stain remover, dispersion agent, whitening agent, suds suppressor, fabric softener, suds booster, enzyme stabilizers, washing assistant, sequestrant, other SYNTHETIC OPTICAL WHITNER, dyestuff, dye transfer inhibitor, spices and composition thereof.

48. according to the bleaching composition of claim 47, wherein said bleaching composition also contains tensio-active agent.

49. according to the bleaching composition of claim 48, wherein said tensio-active agent is a branched chain surfactant.

50. according to the bleaching composition of claim 49, wherein said branched chain surfactant is the mid-chain branched tensio-active agent.

51. according to the bleaching composition of claim 48, wherein said tensio-active agent is an anion surfactant.

52. according to the bleaching composition of claim 41, wherein said bleaching composition also contains sequestrant.

53. according to the bleaching composition of claim 41, wherein said bleaching composition also contains other SYNTHETIC OPTICAL WHITNER that is selected from perborate, percarbonate, superphosphate and composition thereof.

54. according to the bleaching composition of claim 53, wherein said bleaching composition also contains bleach-activating agent.

55. according to the bleaching composition of claim 54, wherein said bleach-activating agent is selected from hydrophobic bleach activator.

56. bleaching composition according to claim 55; wherein said hydrophobic bleach activator is selected from tetra acetyl ethylene diamine (TAED); benzoyl caprolactam (BzCL); 4-nitro benzoyl hexanolactam; 3-chlorobenzene formacyl hexanolactam, benzoyl oxygen base benzene sulfonate (BOBS), nonanoly acyloxy benzene sulfonate (NOBS); phenol benzoate (PhBz), the last of the ten Heavenly stems acyloxy benzene sulfonate (C ₁₀-OBS), benzoyl Valerolactim (BZVL), hot acyloxy benzene sulfonate (C ₈-OBS), can cross the ester of hydrolysis, the amino hexylyloxy of 4-[N-(nonanoyl)]-benzene sulfonate sodium salt (NACA-OBS), lauryl oxygen base benzene sulfonate (LOBS or C ₁₂-OBS), (the 10th has UDOBS or the C that insatiable hunger is closed to 10-undecylene acyloxy benzene sulfonate ₁₁-OBS), caprinoyl aminobenzoic acid (DOBA) and composition thereof.

57. according to the bleaching composition of claim 41, wherein said bleaching composition also contains enzyme.

58. according to the bleaching composition of claim 57, wherein said enzyme is selected from cellulase, lipase, amylase, Phospholipid hydrolase, proteolytic enzyme, peroxidase and composition thereof.

59. a method of washing the need clean textile, said method comprise said fabric is contacted with the laundry solution that contains the described bleaching composition of claim 32.

60. a laundry additive product that contains the modified amine compound, wherein said modified amine compound is selected from modified amine compound shown in following general formula [V]-[X] and composition thereof: R wherein ⁸-R ¹⁰Be independently selected from replacement or unsubstituted group, said group is selected from H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, ketone group, carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ¹¹, when existing, be to be selected to replace or not replacement saturated or unsaturated H, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, heterocycle, silyl, nitro, halogen, cyano group, alkoxyl group, ketone group, carbalkoxy and carry negatively charged ion and/or the group of cationic charge; R ¹²Be leavings group, the pKa value (H of its protonated form ₂The O contrast) belongs to following scope: 37＞pKa＞-2; Precondition is any R ⁸-R ¹², when existing, can be in conjunction with forming fused-aryl, fused iso or annelated heterocycles.

61. according to the laundry additive product of claim 60, wherein R ¹¹Be expressed from the next:

62. according to the laundry additive product of claim 60, wherein said laundry additive product is the dosage form that is selected from pill, tablet, gel capsules or other single dose units.

63. according to the laundry additive product of claim 60, wherein said laundry additive product also contains suitable carrier.