CN1342194A

CN1342194A - Stabilized bleach compositions

Info

Publication number: CN1342194A
Application number: CN00804473A
Authority: CN
Inventors: 雷吉娜·拉贝克
Original assignee: Procter and Gamble Ltd
Current assignee: Procter and Gamble Ltd; Procter and Gamble Co
Priority date: 1999-03-02
Filing date: 2000-02-29
Publication date: 2002-03-27
Also published as: EP1157088A1; DE60025472D1; EP1157088B1; AU772358B2; WO2000052124A1; AR022803A1; CZ20013157A3; ES2255992T3; BR0008715A; MXPA01008890A; KR100453614B1; DE60025472T2; ATE315626T1; JP2002538268A; CA2364538A1; AU3612700A; KR20010103787A

Abstract

The present invention relates to bleaching, pre-soak, pre-treatment, and laundry detergent compositions comprising: A) a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand, for example, 5,12-dimethyl-1,5,8,12-tetraazabicyclo[6.6.2] hexadecane manganese (II) chloride, having formula (a); B) an effective amount of a stabilizing agent, said agent selected from i) one or more anti-oxidants; ii) one or more reducing agents; iii) and mixtures thereof; and C) the balance carriers and other adjunct ingredients; provided said composition is substantially free of any organic or inorganic peroxygen compounds.

Description

Stable bleaching composition

Invention field

The present invention relates to stable bleaching and cleaning composition, said composition comprises the transition metal bleach catalyzer of catalytically effective amount and is used to stablize the antioxidant or the reductive agent of described catalyzer, and transition metal bleach catalyzer wherein is the title complex of the large-scale many ring parts of transition metal and cross-bridge.The invention still further relates to the method with the described stable transition metal bleach catalyzer bleaching/clean textile of catalytically effective amount, this method is to carry out under the condition without any organic or inorganic superoxide or the existence of any organic or inorganic peroxide precursor basically.

Background of invention

The bleaching of fabric is to be exposed to chemical reaction by the fabric that will make dirty or stain to carry out basically, and the purpose of chemical reaction is to remove crude removal or color spot.Simultaneously, bleaching relates to fabric and is exposed to hypochlorite solutions.Therefore, can not handle with SYNTHETIC OPTICAL WHITNER by responsive pigment coloring or painted fabric.For human consumer's interests, formulator has been developed various forms of SYNTHETIC OPTICAL WHITNER, particularly peroxide bleaching system, and this system typically comprises hydrogen peroxide cource and bleach-activating agent.Being combined in safely and effectively of this hydrogen peroxide cource and activator played a leading role in the bleaching composition.Effective example of this peroxide bleaching system is to use perborate (peroxide source) and nonanoyl oxygen benzene sulfonate (activator).

Be the performance of enhancing SYNTHETIC OPTICAL WHITNER, and develop, polyester mixture, cotton, the novel method that the bleach system of nylon safety, formulator are constantly developed the peroxide bleaching system and formed active oxygen the dyeing of any kind or painted fabric, particularly silk.

Yet, in this area stable bleach system being still had needs, described bleach system is bleached woven fabric effectively, and does not need for example superoxide, the chemical that reacts of peroxide source and/or its mixture.Described stable bleach system comprises transition-metal catalyst, and this catalyzer can be because of not losing its effect to the oxidation in the prescription of back and/or the instability of reduction reaction.

Summary of the invention

The present invention has satisfied the demand.The present invention is surprisingly found out that, the bleach system that contains transition-metal catalyst can be stablized well, can prevent the decomposition of unwanted transition-metal catalyst, described transition-metal catalyst can be bleached dirt and color spot under the condition that lacks hydrogen peroxide cource or other peroxide bleaching agent.In other words, the present inventor is surprisingly found out that, adds antioxidant and/or the free-radical scavengers or the reductive agent of significant quantity, can stablize the bleach system of no hydrogen peroxide.

A first aspect of the present invention relates to stable bleaching composition, and said composition comprises:

A) the transition metal bleach catalyzer of catalytically effective amount, this catalyzer is a transition metal

Title complex with the large-scale many ring parts of cross-bridge;

B) effective amount of stabilizer, described stablizer is selected from:

I) one or more antioxidants;

Ii) one or more reductive agents;

Iii) reach their mixture; With

C) carrier of surplus and other ancillary component; Supplementary condition are that described composition is substantially free of any organic or inorganic superoxide.

The invention still further relates to clean and/or bleached woven fabric on dirt and the method for color spot, described method comprises cleans needs and/or step that the fabric of bleaching contacts with the aqueous solution, the described aqueous solution contains the composition that is substantially free of peroxide source, and said composition comprises:

Title complex with the large-scale many ring parts of cross-bridge;

B) effective amount of stabilizer, described stablizer is selected from:

I) one or more antioxidants;

Ii) one or more reductive agents;

Iii) reach their mixture; With

C) carrier of surplus and other auxiliary component; Supplementary condition are that the concentration of described transition metal bleach catalyzer in the aqueous solution is at least about 0.01ppb, and described composition is substantially free of any organic or inorganic superoxide.

The compositions and methods of the invention are suitable for cleaning/bleaching the surface that any needs remove crude removal.For example, hard surface cleaner and automatic washing machine can adopt bleaching catalyst of the present invention, described composition to be substantially free of any organic or inorganic superoxide in application with composition.

By reading following detailed Description Of The Invention and additional claim, those of ordinary skill in the art is to these and other objects, and feature and advantage will be apparent from.

Unless otherwise noted, all per-cents of the present invention, ratio and umber are all by weight.Unless otherwise noted, all temperature all be meant degree centigrade (℃).The relevant portion of the document of all references all is combined in herein as a reference.

Detailed Description Of The Invention

The present invention relates to wonderful discovery, promptly can bleach the transition-metal catalyst of dirt and color spot under not with the situation of peroxide bleaching agent, can suitably be stablized by adding one or more stablizers.The amount of the stablizer that is suitable for using in the present invention depends on prescription, the liquid of Cun Zaiing particularly, solid, gel, and the concentration of transition metal.There is not peroxide source

Composition of the present invention, and use composition of the present invention to clean and/or the method for bleached woven fabric is substantially free of any peroxide source, hydrogen peroxide for example, peroxy acid etc.Composition of the present invention only needs to contain the following catalyzer of the present invention that can effectively bleach of significant quantity.For purpose of the present invention, term " is substantially free of " and is defined as: " in the prescription of composition; not can effectively bleach in the presence of the transition-metal catalyst not having; or in the presence of defined transition-metal catalyst, can improve the amount of bleaching effect as the present invention, contain any superoxide or peroxide source ".Therefore, as following institute further the narration, add the water-based or the non-aqueous solution of catalyzer described herein simply by the fabric of making dirty to quilt, just can effectively bleach dirt, preferred fabric contacts with catalyzer in the aqueous solution.But, should be realized that because the source of formulator out of contior factor, particularly raw materials for production, the unwanted decomposition of one or more compositions is introduced into peroxide source, and/or in product, form unawares.Composition of the present invention is without any need for peroxide source, but any more a spot of existence can not influence the performance of bleaching composition of the present invention.

Usually formulator can comprise a small amount of hydrogen peroxide cource in composition, to reach the purpose of stabilized enzyme, for example, can add more a spot of perborate.But the amount of this perborate generally is less, to such an extent as to can not influence the whitening capacity of the present composition.In prescription, add small amounts agent or other peroxide source with under the situation that reaches the purpose of stablizing ancillary component, for purpose of the present invention, if they do not provide other bleaching activity to dirt under general application conditions, these compositions still are defined as " being substantially free of " peroxide source as defined above.For example, the composition of a kind of " being substantially free of " can comprise a certain amount of peroxide source, and it is basic identical when not having peroxide source that prerequisite is the validity of catalyzer.For purpose of the present invention, contain and be less than 0.1%, preferably be less than 0.01% basic oxygenant, any composition of for example ready-made peracid or hydrogen peroxide cource is considered to as above further " being substantially free of " of definition.In addition, wherein use catalyzer of the present invention, and any laundry liquid that contains the peroxide source of the ready-made or original position formation that is lower than 0.001% (weight), the clothing washing water, the preimpregnation bathing, or other fabric or surface cleaning solution, also be defined as defined above " being substantially free of " herein.In other words, if catalyzer of the present invention is used for the dirt on the bleached woven fabric, perhaps cleaning/bleaching crust or tableware, and the concentration that contains peroxide source in the solution of catalyzer is lower than 0.001%, and this solution is defined as " being substantially free of " peroxide source so herein.Bleaching catalyst

Composition of the present invention contains the bleaching catalyst of significant quantity.Term " significant quantity " is defined as: " exist in the present composition; or the amount of the transition metal bleach catalyzer when using according to method of the present invention; no matter this amount is under comparison or application conditions, all be enough to make the material that will pass through said composition or method oxidation oxidized to small part ".Typically, oxidized material is unwanted material, F﹠B spot particularly, and greasy dirt, the human excrement and urine on the fabric, but range of application of the present invention is not limited to this.The oxidation that lacks peroxide source has extensive applicability, and the present invention is not limited only to bleaching and/or clean textile.For example, the automatic dishwasher composition is one embodiment of the invention, and wherein using composition of " being substantially free of " peroxide source and/or solution bleaching dirt is a part of the present invention.This point is suitable equally with the solution that contains hard-surface cleaning compositions for the hard-surface cleaning compositions of " being substantially free of " peroxide source.

Preferably, composition of the present invention contains the following about 1ppb (0.0000001%) that is limited to composition weight of transition metal bleach catalyzer as described below, more preferably be limited to about 100ppb (0.00001%) down, also more preferably be limited to about 500ppb (0.00005%) down, be limited to about 1ppm (0.0001%) down, on be limited to approximately 99.9%, be limited to about 50% on more preferably, also be limited on more preferably approximately 5%, be limited to about 500ppm (0.05%) on more more preferably.

The most at large, transition metal bleach catalyzer of the present invention comprises:

I) a kind of transition metal is selected from 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 Mn (II), Mn (III), Mn (IV), Fe (II), Fe (III), Fe (IV), Cr (II), Cr (III), Cr (IV), Cr (V), Cr (VI), and composition thereof; Ii) give electronic atom and a kind of cross-bridges of same transition-metal coordination large-scale many ring parts with 4 or 5, described part comprises: a) a kind of organic macrocycle, this ring contain 4 or a plurality of to electronic atom (preferably at least 3,

More preferably at least 4 is N to electronic atom), the described electronic atom of giving is each other by 2

Individual or 3 non-covalency that constitute to electronic atom connect separately, wherein 2～5 (excellent

Select 3～4, more preferably 4) to the same transition in electronic atom and the title complex

Metal-complexing; B) a kind of cross-bridge chain, at least 2 non-adjacent electronic atoms of giving on itself and the organic macrocycle are covalently bound, described covalently bound non-adjacent be that end of the bridge is given electronic atom to electronic atom, same transition-metal coordination in itself and the title complex, and wherein said cross-bridge chain contains 2～about 10 atoms, and (preferred cross-bridge chain is selected from 2,3 or 4 non-gives electronic atom and also has 1 4-6 non-electronic atom of giving giving electronic atom); C) randomly, one or more non-large-scaled many ring parts are preferably selected from H ₂O, ROH, NR ₃, RCN, OH ^-, OOH ^-, RS ^-, RO ^-, RCOO ^-, OCN ^-, SCN ^-, N ₃ ^-, CN ^-, F ^-, Cl ^-, Br ^-, I ^-, O ₂ ^-, NO ₃ ^-, NO ₂ ^-, SO ₄ ^2-, SO ₃ ^2-, PO ₄ ^3-, the organophosphorus acid group, the organic phosphine acid group, the organosulfur acid group, organic sulfonic acid root and fragrant N electron donor, pyridine for example, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, pyrimidine, triazole and thiazole, wherein R is H, the optional alkyl that replaces, the optional aryl that replaces.The large-scale many ring parts of preferred cross-bridge are selected from: the large-scale many ring parts of cross-bridge that a) have the formula (I) of 4 or 5 dentates:

B) have the large-scale many ring parts of the cross-bridge of formula (II) of 5 or 6 dentates:

C) have the large-scale many ring parts of the cross-bridge of formula (III) of 6 or 7 dentates: Wherein the following fragment of general formula is represented in each E unit:

(CR _n) _a-X-(CR _n) _{A '}Wherein X is selected from oxygen, sulphur, and-NR-, phosphorus, or X represents covalent linkage, and wherein the general formula of E is:

(CR _n) _a-(CR _n) _a′

For each E unit, a+a ' and be independently selected from 1～5; Each G unit is (a CR _n) _bFragment; Each R unit is independently selected from H, alkyl, thiazolinyl, alkynyl, aryl, alkaryl and heteroaryl, or the covalently bound formation aromatic ring in two or more R unit, hetero-aromatic ring, cycloalkyl ring or heterocycloalkyl ring; Each D unit is to electronic atom, is independently selected from nitrogen, oxygen, and sulphur and phosphorus, and at least two unitary atoms of formation D are to give electronic atom with the end of the bridge of transition-metal coordination; The B unit is a carbon atom, a D unit, or cycloalkyl ring or heterocycle; Each n is independently selected from 1 and 2 integer, satisfies the valency of the covalently bound carbon atom in R unit; Each n ' is independently selected from 0 and 1 integer, satisfies the valency that the covalently bound D of R fragment gives electronic atom; Each n " is to be independently selected from 0,1 and 2 integer, satisfies the valency of the covalently bound B atom of R fragment; Each a and a ' are independently selected from 0～5 integer, wherein in the part of formula (I) all a+a ' values and scope be about 8～about 12; In the part of formula (II) all a+a ' values and scope be about 10～about 15; In the part of formula (III) all a+a ' values and scope be about 12～about 18; Each b is independently selected from 0～9 integer, or in above-mentioned any one general formula, as long as in general formula, have two (CR at least _n) _bTwo D are covalently bound on the B atom to electronic atom, then covalently bind in the interatomic one or more (CR of D and B _n) _bFragment can not exist, and all b values and in about 2～about 5 scopes.

WO 98/39406 A1 that bleaching catalyst of the present invention was announced on September 11st, 1998, WO 98/39098 A1 that on September 11st, 1998 announced, with further describe among the WO 98/39335A1 that announced on September 11st, 1998, all the elements of these three pieces of patents are combined in herein as a reference.

What run through this patent is used to that to describe the nomenclature of transition metal bleach catalyzer identical with the naming method of above-mentioned reference.But the chemical name of one or more parts disclosed in this invention may be different from the chemical name of purely international and the regular defined of applied chemistry federation (IUPAC).For example, the preferred part 5 of a kind of the present invention, 12-dimethyl-1,5,8, the IUPAC called after 4 of 12-four aza-bicyclos [6.6.2] n-Hexadecane, 11-dimethyl-1,4,8,11-4-azabicyclo [6.6.2] n-Hexadecane.

Generally speaking the transition metal bleach catalyzer that can be used for the present composition can comprise the compound known that meets the present invention definition, and more preferably comprises any a large amount of novel cpds that design for laundry of the present invention or cleaning applications specially.The non-limiting example of appropriate catalyst of the present invention comprises: and dichloro (5,12-dimethyl-1,5; 8,12-4-azabicyclo [6.6.2] n-Hexadecane) close manganese (II) dichloro (4,10-dimethyl-1; 4,7,10-4-azabicyclo [5.5.2] tetradecane) closes manganese (II) two water (5; 12-dimethyl-1,5,8; 12-4-azabicyclo [6.6.2] n-Hexadecane) close manganese (II) hexafluoro close phosphoric acid salt one water hydroxide radical (5,12-dimethyl-1,5; 8,12-4-azabicyclo [6.6.2] n-Hexadecane) close manganese (III) hexafluoro close the phosphoric acid monocalcium salt (4,10-dimethyl-1; 4,7,10-4-azabicyclo [5.5.2] tetradecane) closing manganese (II) hexafluoro closes phosphoric acid monocalcium salt (5; 12-dimethyl-1,5,8; 12-4-azabicyclo [6.6.2] n-Hexadecane) close manganese (II) tetrafluoro close the boric acid monocalcium salt (4,10-dimethyl-1,4; 7,10-4-azabicyclo [5.5.2] tetradecane) close manganese (II) tetrafluoro close the borate dichloro (5,12-dimethyl-1; 5,8,12-4-azabicyclo [6.6.2] n-Hexadecane) closing manganese (III) hexafluoro closes phosphoric acid salt dichloro (5; 12-di-n-butyl-1,5,8; 12-four aza-bicyclos [6.6.2] n-Hexadecane) close manganese (II) dichloro (5,12-dibenzyl-1,5; 8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) dichloro (5-normal-butyl-12-methyl isophthalic acid, 5; 8,12-four aza-bicyclos [6.6.2] n-Hexadecane) closes manganese (II) dichloro (5-n-octylcyclam 2-methyl isophthalic acid, 5; 8,12-four aza-bicyclos [6.6.2] n-Hexadecane) closes manganese (II) dichloro (5-normal-butyl-12-methyl isophthalic acid, 5; 8,12-four aza-bicyclos [6.6.2] n-Hexadecane) close manganese (II) dichloro (5,12-dimethyl-1; 5,8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes iron (II) dichloro (4; 10-dimethyl-1,4,7; 10-4-azabicyclo [5.5.2] tetradecane) close iron (II) dichloro (5,12-dimethyl-1,5; 8,12-4-azabicyclo [6.6.2] n-Hexadecane) close copper (II) dichloro (4,10-dimethyl-1; 4,7,10-4-azabicyclo [5.5.2] tetradecane) closes copper (II) dichloro (5; 12-dimethyl-1,5,8; 12-4-azabicyclo [6.6.2] n-Hexadecane) close cobalt (II) dichloro (4,10-dimethyl-1,4; 7,10-4-azabicyclo [5.5.2] tetradecane) close cobalt (II) dichloro (5,12-dimethyl-4-phenyl-1; 5,8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) dichloro (4; 10-dimethyl-3-phenyl-1,4,7; 10-4-azabicyclo [5.5.2] tetradecane) close manganese (II) dichloro (5,12-dimethyl-4,9-phenylbenzene-1; 5,8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) dichloro (4; 10-dimethyl-3,8-phenylbenzene-1,4; 7,1 0-4-azabicyclo [5.5.2] tetradecanes) close manganese (II) dichloro (5,12-dimethyl-2; 11-phenylbenzene-1,5,8; 12-4-azabicyclo [6.6.2] n-Hexadecane) close manganese (II) dichloro (4,10-dimethyl-4,9-phenylbenzene-1; 4,7,10-4-azabicyclo [5.5.2] tetradecane) closes manganese (II) dichloro (2; 4,5,9; 11,12-vegolysen, 5; 8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) dichloro (2,3; 5,9,10; the 12-vegolysen; 5,8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) dichloro (2; 2; 4,5,9; 9; 11,12-prestox-1,5; 8; 12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) dichloro (2,2,4; 5; 9,11,11; 12-prestox-1; 5,8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) dichloro (3; 3; 5,10,10; the 12-vegolysen; 5,8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) dichloro (3; 5; 10,12-tetramethyl--1,5; 8; 12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) dichloro (3-butyl-5,10,12-trimethylammonium-1; 5; 8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) dichloro (1,5; 8; 12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) dichloro (1,4,7; 10-4-azabicyclo [5.5.2] tetradecane) closes manganese (II) dichloro (1; 5,8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes iron (II) dichloro (1; 4; 7,10-4-azabicyclo [5.5.2] tetradecane) closes iron (II) water chlorine (2-(2-hydroxy phenyl)-5,12-dimethyl-1; 5; 8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) water chlorine (10-(2-hydroxybenzyl)-4,10-dimethyl-1; 4; 7,10-4-azabicyclo [5.5.2] tetradecane) closes manganese (II) chlorine (2-(2-hydroxybenzyl)-5-methyl isophthalic acid, 5; 8; 12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) chlorine (10-(2-hydroxybenzyl)-4-methyl isophthalic acid, 4,7; 10-4-azabicyclo [5.5.2] tetradecane) closes manganese (II) chlorine (5-methyl isophthalic acid 2-(2-picolyl)-1; 5,8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) muriate chlorine (4-methyl isophthalic acid 0-(2-picolyl)-1; 4; 7,10-4-azabicyclo [5.5.2] tetradecane) closes manganese (II) muriate dichloro (5-(2-sulfato) dodecyl-12-methyl isophthalic acid, 5; 8; 12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (III) water chlorine (5-(2-sulfato) dodecyl-12-methyl isophthalic acid, 5,8; 12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) water chlorine (5-(3-alkylsulfonyl propyl group)-12-methyl isophthalic acid; 5,8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) dichloro (5-(trimethylammonium amido propyl group) dodecyl-12-methyl isophthalic acid; 5; 8,12-4-azabicyclo [6.6.2] n-Hexadecane) close manganese (III) muriate dichloro (5,12-dimethyl-1; 4; 7,10,13-pentaaza two ring [8.5.2] heptadecanes) close manganese (II) dichloro (14; 20-dimethyl-1; 10,14,20-four aza-tricycles [8.6.6] docosane-3 (8); 4; the 6-triolefin) close manganese (II) dichloro (4,11-dimethyl-1,4; 7; 11-4-azabicyclo [6.5.2] pentadecane) close manganese (II) dichloro (5,12-dimethyl-1,5; 8; 12-4-azabicyclo [7.6.2] heptadecane) close manganese (II) dichloro (5,13-dimethyl-1,5; 9; 13-4-azabicyclo [7.7.2] heptadecane) close manganese (II) dichloro (3,10-two (fourth carboxyl)-5,12-dimethyl-1; 5; 8,12-4-azabicyclo [6.6.2] n-Hexadecane) close manganese (II) two water (3,10-dicarboxyl-5; 12-dimethyl-1; 5,8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) chlorine (20-methyl isophthalic acid; 9; 20,24,25-pentaaza-Fourth Ring [7.7.7.1 ^3,7.1 ^11,15] pentacosane-3,5,7 (24), 11,13,15 (25)-six alkene) close manganese (II) hexafluoro and close phosphoric acid salt trifluoromethane sulfonic acid root (20-methyl isophthalic acid, 9,20,24,25-pentaaza-Fourth Ring [7.7.7.1 ^3,7.1 ^11,15] pentacosane-3,5,7 (24), 11,13,15 (25)-six alkene) close manganese (II) trifluoromethyl sulfonic acid trifluoromethane sulfonic acid root (20-methyl isophthalic acid, 9,20,24,25-pentaaza-Fourth Ring [7.7.7.1 ^3,7.1 ^11,15] pentacosane-3,5,7 (24), 11,13,15 (25)-six alkene) close iron (II) trifluoromethyl sulfonic acid chlorine (5,12,17-trimethylammonium-1,5,8,12,17-pentaaza two ring [6.6.5] nonadecanes) closing manganese (II) hexafluoro closes phosphoric acid salt chlorine (4,10,15-trimethylammonium-1,4,7,10,15-pentaaza two ring [5.5.5] heptadecanes) closing manganese (II) hexafluoro closes phosphoric acid salt chlorine (5,12,17-trimethylammonium-1,5,8,12,17-pentaaza two ring [6.6.5] nonadecanes) close manganese (II) muriate chlorine (4,10,15-trimethylammonium-1,4,7,10,15-pentaaza two ring [5.5.5] heptadecanes) close manganese (II) muriate dichloro (5,12,15,16-tetramethyl--1,5,8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II) chlorine (5-methyl isophthalic acid 2-(2 '-oxygen benzyl)-1,5,8,12-4-azabicyclo [6.6.2] n-Hexadecane) closes manganese (II)

Preferred title complex as the transition metal bleach catalyzer more generally, not only comprises the monometallic monokaryon type of act as listed above, also comprises bimetal, the title complex of three metals or bunch type.The title complex of preferred monometallic monokaryon.Define as the present invention, for monometallic transition metal bleach catalyzer, every mole of title complex only contains a transition metal atoms.The monometallic mononuclear coordination compound is a kind of like this compound, and any on the wherein basic macrocyclic ligand is attached on the same transition metal atoms to electronic atom, and promptly basic part not " bridge " connects two or more transition metal atoms.Stablizer

Antioxidant

A kind of preferred stablizer of the present invention is an antioxidant.Composition of the present invention contains the antioxidant of significant quantity, and by weight, the following of preferred anti-oxidant content is limited to about 0.01%, more preferably be limited to down about 0.1%, most preferably be limited to down about 0.2%, on be limited to about 10%, preferred upper limit is about 5%, is limited to about 1% on more preferably.Preferred anti-oxidant is a free-radical scavengers.

The antioxidizing agent that is suitable for using in the present invention is the following alkylphenol of general formula: Wherein R is C ₁-C ₂₂Linearity or branched-alkyl, the C of preferable methyl or branching ₃-C ₆Alkyl; C ₃-C ₆Alkoxyl group, preferred methoxyl group; R ¹Be C ₃-C ₆The alkyl of branching, the preferred tertiary butyl; X is 1 or 2.

The another kind of antioxidant that is suitable for using in the present invention is the following benzofuran derivative of general formula:

R wherein ¹And R ²Be C independently of one another ₁-C ₄Alkyl, or R ¹And R ²Can constitute C together ₅-C ₆The cyclic hydrocarbon fragment; R ⁴Be C ₁-C ₆Alkyl; R ⁵For hydrogen or-C (O) R ³, R wherein ³Be hydrogen or C ₁-C ₁₉Alkyl; R ⁶Be C ₁-C ₆Alkyl; R ⁷Be hydrogen or C ₁-C ₆Alkyl; X is-CH ₂OH, or-CH ₂A, wherein A is nitrogenous unit, phenyl, or the phenyl that replaces.Preferred nitrogenous A unit comprises amino, pyrrolidino, piperidino-(1-position only), morpholino, Piperazino and composition thereof.

The non-limiting example of the antioxidant that is suitable for using in the present invention comprises phenol, 2,6 di t butyl phenol particularly, 2, the 6-di-tert-butyl-4-methy phenol, the mixture of 2-and the 3-tertiary butyl-4-methoxyphenol, and other component comprise Tenox PG, Tert. Butyl Hydroquinone, benzoic acid derivative, for example methoxybenzoic acid, tolyl acid, dichlorobenzoic acid, mesitylenic acid, 5-hydroxyl-2,2,4,6,7-pentamethyl--2,3-dihydro-1-cumarone-3-ketone, 5-hydroxyl-3-methylene radical-2,2,4,6,7-pentamethyl--2,3-dihydro-cumarone, 5-benzyloxy-3-methylol-2,2,4,6,7-pentamethyl--2,3-dihydro-1-cumarone, 3-methylol-5-methoxyl group-2,2,4,6,7-pentamethyl--2,3-dihydro-1-cumarone.

Reductive agent

A kind of preferred stablizer of the present invention is a reductive agent.Composition of the present invention contains one or more reductive agents of significant quantity, and by weight, preferred the following of reductive agent content is limited to about 0.001%, more preferably be limited to down about 0.01%, most preferably be limited to down about 0.02%, on be limited to about 1%, preferred upper limit is 0.5%, is limited to about 0.1% on more preferably.Preferred reductive agent is a mineral compound.

The non-limiting example of reductive agent comprises the compound that can produce sulfite ion, S-WAT for example, potassium sulfite, ammonium sulphite, sodium bisulfite, sodium metabisulfite, inclined to one side Potassium hydrogen sulfite, Potassium hydrogen sulfite, pyrosulfite, sodium borohydride, lithium borohydride, aluminum isopropylate lithium and composition thereof.Using method

The invention still further relates to use does not need the stable bleaching catalyst of peroxide source to come the dirt on the clean textile and the method for color spot.

Therefore, the present invention relates in the method that lacks the dirt on the bleached woven fabric and color spot under the situation of SYNTHETIC OPTICAL WHITNER, described method comprises the step that fabric that needs are cleaned contacts with water-based or non-aqueous solution, and described solution contains the composition that is substantially free of peroxide source, and said composition comprises:

Title complex with the large-scale many ring parts of cross-bridge;

B) effective amount of stabilizer, described stablizer is selected from:

I) one or more antioxidants;

Ii) one or more reductive agents;

Iii) reach their mixture; With

C) carrier of surplus and other ancillary component; Supplementary condition are that the concentration of described transition metal bleach catalyzer in solution is at least about 0.01ppb, and described composition is substantially free of any organic or inorganic superoxide.

Contain in the solution of transition metal bleach catalyzer, the strength of solution of catalyzer is preferably about 1ppb, more preferably about 10ppb, more about 100ppb.For example, 100ppb (1,000,000,000/umber) is meant the solution that contains 0.00001% (weight) catalyzer.As defined above, containing the solution that is less than 0.001% peroxide source is " being substantially free of " any organic or inorganic peroxide solution.

The method that relates to extensive bleaching itself fully, for example industrialization or production process can be used the catalyzer of higher concentration, for example use the catalyzer of 1ppm or greater concn, to reduce fabric and the duration of contact that contains the solution of catalyzer.Ancillary component

Bleaching of the present invention, pre-soaking, pre-treatment, clothing with or automatic dishwasher usefulness, no matter the or composition used of hard-surface cleaning is particle, solid (rod), colloid or liquid can also contain one or more carriers and ancillary component.

Composition of the present invention can contain:

A) the transition metal bleach catalyzer of catalytically effective amount, this catalyzer are the title complexs of the large-scale many ring parts of transition metal and cross-bridge; With

B) one or more dye-fixing agents of Ren Xuan about 0.001%～about 90% (weight);

C) one or more fibrin reaction dye-fixing agents of Ren Xuan about 0.01%～about 50% (weight);

D) Ren Xuan about chlorine scavenger of 0.01%～about 15% (weight);

E) one or more crystal growth inhibitors of Ren Xuan about 0.005%～about 1% (weight):

F) polymkeric substance of the minimizing fabric abrasion of Ren Xuan about 0.01%～about 20% (weight);

G) one or more liquid vehicles of Ren Xuan about 1%～about 12% (weight);

H) Ren Xuan about enzyme of 0.001%～about 1% (weight);

I) Ren Xuan about 0.01%～about 8% (weight) polyolefin emulsion or suspension;

J) Ren Xuan about stablizer of 0.01%～about 0.2% (weight);

K) Ren Xuan about fabric softener of 1%～about 80% (weight);

L) the Ren Xuan primary solvent that is less than about 15% (weight); With

M) optionally be limited to approximately 0.01% down, preferred lower limit is about 0.1%, on be limited to about 60%,

Preferred upper limit is one or more tensio-active agents of about 30% (weight), described surface

Promoting agent is selected from anion surfactant, cats product, and non-ionic surface is lived

The property agent, amphoterics, zwitterionics, and compound.Tensio-active agent

Bleaching of the present invention, pre-soaking, pre-treatment, can contain at least about 0.01% (weight) with laundry detergent compositions, preferred lower limit is about 0.1%, on be limited to about 60%, preferred upper limit is the cleansing surfactants system of about 30% (weight), and described system contains a class or multiclass tensio-active agent according to different embodiments, described kinds of surfactants is selected from anion surfactant, cats product, nonionogenic tenside, zwitterionics, amphoterics, and compound.In every class tensio-active agent, there is more than one surfactant types to select.For example, preferably, in solid of the present invention (being particle) and thick semisolid (being gel, pasty state etc.) system, the content of preferred surfactant is the about 0.1%～60% of composition weight, and preferred upper limit is about 30%.

The non-limiting example that can be used for tensio-active agent of the present invention comprises:

A) C ₁₁-C ₁₈Alkylbenzene sulfonate (LAS);

B) C ₁₀-C ₂₀One-level, side chain and random alkylsulfonate (AS);

C) the following C of general formula ₁₀-C ₁₈Secondary (2,3) alkylsulfonate:

Wherein x and (y+1) be to be at least about 7 integer preferably is at least about 9; Described tensio-active agent is disclosed in the U.S.3 of the Morris that announced on February 8th, 1966,234,258; The U.S.5 of the Lutz that on December 24th, 1991 announced, 075,041; The U.S.5 of the Lutz that on September 20th, 1994 announced etc., 349,101; With the U.S.5 of the Prieto that announces February 14 nineteen ninety-five, 389,277, every piece of patent all is combined in herein as a reference;

D) C ₁₀-C ₁₈Alkyl alkoxy sulfate (AE _xS), wherein preferred x is 1-7;

E) C ₁₀-C ₁₈The alkyl alkoxy carboxylate salt preferably contains 1-5 ethoxy unit;

F) C ₁₂-C ₁₈Alkyl ethoxylates, C ₆-C ₁₂Alkylphenol alkoxylates, wherein alkoxide

The unit is inferior ethoxyl and the unitary mixture of inferior propoxy-, C ₁₂-C ₁₈Pure and mild C ₆-C ₁₂Alkane

The condenses, particularly BASF of base phenol and ethylene oxide/propylene oxide segmented copolymer

Pluronic ^, it is disclosed in the U.S. of the Laughlin that announced on December 30th, 1975 etc.

3,929,678, this patent is combined in herein as a reference;

G) be disclosed in the U.S.4 of the Llenado that published on January 26th, 1986, the alkyl in 565,647

Polysaccharide, this patent is combined in herein as a reference;

H) the following polyhydroxy fatty acid amide of general formula:

R wherein ⁷Be C ₅-C ₃₁Alkyl; R ⁸Be selected from hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl, Q are the polyhydroxy alkyl fragments, and this fragment is the linear alkyl chain with at least 3 hydroxyls that directly link to each other with chain, or its oxidation alkyl derivative; Alkoxyl group is preferably oxyethyl group or propoxy-, and composition thereof; Preferred Q is derived from the reducing sugar in reduction amination, and more preferably Q is the glycityl fragment; More preferably Q is selected from-CH ₂(CHOH) _nCH ₂OH ,-CH (CH ₂OH) (CHOH) _N-1CH ₂OH ,-CH ₂(CHOH) ₂-(CHOR ') be CH (CHOH) ₂OH, and oxidation alkyl derivative, wherein n is 3～5 integer (comprising 3 and 5), and R ' is hydrogen or ring-type or aliphatics monose, it is disclosed in the U.S.5 of the Connor that announced on February 6th, 1996 etc., 489,393; With the U.S.5 of the Murch that announces October 3 nineteen ninety-five etc., 45,982, these two pieces of patents all are combined in herein as a reference.

Bleaching of the present invention, pre-soaking, pre-treatment and laundry detergent compositions also can contain the tensio-active agent of branching in 0.001%～about 100% one or more (preferably two or more the mixture) chains of having an appointment, the alkyl alkoxy alcohol of branching in the following chain of preferred formula:

The alkyl-sulphate of branching in the following chain of general formula: Alkyl alkoxide vitriol with branching in the following chain of general formula:

Wherein the one-level alkyl fragment in the branching of these general formulas (comprises R, R ¹And R ²Side chain, but do not comprise and constitute the segmental carbon atom of any EO/PO alkoxyl group) the total number of carbon atoms be 14～20, further, for this surfactant mixture, be (being preferably about 15～about 17) between greater than 14.5 to about 17.5 at segmental average the total number of carbon atoms of branching one-level alkyl with above-mentioned general formula; R, R ¹, and R ²Be selected from hydrogen independently of one another, C ₁-C ₃Alkyl, and composition thereof, preferable methyl; Supplementary condition are R, R ¹, and R ²Not all be hydrogen, and when z is 1, R or R at least ¹Be not hydrogen.M is water-soluble cationic and the positively charged ion that can contain more than one, for example mixture of sodium and potassium.Index w is 0～13 integer; X is 0～13 integer; Y is 0～13 integer; Z is at least 1 integer; Supplementary condition are that w+x+y+z is 8～14.EO and PO represent following inferior ethoxyl unit of general formula and inferior propoxy-unit respectively: But, other oxyalkyl units, particularly 1, the inferior propoxy-of 3-, butoxy and composition thereof also is suitable for as the oxyalkyl units on the alkyl fragment that is suspended on branching in the chain.

The tensio-active agent of branching preferably contains the mixture of surfactant system in this chain.Therefore, when surfactant system contains oxyalkylated tensio-active agent, the average alkoxide degree of exponent m presentation surface active agent intermixture.Like this, it is about 0.01 that exponent m is at least, and preferred lower limit is about 0.1, more preferably be limited to down about 0.5, most preferably be limited to down about 1, on be limited to approximately 30, preferred upper limit is 10, is limited to about 5 on more preferably.When in the chain of considering only to comprise the alkoxide tensio-active agent during branched surfactants system, on behalf of average alkoxide degree, the value of exponent m be equivalent to the distribution of m, or it can be that the unitary accurate quantity of alkylation (for example ethoxyquin and/or third oxidation) is the single specific chains of m.

Be suitable for the tensio-active agent of branching in the preferred chain of the present invention of surfactant system of the present invention, have following general formula:

Or following general formula:

A wherein, b, d and e are integers, and a+b is 10～16, and d+e is 8～14; M is selected from sodium, potassium, and magnesium, the ammonium of ammonium and replacement, and composition thereof.

The surfactant system that contains the tensio-active agent of branching in the chain of the present invention is preferred for two prescriptions in the embodiment.First preferred embodiment contain by comprise 25% or still less chain in the tensio-active agent of branching in the chain that forms of the raw material of alkyl unit of branching.Therefore, with before any other conventional surfactants is mixed, the surface active agent composition of branching will contain 25% or nonlinear surfactant molecule still less in this chain.

Second preferred embodiment contains the tensio-active agent of branching in the chain that is formed by the raw material that comprises the alkyl unit of branching in about chain of 25%～about 70%.Therefore, with before any other conventional surfactants is mixed, the surface active agent composition of branching will contain 25%～about 70% the nonlinear surfactant molecule of having an appointment in this chain.

The surfactant system of laundry detergent compositions of the present invention, the alkylaryl sulfonate surfactants that also can contain branching in one or more (preferably two or more mixture) chains, in surfactant system weight, be limited to about 0.001% under its content, preferred lower limit is about 1%, more preferably be limited to about 5% down, most preferably be limited to about 10% down, on be limited to about 100%, preferred upper limit is about 60%, be limited to approximately 30% more preferably, aryl unit is the following phenyl ring of general formula in the preferred surfactant:

Wherein L is the non-cyclic hydrocarbon substrate section that contains 6～18 carbon atoms; R ¹, R ², and R ³Be hydrogen or C independently of one another ₁-C ₃Alkyl, supplementary condition are R ¹And R ²Be not connected the unitary end of L; M is that electric charge is the water-soluble cationic of q, and wherein a and b satisfy charge balance together.Washing assistant

Composition of the present invention particularly when containing tensio-active agent, preferably contains one or more detergent builder compounds or builder system.When having detergent builder compound, by weight, comprise about 1% washing assistant at least in the general composition, preferred lower limit is about 5%, and more preferably lower limit is about 10%, and the upper limit is about 80%, and preferred upper limit is about 50%, and more preferably the upper limit about 30%.

According to the end-use and the needed physical form of composition, the content of washing assistant can change in very wide scope.When having washing assistant, composition generally contains 1% the washing assistant of having an appointment at least.Generally contain in the prescription have an appointment 5%～about 50%, 5%～about 30% (weight) detergent builder compound more preferably from about.Granular prescription generally contain have an appointment 10%～about 80%, 15%～about 50% (weight) detergent builder compound more preferably from about.But, be not the washing assistant that can not adopt lower or high level.

Inorganic or the detergent builder compound that contains P is including, but not limited to basic metal, (example has tri-polyphosphate to the polyphosphate of ammonium and alkanol ammonium, pyrophosphate salt and glass polymetaphosphate), phosphonate, phytate, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.But, require nonphosphate builders in certain areas.Importantly, even when having so-called " weak " washing assistant (comparing with phosphoric acid salt) as Citrate trianion, or under what is called " basis is strengthened " condition that occurs when using zeolite or lamellated silicate-like builder, the function of the present composition is good astoundingly.

The example of silicate-like builder is an alkalimetal silicate, is disclosed in the U.S.4 of the Rieck that announced on May 12nd, 1987,664,839.NaSKS-6 is the trade mark (generally abbreviating " SKS-6 " herein as) of the crystalline layered silicate of Hoechst sale.

The example of carbonate builders is alkaline-earth metal and alkaline carbonate, as is disclosed in the German patent application No.2 that announced on November 15th, 1973, the carbonate in 321,001.

The silico-aluminate washing assistant is epochmaking in the heavy duty type granular detergent composition of the most generally selling, and also is a kind of important washing assistant composition in the liquid detergent prescription.The silico-aluminate washing assistant comprises the compound that empirical formula is following:

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 1.0～about 0.5, and x is about integer of 15～about 264.The available name that can be used for preferred synthetic crystallization aluminosilicate ion exchange material herein is called zeolite A, zeolite P (B), zeolite MAP and X zeolite.

The organic washing-assisting detergent that is suitable for the object of the invention comprises various multi-carboxylate's compounds, but is not limited to this.When using herein, term " multi-carboxylate " is meant the compound with a plurality of carboxylate group, preferably has 3 carboxylate group at least.The multi-carboxy acid salt washing agent can join with the form of acid in the described composition usually, but also can add with the form of neutralized salt.When using with the form of salt, basic metal, sodium for example, potassium, and lithium, or alkanol ammonium salts is preferred.

Suitable multi-carboxy acid salt washing agent is disclosed in the U.S.3 of the Berg that announced on April 7th, 1964, the U.S.3 of the Lamberti that on January 18th, 128,287 and 1972 announced etc., 635, the U.S.4 of the Bush that on May 5th, 830,1987 announced etc., 663,071, the U.S.3 of the Rapko that on December 2nd, 1975 announced, 923,679; The U.S.4 of the Crutchfield that on June 19th, 1979 announced etc., 158,635; The U.S.4 of the Crutchfield that on October 17th, 1978 announced etc., 120,874; The U.S.4 of the Bush that on January 28th, 1986 announced, the U.S.4 of the Crutchfield that on March 13rd, 566,984,1979 announced etc., the U.S.3 of the Diehl that on March 7th, 144,226 and 1967 announced, 308,067, the U.S.P.3 of Diehl, 723,322, with the U.S.4 of the Crutchfield that announced on July 25th, 1978 etc., 102,903, also has U.S.P.3,159,581,3,213,030; 3,422,021; 3,400,148 and 3,422,137.

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 the particularly important of heavy duty liquid detergent prescription, because it can be obtained by renewable resources, and are biodegradable.Citrate trianion also can be used in the granular composition, particularly unites use with zeolite and/or layered silicate washing assistant.In this based composition and mixture, the oxygen disuccinate also is useful especially.Dispersion agent

The suitable polyalkyleneimine dispersants that other can be randomly disperses thing to be used in combination with bleach stable of the present invention is disclosed in the U.S.4 of the Vander Meer that announced on July 1st, 1986,597,898; Oh that on June 27th, 1984 announced and the european patent application 111,965 of Gosselink; The european patent application 111,984 of the Gosselink that on June 27th, 1984 announced; The european patent application 112,592 of the Gosselink that on July 4th, 1984 announced; The U.S.4 of the Connor that on October 22nd, 1985 announced, 548,744; With the U.S.5 of the Watson that announced on October 15th, 1996 etc., 565,145; All these patents are combined in herein as a reference.But, in laundry composition of the present invention, can use any suitable earth/dirt dispersion agent or anti redeposition agent.

In addition, comprise the suitable use in the present invention of polymeric dispersant of multi-carboxylate polymer and polyoxyethylene glycol.The polymeric polycarboxylic acid salt material can be by suitable polymerization of unsaturated monomers or the incompatible preparation of copolymerization, and described monomer is preferably with the form polymerization of acid.The unsaturated monomer acid that can polymerization forms suitable multi-carboxylate polymer comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, aconic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.In multi-carboxylate polymer described herein, also can there be the not monomer fragment of carboxylate-containing base, vinyl methyl ether for example, vinylbenzene, ethene etc., supplementary condition are that these fragments surpass about 40% of polymer weight.

Specially suitable multi-carboxylate polymer can be derived by vinylformic acid and obtain.The acrylic acid based polymer that can be used for herein is polyacrylic water-soluble salt.It is about 2,000～10,000 that the molecular-weight average of polymkeric substance of acid form is preferably, more preferably about 4,000～7,000, most preferably is about 4,000～5,000.Polyacrylic water-soluble salt like this can comprise for example basic metal, the salt of ammonium and replacement ammonium.This class soluble polymer is known material.This class polyacrylate application in detergent composition has been disclosed in for example U.S.P.3 of the Diehl of announcement on March 7th, 1967,308,067.

Vinylformic acid/maleic copolymer also can be as preferred dispersion/anti redeposition agent component.Such material comprises the water-soluble salt of vinylformic acid and maleic acid.The average molecular weight range of this multipolymer of acid form is preferably: be limited to approximately 2,000 down, preferred lower limit is about 5,000, more preferably be limited to down about 7,000, on be limited to 100,000, be limited to 75,000 on more preferably, be limited to 65,000 on most preferably.In this multipolymer, the segmental ratio of acrylate and maleate was generally about 30: 1～about 1: 1, more preferably from about 10: 1～2: 1.The water-soluble salt of this vinylformic acid/maleic acid for example can comprise, basic metal, the salt of ammonium and replacement ammonium.Such solubility acrylate/maleate copolymer is known material, it is disclosed in the european patent application No.66915 that announces December 15 nineteen eighty-two, and the EP 193,360 of announcement on September 3rd, 1986, the latter also discloses this polymkeric substance that comprises the hydroxypropyl acrylate.Other useful dispersion agent comprises toxilic acid/vinylformic acid/vinyl alcohol terpolymer.This material also is disclosed among the EP 193,360, comprises 45/45/10 terpolymer as vinylformic acid/toxilic acid/vinyl alcohol.

The another kind of polymkeric substance that can comprise is poly-7 glycol (PEG).PEG has dispersing agent performance, and can be used as earth dirt remover-anti redeposition agent.The typical molecular weight scope of the polymkeric substance that uses as this purpose for about 500～about 100,000, preferred about 1,000～about 50,000, more preferably from about 1,500～about 10,000.

Also can use polyaspartic acid salts and polyglutamic acid dipersant, particularly unite use with zeolite builders.Dispersion agent, for example the molecular weight of polyaspartic acid salts (on average) is preferably about 10,000.

Stain remover

Composition of the present invention can randomly contain one or more stain removers.If the use stain remover in the weight of composition, is limited to approximately 0.01% under the content of general stain remover, preferred lower limit is about 0.1%, more preferably be limited to down about 0.2%, on be limited to approximately 10%, preferred upper limit is about 5%, is limited to about 3% on more preferably.The feature of polymkeric substance stain remover is existing hydrophilic segment, makes the surface hydrophilic of hydrophobic fiber such as polyester and nylon, and hydrophobic fragment is arranged again, being deposited on the hydrophobic fiber, and on can both be attached to fiber in whole cycles of washing process, serves as the anchorage of hydrophilic segment.This just makes the dirt easier cleaning in the washing process of back after the detergent-treatment.

Below patent disclosure be suitable for stain remover of the present invention, these patents all are combined in herein as a reference: the U.S.5 of the Rohrbaugh that announced on March 17th, 1998 etc., 728,671; The U.S.5 of the Gosselink that on November 25th, 1997 announced etc., 691,298; The U.S.5 of the Pan that on February 4th, 1997 announced etc., 599,782; The U.S.5 of the Gosselink that announce May 16 nineteen ninety-five etc., 415,807; The U.S.5 of the Morrall that on January 26th, 1993 announced etc., 182,043; The U.S.4 of the Gosselink that announce September 11 nineteen ninety etc., 956,447; The U.S.4 of the Maldonado that announce December 11 nineteen ninety etc., 976,879; The U.S.4 of the Scheibel that announce November 6 nineteen ninety etc., 968,451; The U.S.4 of the Borcher Sr. that announce May 15 nineteen ninety etc., 925,577; The U.S.4 of the Gosselink that on August 29th, 1989 announced, 861,512; The U.S.4 of the Maldonado that on October 31st, 1989 announced etc., 877,896; The U.S.4 of the Gosselink that on October 27th, 1987 announced etc., 771,730; The U.S.711 of the Gosselink that on December 8th, 1987 announced etc., 730; The U.S.4 of the Gosselink that on January 26th, 1988 announced, 721,580; The U.S.4 of the Nicol that on December 28th, 1976 announced etc., 000,093; The U.S.3 of the Hayes that on May 25th, 1976 announced, 959,230; The U.S.3 of the Basadur that on July 8th, 1975 announced, 893,929; European patent application 0219048 with the Kud that announced on April 22nd, 1987 etc.

Also have, suitable stain remover is disclosed in the U.S.4 of Voilland etc., 201,824; The U.S.4 of Lagasse etc., 240,918; The U.S.4 of Tung etc., 525,524; The U.S.4 of Ruppert etc., 579,681; U.S.4,220,918; U.S.4,787,989; EP 279,134 A of Rhone-Poulenc Chemie, 1988; EP 457,205 A (1991) of BASF; DE 2,335,044,1974 with Unilever N.V.; All these patents are combined in herein as a reference.Enzyme

Washing of the present invention and cleaning compositions can also randomly contain one or more detersive enzymes.Proteolytic enzyme, amylase, cellulase and the lipase that can comprise other in such enzyme.These materials are known in this area, and can be commercially available with its trade(brand)name.These enzymes can be with suspension, and " marumes " or " particulate state " form is in conjunction with entering in the non-aqueous liquid detergent composition of the present invention.Another kind of suitable enzyme comprises the enzyme that those exist with the slurries form in nonionogenic tenside, the enzyme of the commodity " SL " by name of for example Novo Nordisk sale, or the micro encapsulation enzyme of the commodity " LDP " by name of NovoNordisk sale.Suitable enzyme and consumption thereof are disclosed in U.S.P.5, and 576,282,5,705,464 and 5,710,115.

Especially preferably the enzyme bead form of enzyme with routine joined in the composition of the present invention herein.The magnitude range of this bead is generally about 100～1,000 micron, and more preferably from about 200～800 microns, and be suspended in the whole non-aqueous liquid phase of composition.Enzyme bead in the present composition is compared with the enzyme of other form, aspect the long-term confining force of enzymic activity, demonstrates the enzyme stability of special needs.Therefore, use the composition of enzyme bead needn't contain conventional enzyme stabilizers, the enzyme stabilizers that often must use when enzyme being attached in the waterborne liquid washing composition.

But the enzyme that joins in the present composition can be a particle form, preferred T-particle form.

Used term " cleaning enzymes " among the present invention is meant anyly in clothing usefulness, has cleaning in hard-surface cleaning or the personal care detergent composition, the enzyme of decontamination or other beneficial effect.Preferred cleaning enzymes is a lytic enzyme, for example proteolytic enzyme, amylase and lipase.The enzyme of preferred laundry usefulness is including, but not limited to proteolytic enzyme, cellulase, lipase and peroxidase.The enzyme that highly preferred automatic bowl is used is amylase and/or proteolytic enzyme, comprises that present commercially available type and its improve type, although by constantly improving, they are more and more compatible with SYNTHETIC OPTICAL WHITNER, and they are inactivation under the SYNTHETIC OPTICAL WHITNER effect easily still.

The example of suitable enzyme is including, but not limited to hemicellulase, peroxidase, proteolytic enzyme, cellulase, zytase, lipase, Phospholipid hydrolase, esterase, at (cutinases), polygalacturonase, M-Zyme, reductase enzyme, oxydase, phenol oxidase, lipoxygenase, lignoenzyme (ligninases), Starch debranching enzyme, tannase, pentosanase, malanases, beta-glucanase, arabinofuranosidase/xylosidase, Unidasa, chondroitinase, laccase, with known amylase, or its mixture.

The example of the enzyme that this class is suitable is disclosed in U.S.P.5, and 705,464,5,710,115,5,576,282,5,728,671 and 5,707,950.

Be used for cellulase of the present invention and comprise bacterium or fungal cellulase.Preferably, their pH value optimum range is 5～12, and specific activity is greater than 50 CEVU/mg (Mierocrystalline cellulose viscosity unit).Suitable cellulase is disclosed in U.S.P.4, and 435,307, J61078384 and WO96/02653, these patent disclosures respectively by Humicola insolens, Trichoderma (Trichoderma), the fungal cellulase that Thielavia and Sporotrichum (Sporotrichum) produce.EP 739 982 discloses by separating the cellulase that obtains in the novel bacteria bacterial classification.Suitable cellulase also is disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and WO95/26398.

The example of the plain enzyme of this fibrid is by Humicola insolens (Humicola grisea var.thermoidea) bacterial strain, particularly the cellulase of Humicola strain DSM 1800 generations.

Other suitable cellulase is the cellulase that is derived from Humicola insolens, and molecular weight is about 50KDa, and iso-electric point is 5.5, and contains 415 amino acid; With a kind of Humicolainsolens that is derived from, DSM 1800～endoglucanase of the plain enzymic activity of the display fibers of 43 kD; A kind of aminoacid sequence of preferred endoglucanase component is disclosed in WO91/17243.Being disclosed in the EGIII cellulase that derives from Trichoderma longibrachiatum of the WO94/21801 of Genencor, also is suitable cellulase.Cellulase with benefit of protection color is specially suitable.The example of the plain enzyme of this fibrid is disclosed in No. the 91202879.2nd, the european patent application of submitting on November 6th, 1991 (Novo).Carezyme and Celluzyme (Novo Nordisk A/S) are particularly useful.Also can be referring to WO91/17244 and WO91/21801.Other suitable cellulase with fabric nursing and/or washing character is disclosed in WO96/34092, WO96/17994 and WO95/24471.

When having cellulase, the content that generally is combined in the pure enzyme in the cleaning compositions is 0.0001%～2% of cleaning compositions weight.

Other preferred enzyme that can be included in the cleaning compositions of the present invention comprises lipase.The suitable lipase that is used for washing composition comprises pseudomonas group's microorganism, and for example those lipase of being produced of Pseudomonasstutzeri ATCC 19.154 are disclosed in British Patent1,372,034.Suitable lipase comprises that those antibody to the lipase that produced by microorganism Pseudomonas fluorescentIAM 1057 show the report to the leadship after accomplishing a task lipase of reaction of positive immunology.This lipase can be by Amano Pharmaceutical Co.Ltd., Nagoya, and Japan obtains, and commodity are called lipase P " Amano ", after this are called " Amano-P ".Other suitable business-like lipase comprises Amano-CES, by Toyo Jozo Co., and Tagata, the Chromobacterviscosum that Japan obtains is as the lipase of Chromobacter viscosum var.lipolyticum NRRLB 3673 generations; By U.S.Biochemical Corp., U.S.A. and Disoynth Co., Chromobacter viscosum lipase that The Netherlands obtains and the lipase that produces as Pseudomonas gladioli.Specially suitable lipase is M1 Lipase for example ^RAnd Lipomax ^R(Gist-Brocades) and Lipolase ^RWith Lipolase Ultra ^R(Novo), the inventor finds that be very effective when they and combination of compositions of the present invention use.The EP 258 068 of Novo Nordisk, the WO94/03578 of WO92/05249 and WO95/22615 and Unilever, disclosed lipolytic enzyme also is suitable among WO95/35381 and the WO96/00292.

At [EC 3.1.1.50] also is suitable, and it is considered to a kind of special lipase, does not promptly require the lipase of interface activation.At for example WO-A-88/09367 (Genencor); The technical scheme that adds in cleaning compositions is disclosed among WO90/09446 (Plant Genetic System) and WO94/14963 and the WO94/14964 (Unilever).

When having lipase and/or at, the content that generally is combined in the pure enzyme in the cleaning compositions is 0.0001%～2% of cleaning compositions weight.

Except that the above-mentioned lipase of mentioning, Phospholipid hydrolase also can be incorporated in the cleaning compositions of the present invention.The non-limiting example of suitable Phospholipid hydrolase comprises: EC 3.1.1.32 phospholipase A1; EC 3.1.1.4 Phospholipase A2; EC 3.1.1.5 Lysopholipase; EC 3.1.4.3 Phospholipase C, EC 3.1.4.4 Phospholipase D.Commercially available Phospholipid hydrolase comprises the LECITASE by the Novo Nordisk A/S acquisition of Denmark ^And the Phospholipase A2 that obtains by Sigma.When in composition of the present invention, comprising Phospholipid hydrolase, preferably also comprise amylase.Although do not wish to be bound by theory, believe that Phospholipid hydrolase and diastatic compound action provide substantial soil-removing action, particularly for the fats/oils dirt, starch based, the stain of altitudinal belt look and argillous removal effect.When having Phospholipid hydrolase and amylase, the part by weight of the two pure enzyme in composition of the present invention is preferably 4500: 1～and 1: 5, more preferably 50: 1～1: 1.

Suitable proteolytic enzyme is subtilisin, and it can obtain (subtilisin BPN and BPN ') from specific bacterial strain B.Subtilis and B.licheniformis.A kind of suitable proteolytic enzyme derives from the Bacillus bacterial strain, all has maximum activity in 8～12 whole pH value scope, and by Novo Industries A/S (after this being called " the Novo ") exploitation and the sale of Denmark, commodity are called ESPERASE .The preparation of this enzyme and similar enzyme is disclosed in the GB 1,243,784 of Novo.Proteolytic ferment also comprises the bacterial serine proteolytic enzyme of modification, for example be disclosed in the european patent application submitted on April 28th, 1987 the 87 No. 303761.8 (particularly 17,24 and 98 pages) proteolytic enzyme, and this enzyme is called " proteolytic enzyme B " at this, european patent application 199 with the Venegas that is disclosed in the bacterial serine proteolytic ferment of submitting on October 29th, 1986 that relates to modification, 404 proteolytic enzyme, and this enzyme is called " protease A " at this.At this proteolytic enzyme that is called " proteolytic enzyme C " also is suitable, this enzyme is the variant that derives from the alkaline serine protease of Bacillus, wherein replaced arginine at 27 Methionins, replaced Xie Ansuan at 104 tyrosine, replaced l-asparagine at 123 Serines, replaced Threonine at 274 L-Ala.Proteolytic enzyme C is disclosed in EP 90915958:4, corresponding to the WO91/06637 that published on May 16th, 1991.The variant of the genetics modification of the variant of genetics modification, particularly proteolytic enzyme C is also included within this.

The preferred proteolytic enzyme that is called as " proteolytic enzyme D " is as being disclosed in U.S.P.5,677,272 and the carbonylic hydrolase of WO95/10591.The carbonylic hydrolase variant that is disclosed in the proteolytic enzyme of WO95/10591 also is suitable, and the aminoacid sequence of this enzyme is to obtain by a plurality of amino-acid residues of replacing pre-enzyme, and amino acid is replaced the site corresponding to+210, and in conjunction with replacing one or more following residues :+33 ,+62 ,+67, + 76 ,+100 ,+101, + 103 ,+104 ,+107, + 128 ,+129 ,+130, + 132, + 135 ,+156 ,+158, + 164, + 166 ,+167 ,+170, + 209, + 215 ,+217 ,+218, with+222, wherein Ji Shuo site is corresponding to the naturally occurring subtilisin that derives from bacillus amyloliquefaciens (Bacillusamyloliquefaciens), or at other carbonylic hydrolase or subtilisin, for example bacillus lentus (Bacillus lentus) subtilisin (undelegated patent application US60/048,550, be filed in the corresponding amino-acid residue on June 4th, 1997 and the PCT International Application PCT/IB98/00853).

Be disclosed in the proteolytic enzyme of patent application EP 251 446 and WO91/06637, be disclosed in the proteolytic enzyme BLAP of WO91/02792 ^, and their variant that is disclosed in WO95/23221, also be applicable to the present invention.

Be also shown in a kind of high pH value proteolytic enzyme, derive from Bacillus sp.NCIMB 40338, be disclosed in the WO93/18140 A of Novo.The WO92/03529 A of Novo discloses the washing composition that contains enzyme, comprises proteolytic enzyme, one or more other enzymes and a kind of reversible proteinase inhibitor.When needs, can obtain to have the water-disintegrable proteolytic enzyme of the adsorption and the increase of reduction, be disclosed in Procter﹠amp; The WO95/07791 of Gamble.A kind of proteolytic enzyme recombinant chou of the trypsin-like that is used for washing composition herein that is applicable to is disclosed in the WO94/25583 of Novo.Other suitable proteolytic enzyme is disclosed in the EP 516 200 of Unilever.

Useful especially proteolytic enzyme is disclosed in PCT application: WO95/30010; WO95/30011; And WO95/29979.Suitable proteolytic enzyme is commercially available, and commodity are called ESPERASE ^, ALCALASE ^, DURAZYM ^, SAVINASE ^, EVERLASE ^And KANNASE ^, these all are the Novo Nordisk A/S acquisitions from Denmark, and MAXATASE ^, MAXACAL ^, PROPERASE ^And MAXAPEM ^, these can obtain from Genencor International (before Dutch Gist-Brocades).

When having these proteolytic ferments, the content that is combined in the pure enzyme in the cleaning compositions of the present invention is 0.0001%～2% of composition weight, and is preferred 0.001%～0.2%, more preferably 0.005%～0.1%.

Composition of the present invention can comprise amylase (α and/or β), to remove the carbohydrate-based stain.WO94/02597 discloses and has comprised the diastatic cleaning compositions of sudden change.Also can be referring to WO95/10603.Other amylase that becomes known for cleaning compositions comprises α-and beta-amylase.α-Dian Fenmei is known in the art, and comprises and be disclosed in U.S.Pat.5,003,257; EP 252,666; WO/91/00353; FR 2,676, and 456; EP 285,123; EP 525,610; EP 368,341; With british patent specification 1,296, those amylase among 839 (Novo).Other suitable amylase is disclosed stability-enhanced amylase among WO94/18314 and the WO96/05295 (Genencor), with the amylase variant of disclosed other modification among the WO95/10603, the direct parent of this amylase variant can be obtained by Novo Nordisk A/S.Disclosed amylase also is suitable among the EP 277 216.

The example of business-like α-Dian Fenmei product is can be by the Purafect OxAm of Genencor acquisition ^With the Termamyl that can obtain by the Novo Nordisk A/S of Denmark ^, Ban ^, Fungamyl ^And Duramyl ^WO95/26397 discloses other suitable amylase: α-Dian Fenmei is characterized in that in 25 ℃～55 ℃ temperature range, in 8～10 pH value scope, its specific activity compares Termamyl ^Specific activity high at least by 25%, described specific activity is by Phadebas ^The alpha-amylase activity analytical procedure is measured.The variant of disclosed above-mentioned enzyme also is suitable among the WO96/23873 (Novo Nordisk).Other amylolytic enzyme that improves in the combined aspects performance of activity level and thermostability and high reactivity level is disclosed in WO95/35382.

When having these amylolytic enzymes, the content that is combined in the pure enzyme in the cleaning compositions of the present invention is 0.0001%～2% of composition weight, is preferably 0.00018～0.06%, more preferably 0.00024%～0.048%.

Above-mentioned enzyme can derive from any suitable source, for example plant, animal, bacterium, fungi and yeast.The source can also be mesophile or extremophilic (have a liking for cold bacterium, suitable cold bacterium, thermophile bacteria, barophilic bacteria is had a liking for the alkali bacterium, acidophilic bacteria, halophilic bacterium etc.).The form purifying of these enzymes or non-purifying can be used.Now, in order to make the impact of performance optimizing of enzyme in laundry detergent of the present invention and/or Fabrid care composition, by protein/gene engineering wild-type enzyme is carried out modification usually.For example, can design described variant, enzyme is improved to the consistency of the composition that often runs in this based composition.Perhaps, can design described variant, make the optimal ph of enzyme variants, bleaching or chelate stability, catalytic activitys etc. are cut into and are fit to specific cleaning applications.

Especially, when considering bleach stability, the susceptibility of amino acid should be noted, when considering surfactant compatibility, surface charge should be noted oxidizing reaction.This zymoid iso-electric point can change by substituting some charged amino acid, for example improves iso-electric point and helps to improve consistency with anion surfactant.By producing for example additional salt bridge and strengthening the calcium bonding point, can further improve the stability of enzyme to improve chelate stability.

When having these optional cleaning enzymes, the content that generally is combined in the pure enzyme in the cleaning compositions is 0.0001%～2% of cleaning compositions weight.Described enzyme can be used as independent component (bead that contains a kind of enzyme, particle, stable forms such as liquid) and adds, or adds with mixture (for example granulation altogether) form of two or more enzymes.

Other suitable detergent ingredients that can add is an oxydasis reaction scavenging agent.The example of this kind of enzyme oxidizing reaction scavenging agent is ethoxyquin four ethylidene polyamines.

Some enzyme materials and the mode in the synthetic detergent composition of being incorporated into thereof also are disclosed in WO9307263 and the WO9307260 of Genencor International, the U.S.3 of WO8908694 and McCarty etc., on January 5th, 553,139,1971.Enzyme also is disclosed in U.S.4, and 101,457 and U.S.4,507,219.U.S.4,261,868 disclose for the useful enzyme material of liquid detergent formula, and the combination in these prescriptions.

Amylase is adapted at using in the composition of the present invention.In the present invention amylase of Shi Yonging and variant including, but not limited to, be disclosed in the amylase among WO95/26397 and the WO96/23873 (Novo).Weight in cleaning compositions, be incorporated under the pure enzyme content of these enzymes in the cleaning compositions and be limited to about 0.0001%, preferred lower limit is about 0.00018%, more preferably be limited to about 0.00024% down, most preferably be limited to about 0.05% down, on be limited to approximately 0.1%, preferred upper limit is about 0.060%, is limited to about 0.048% on more preferably.

Amylase variant is preferably selected from alpha-amylase variants.

Be used for suitable alpha-amylase variants of the present invention including, but not limited to following α-Dian Fenmei:

(i) α-Dian Fenmei is characterized in that, in 25 ℃～55 ℃ temperature range, 8～

In 10 the pH value scope, its specific activity compares Termamyl ^Specific activity high at least by 25%, institute

State specific activity by Phadebas ^The alpha-amylase activity analytical procedure is measured, and/or;

(ii), contain the aminoacid sequence that shows among the SEQ ID No.1 according to the α-Dian Fenmei of (i),

Or the α-Dian Fenmei identical with the aminoacid sequence that shows at least 80% among the SEQ ID No.1 and

/ or:

(iii), contain the amino acid preface that shows among the SEQ ID No.2 according to the α-Dian Fenmei of (i)

Row, or the Alpha-starch identical with the aminoacid sequence that shows at least 80% among the SEQ ID No.2

Enzyme, and/or:

(iv) according to the α-Dian Fenmei of (i), contain following amino acid sequences: His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp (SEQ ID No.3) at the N-end, or N-end with shown in the identical α-Dian Fenmei of aminoacid sequence (SEQ ID No.3) at least 80%, and/or:

(v) according to the α-Dian Fenmei of (i-iv), wherein α-Dian Fenmei derives from the bacillus category of having a liking for alkali, and/or;

(vi) according to (α-Dian Fenmei v), wherein amylase derives from NCIB 12289, NCIB12512 is any in NCIB 12513 and DSM 935 bacterial strains, and/or;

(vii) α-Dian Fenmei, to aminoacid sequence respectively corresponding to SEQ ID No.1, ID No.2, or the antibody of the α-Dian Fenmei of ID No.3 demonstrates positive immunological cross-reaction, and/or;

(the viii) variant of parent α-Dian Fenmei, wherein parent α-Dian Fenmei (1) has SEQ ID No.1, ID No.2, one of or the aminoacid sequence shown in the ID No.4 difference, or (2) demonstrate identical with described one or more aminoacid sequence at least 80%, and/or the antibody of α-Dian Fenmei with one of described aminoacid sequence demonstrated immunological cross-reaction, and/or by a kind of like this dna sequence encoding, this dna sequence dna is hybridized with making the α-Dian Fenmei coded DNA sequence same probe with one of described aminoacid sequence, and variant wherein: (A) at least one amino-acid residue of described parent α-Dian Fenmei is deleted; And/or (B) at least one amino-acid residue of described parent α-Dian Fenmei is replaced by different amino-acid residue; And/or (C) at least one amino-acid residue is inserted in the described parent α-Dian Fenmei; Described variant has alpha-amylase activity, and with respect to described parent α-Dian Fenmei, shows at least one following performance: the enhanced thermostability; The enhanced oxidative stability; The Ca ion dependence that reduces; Enhanced stability and/or Alpha-starch hydrolytic activity in neutrality arrives high relatively pH value scope; Enhanced Alpha-starch hydrolytic activity under high relatively temperature; With the iso-electric point (pI) that improves or reduce, so that the pI value of alpha-amylase variants is mated with the pH value of medium better.

If by for example Lipman and Pearson, Science 227,1985, p.1435 disclosed algorithm is carried out computing in, come comparison polypeptide and parent amylase aminoacid sequence separately, demonstrating identity is X%, and then polypeptide is considered to similar with parent amylase X%.

In the present invention, term " by ... obtain ", not only be meant amylase, also refer to use from this Bacillus strain and separate the amylase that produces in the amylase of the dna sequence encoding that obtains and the main body organism that this dna sequence dna is transcribed by Bacillus strain preparation.Enzyme stabilizers

The enzyme that is used for washing composition can be stablized by various technology.U.S.3,600,319, EP199,405 and EP 200,586 in open and illustrated the enzyme stabilization technique.The enzyme stabilising system also is disclosed in for example U.S.3,519,570.Disclose among the WO9401532 and can provide proteolytic enzyme, a kind of useful genus bacillus of zytase and cellulase, sp.AC 13.The enzyme that uses among the present invention can be stable by the water miscible calcium ion and/or the magnesium ion source that exist in final composition, and final composition offers enzyme with these ions.Suitable enzyme stabilizers and consumption are disclosed in U.S.P.5, and 705,464,5,710,115 and 5,576,282.

Be the non-limiting example of preparation bleaching catalyst below, this bleaching catalyst can be bleached color spot effectively lacking under the condition of peroxide source.

Manganese (II) is closed in the chlorination that embodiment 1 synthetic chemistry formula is following (5,12-dimethyl-1,5,8,12-four aza-bicyclos [6.6.2] n-Hexadecane):

To thermometer is housed, in 3 mouthfuls of round-bottomed flasks of the 250mL of nitrogen conduit and magnetic stirrer, add N, N '-two (2-aminoethyl)-l, the 3-propylene diamine (5.00g, 31.3mmol) and dehydrated alcohol (100mL).This solution stirs under argon atmospher and uses ice bath to be cooled to 15 ℃.Under agitation drip glyoxal water solution (4.78g, 33mmol, 40% the aqueous solution).After being added dropwise to complete, decompression concentrated solution obtains water white oily matter at once.Separate the oily matter that obtains Chemical formula 1:

And productive rate is 100% (6.0g).

Cyclammonium 1 (6.0g) is suspended in the acetonitrile (100mL).Add salt of wormwood (25g) and 1, and the ammediol xylene sulfonate (12.61g, 32.8mmol).This solution at room temperature vigorous stirring spends the night.Then this reactant is heated to 70 ℃, and carries out heat filtering with glass fiber filter paper and vacuum filter.The solid that obtains washs with acetonitrile (100mL).Concentrating under reduced pressure acetonitrile filtrate obtains the light green oily matter of Chemical formula 2: And productive rate is 100% (7.0g).

Tetramine 2 (7.0g) is dissolved in the acetonitrile (150mL).Add methyl sulfate (2.5 equivalent), reactant is heated to 65 ℃ and stirred 9 days.Removal of solvent under reduced pressure obtains the brown oil of chemical formula 3:

And productive rate is about 85%.

In the 250mL round-bottomed flask, add distilled water (25mL) and salt of wormwood (13.8g).Add dehydrated alcohol (75mL), stir the two phase liquid that obtains and be heated to 60 ℃ with oil bath.In solution, add sodium borohydride (1.60g, 42.3mmol) and 3 (10.0g, 21.1mmol).This is reflected at 60 ℃ and stirred 75 minutes.This reaction mixture is placed separating funnel and collects alcohol layer.Removal of solvent under reduced pressure then is dissolved in the brown solid/oily matter that obtains among the 5N KOH (5mL) and with toluene extraction (2 * 50mL).The decompression remove toluene, obtain chemical formula following 5,12-dimethyl-1,5,8,12-four aza-bicyclos [6.6.2] n-Hexadecane oily matter:

Distillation back productive rate is 95% (5.2g).

To heating mantles is housed, in the dry 12 liters of 3 mouthfuls of round-bottomed flasks crossing of the flame of the condenser that stirring rod and oven drying are crossed, add anhydrous acetonitrile (5L) and obtain 5,12-dimethyl-1,5,8,12-four aza-bicyclos [6.6.2] n-Hexadecane (484gm., 1.9moles).This milk-white coloured suspension is placed under the 10mm vacuum up to the suspension boiling, use the argon cleaning reactor then.This degasification process is carried out 7 times.After the degassing is finished, and adding Manganous chloride tetrahydrate (II) (228gm, 1.81moles).Under vigorous stirring, behind the backflow 4h, at once this suspension is passed through the glass filter paper filtering.Remove solvent in the filtrate 45 ℃ of decompressions, obtain solid.Then with this solid suspension in 500ml toluene, and decantation supernatant liquid.Repeat this washing process until supernatant liquid colourless (being generally 7 times) with about 7 * 500ml toluene.Dry remaining solid obtains 575g (84%) chlorination (5,12-dimethyl-1,5,8,12-four aza-bicyclos [6.6.2] n-Hexadecane) and closes manganese (II) under vacuum.By further washing solid material, handle the solid that obtains with similar fashion subsequently, obtain second batch of product.Overall yield is 636g (93%).

Be the non-limiting example of heavy duty type liquid of the present invention (HDL) laundry detergent compositions below:

Table I

Weight %

Composition	????2	????3	????4	????5
Composition	????2	????3	????4	????5	????C ₁₄-C ₁₅Alkyl E1.0 vitriol	????22.5	????22.5	????22.5	????22.5
Linear alkyl benzene sulfonate	????3.0	????3.0	????3.0	????3.0	????C ₁₄-C ₁₅Alkyl E1.0 vitriol	????22.5	????22.5	????22.5	????22.5
Linear alkyl benzene sulfonate	????3.0	????3.0	????3.0	????3.0	????C ₁₀Amido propyl group DMA	????1.5	????1.5	????1.5	????1.5
????C ₁₂-C ₁₄Alkyl E7.0	????3.0	????3.0	????3.0	????3.0	????C ₁₀Amido propyl group DMA	????1.5	????1.5	????1.5	????1.5
????C ₁₂-C ₁₄Alkyl E7.0	????3.0	????3.0	????3.0	????3.0	Citric acid	????2.5	????2.5	????2.5	????2.5
????C ₁₂-C ₁₈Alkyl fatty acid	????3.5	????3.5	????3.5	????3.5	Citric acid	????2.5	????2.5	????2.5	????2.5
????C ₁₂-C ₁₈Alkyl fatty acid	????3.5	????3.5	????3.5	????3.5	Semen Brassicae campestris lipid acid	????5.0	????5.0	????5.0	????5.0
Proteolytic enzyme	????0.8	????1.57	????1.57	????1.57	Semen Brassicae campestris lipid acid	????5.0	????5.0	????5.0	????5.0
Proteolytic enzyme	????0.8	????1.57	????1.57	????1.57	Amylase	????0.055	????0.088	????0.088	????0.088
Cellulase	????0.188	????0.055	????0.055	????0.055	Amylase	????0.055	????0.088	????0.088	????0.088
Cellulase	????0.188	????0.055	????0.055	????0.055	Lipase	????0.06	????-	????-	????-
Mannase	????0.007	????0.0033	????0.0033	????0.0033	Lipase	????0.06	????-	????-	????-
Mannase	????0.007	????0.0033	????0.0033	????0.0033	Sodium metaborate	????2.0	????2.5	????2.5	????2.5
Calcium formiate/CaCl ₂	????0.02	????0.10	????0.10	????0.10	Sodium metaborate	????2.0	????2.5	????2.5	????2.5
Calcium formiate/CaCl ₂	????0.02	????0.10	????0.10	????0.10	Bleaching catalyst ¹	????0.035	????0.034	????0.034	????0.034
Antioxidant ²	????0.23	????0.25	????0.25	????0.25	Bleaching catalyst ¹	????0.035	????0.034	????0.034	????0.034
Antioxidant ²	????0.23	????0.25	????0.25	????0.25	Reductive agent ³	????0.02	????--	????--	????--
Reductive agent ⁴	????--	????--	????0.0042	????0.0083	Reductive agent ³	????0.02	????--	????--	????--
Reductive agent ⁴	????--	????--	????0.0042	????0.0083	Hydrophobic dispersants ⁵	????0.65	????0.76	????0.76	????0.76
Stain remover ⁶	????0.147	????--	????--	????--	Hydrophobic dispersants ⁵	????0.65	????0.76	????0.76	????0.76
Stain remover ⁶	????0.147	????--	????--	????--	Stain remover ⁷	????--	????0.10	????0.10	????0.10
Suds suppressor	????0.60	????0.60	????0.60	????0.60	Stain remover ⁷	????--	????0.10	????0.10	????0.10
Suds suppressor	????0.60	????0.60	????0.60	????0.60	Water and micro substance	Surplus	Surplus	Surplus	Surplus

1. manganese (II) is closed in chlorination (5,12-dimethyl-1,5,8,12-four aza-bicyclos [6.6.2] n-Hexadecane).2. Yoshinox BHT.3. inclined to one side Potassium hydrogen sulfite.4. potassium sulfite.5. according to the U.S.P.4 of the Vander Meer that announced on July 1st, 1986,597,898 PEI 189 E15-18.6. according to the U.S.P.4 of the Gosselink that announced on October 27th, 1987,702,857 stain remover.7. according to the U.S.P.4 of the Scheibel that announces November 6 nineteen ninety etc., 968,451 stain remover.

Table II

Weight %

Composition	????6	????7	?????8	????9
Composition	????6	????7	?????8	????9	?C ₁₄-C ₁₅Alkyl E1.0 vitriol	????22.5	????22.5	?????--	????--
?C ₁₂-C ₁₅Alkyl E1.8 vitriol	????--	????--	?????23.5	????23.5	?C ₁₄-C ₁₅Alkyl E1.0 vitriol	????22.5	????22.5	?????--	????--
?C ₁₂-C ₁₅Alkyl E1.8 vitriol	????--	????--	?????23.5	????23.5	Linear alkyl benzene sulfonate	????3.0	????3.0	?????3.0	????3.0
???C ₁₀Amido propyl group DMA	????1.5	????1.5	?????--	????--	Linear alkyl benzene sulfonate	????3.0	????3.0	?????3.0	????3.0
???C ₁₀Amido propyl group DMA	????1.5	????1.5	?????--	????--	???C ₁₂-C ₁₄Alkyl E7.0	????3.0	????3.0	?????2.0	????2.0
Citric acid	????2.5	????2.5	?????2.5	????2.5	???C ₁₂-C ₁₄Alkyl E7.0	????3.0	????3.0	?????2.0	????2.0
Citric acid	????2.5	????2.5	?????2.5	????2.5	Sodium sulfate	????--	????--	?????1.75	????1.75
???C ₁₂-C ₁₈Alkyl fatty acid	????3.5	????3.5	?????5.0	????5.0	Sodium sulfate	????--	????--	?????1.75	????1.75
???C ₁₂-C ₁₈Alkyl fatty acid	????3.5	????3.5	?????5.0	????5.0	Semen Brassicae campestris lipid acid	????5.0	????5.0	?????6.5	????6.5
Proteolytic enzyme	????1.57	????1.57	?????1.57	????1.57	Semen Brassicae campestris lipid acid	????5.0	????5.0	?????6.5	????6.5
Proteolytic enzyme	????1.57	????1.57	?????1.57	????1.57	Amylase	????0.088	????0.088	?????0.088	????0.088
Cellulase	????0.055	????0.055	?????0.055	????0.055	Amylase	????0.088	????0.088	?????0.088	????0.088
Cellulase	????0.055	????0.055	?????0.055	????0.055	Mannase	????0.0033	????0.0033	?????0.0033	????0.0033
Sodium metaborate	????2.5	????2.5	?????2.5	????2.5	Mannase	????0.0033	????0.0033	?????0.0033	????0.0033
Sodium metaborate	????2.5	????2.5	?????2.5	????2.5	Calcium formiate/CaCl ₂	????0.10	????0.10	?????0.10	????0.10
Bleaching catalyst ¹	????0.034	????0.004	?????0.04	????0.04	Calcium formiate/CaCl ₂	????0.10	????0.10	?????0.10	????0.10
Bleaching catalyst ¹	????0.034	????0.004	?????0.04	????0.04	Antioxidant ²	????0.25	????0.025	?????0.25	????0.25

Reductive agent ³	????--	????--	????0.01	???--
Reductive agent ³	????--	????--	????0.01	???--	Reductive agent ⁴	????0.0083	????0.001	????--	???0.01
Hydrophobic dispersants ⁵	????0.76	????0.76	????1.20	???1.20	Reductive agent ⁴	????0.0083	????0.001	????--	???0.01
Hydrophobic dispersants ⁵	????0.76	????0.76	????1.20	???1.20	Stain remover ⁶	????--	????--	????--	???--
Stain remover ⁷	????0.10	????0.10	????0.10	???0.10	Stain remover ⁶	????--	????--	????--	???--
Stain remover ⁷	????0.10	????0.10	????0.10	???0.10	Suds suppressor	????0.60	????0.60	????0.60	???0.60
Water and micro substance	Surplus	Surplus	Surplus	Surplus	Suds suppressor	????0.60	????0.60	????0.60	???0.60

Claims

1. bleaching composition comprises:

Title complex with the large-scale many ring parts of cross-bridge;

B) effective amount of stabilizer, described stablizer is selected from:

I) one or more antioxidants;

Ii) one or more reductive agents;

Iii) reach their mixture; With

2. according to the composition of claim 1, wherein said transition metal bleach catalyzer comprises: i) a kind of transition metal is selected from 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), and composition thereof; Ii) with 4 or 5 the large-scale many ring parts of a kind of cross-bridge of giving electronic atom and same transition-metal coordination, described part comprises:

A) a kind of organic macrocycle, this ring contain 4 or a plurality of electronic atom of giving, described giving

Sub-atom is each other by 2 or 3 non-covalency connection branches that constitute to electronic atom

Open, wherein give the same transition metal in electronic atom and the title complex for 2～5

Atomic coordinate;

B) at least 2 non-adjacent electronics of giving on a kind of cross-bridge chain, itself and organic macrocycle are former

Son is covalently bound, described covalently bound non-adjacent be end of the bridge to electronic atom

Give electronic atom, same transition-metal coordination in itself and the title complex, and wherein

Described cross-bridge chain contains 2～about 10 atoms;

C) randomly, one or more non-large-scaled many ring parts are preferably selected from H ₂O, ROH,

NR ₃，RCN，OH ^-，OOH ^-，RS ^-，RO ^-，RCOO ^-，OCN ^-，SCN ^-，N ₃ ^-，

CN ^-, F ^-, Cl ^-, Br ^-, I ^-, O ₂ ^-, NO ₃ ^-, NO ₂ ^-, SO ₄ ^2-, SO ₃ ^2-, PO ₄ ^3-, organophosphorus

Acid group, the organic phosphine acid group, the organosulfur acid group, organic sulfonic acid root and fragrant N give

Electron, pyridine for example, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, pyrimidine,

Triazole and thiazole, wherein R is H, the optional alkyl that replaces, the optional virtue that replaces

Base.

3. according to the composition of claim 1 or 2, wherein said organic macrocycle contains at least 4 electronic atoms of giving for N, the described electronic atom of giving is connected separately by 2～4 non-covalency that constitute to electronic atom each other, and is described to electronic atom and same transition metal atoms coordination.

4. according to the composition of claim 1, it contains the transition metal bleach catalyzer at least about 1ppb.

5. according to the composition of claim 1, wherein said transition metal bleach catalyzer is that manganese (II) is closed in chlorination (5,12-dimethyl-1,5,8,12-four aza-bicyclos [6.6.2] n-Hexadecane).

6. according to the composition of claim 1, wherein said stablizer is an antioxidant, is selected from 2,6 di t butyl phenol, 2,6 di tert butyl 4 methyl phenol, the mixture of 2-and the 3-tertiary butyl-4-methoxyphenol, 5-hydroxyl-2,2,4,6,7-pentamethyl--2,3-dihydro-1-cumarone-3-ketone, 5-hydroxyl-3-methylene radical-2,2,4,6,7-pentamethyl--2,3-dihydro-cumarone, 5-benzyloxy-3-methylol-2,2,4,6,7-pentamethyl--2,3-dihydro-1-cumarone, 3-methylol-5-methoxyl group-2,2,4,6,7-pentamethyl--2,3-dihydro-1-cumarone, and composition thereof.

7. according to the composition of claim 1, wherein said stablizer is a reductive agent, is selected from S-WAT, potassium sulfite and composition thereof.

8. liquid laundry, laundry pre-soaking, or pretreated composition comprise:

Title complex with the large-scale many ring parts of cross-bridge;

B) effective amount of stabilizer, described stablizer is selected from:

I) one or more antioxidants;

Ii) one or more reductive agents;

Iii) reach their mixture; With

9. composition according to Claim 8, wherein said catalyzer comprises: i) a kind of transition metal is selected from 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) and; The large-scale many ring parts of ii) a kind of cross-bridge, described part is selected from:

A) have the large-scale many ring parts of the cross-bridge of formula (I) of 4 or 5 dentates:

C) have the large-scale many ring parts of the cross-bridge of formula (III) of 6 or 7 dentates:

Wherein the following fragment of general formula is represented in each E unit:

(CR _n) _a-X-(CR _n) _a′

Wherein X is selected from oxygen, sulphur, and-NR-, phosphorus, or X represents covalent linkage, and wherein the general formula of E is:

(CR _n) _a-(CR _n) _a′

For each E unit, a+a ' and be independently selected from 1～5; Each G unit is (a CR _n) _bFragment; Each R unit is independently selected from H, alkyl, thiazolinyl, alkynyl, aryl, alkaryl and heteroaryl, or the covalently bound formation aromatic ring in two or more R unit, hetero-aromatic ring, cycloalkyl ring or heterocycloalkyl ring; Each D unit is one and gives electronic atom, is independently selected from nitrogen, oxygen, and sulphur and phosphorus, and at least two unitary atoms of formation D are to give electronic atom with the end of the bridge of transition-metal coordination; The B unit is a carbon atom, a D unit, or cycloalkyl ring or heterocycloalkyl ring; Each n is independently selected from 1 and 2 integer, satisfies the valency of the covalently bound carbon atom in R unit; Each n ' is independently selected from 0 and 1 integer, satisfies the valency that the covalently bound D of R fragment gives electronic atom; Each n " is to be independently selected from 0,1 and 2 integer, satisfies the valency of the covalently bound B atom of R fragment; Each a and a ' are independently selected from 0～5 integer, wherein in the part of formula (I), all a+a ' values and scope be about 8～about 12; In the part of formula (II), all a+a ' values and scope be about 10～about 15; In the part of formula (III), all a+a ' values and scope be about 12～about 18; Each b is independently selected from 0～9 integer, or in above-mentioned any one general formula, as long as in general formula, have two (CR at least _n) _bTwo D are covalently bound on the B atom to electronic atom, then covalently bind in the interatomic one or more (CR of D and B _n) _bFragment can not exist, and all b values and in about 2～about 5 scopes; With

D) randomly, one or more non-large-scaled many ring parts.

10. according to the composition of claim 9, wherein said catalyzer contains non-large-scaled many ring parts, and this part is selected from H ₂O, ROH, NR ₃, RCN, OH ^-, OOH ^-, RS ^-, RO ^-, RCOO ^-, OCN ^-, SCN ^-, N ₃ ^-, CN ^-, F ^-, Cl ^-, Br ^-, I ^-, O ₂ ^-, NO ₃ ^-, NO ₂ ^-, SO ₄ ^2-, SO ₃ ^2-, PO ₄ ^3-, the organophosphorus acid group, the organic phosphine acid group, the organosulfur acid group, organic sulfonic acid root and fragrant N electron donor, pyridine for example, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, pyrimidine, triazole and thiazole, wherein R is H, the optional alkyl that replaces, the optional aryl that replaces.

11. the dirt on the bleached woven fabric and the method for color spot, described method comprise the step that fabric that needs are cleaned contacts with water-based or non-aqueous solution, described solution contains the composition that comprises following component:

Title complex with the large-scale many ring parts of cross-bridge;

B) effective amount of stabilizer, described stablizer is selected from:

I) one or more antioxidants;

Ii) one or more reductive agents;

Iii) reach their mixture; With