CN1384870A

CN1384870A - Method of bleaching stained fabrics

Info

Publication number: CN1384870A
Application number: CN00815030A
Authority: CN
Inventors: M·G·J·德尔罗伊泽; D·A·R·琼斯; R·G·史密斯; J·F·维尔斯
Original assignee: Unilever NV
Current assignee: Unilever NV
Priority date: 1999-09-01
Filing date: 2000-08-04
Publication date: 2002-12-11
Also published as: WO2001016269A1; EP1208187A1; CA2382115A1; AU7272000A

Abstract

A method for bleaching stained fabrics is provided by washing a stained fabric in an aqueous wash liquor in the presence of a wash additive that comprises a ligand that forms a transition metal complex as bleach catalyst, the complex catalysing bleaching of stains by atmospheric oxygen. The wash additive preferably comprises an iron complex comprising the ligand N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane. One or both of the wash additive and the wash liquor are substantially devoid of peroxygen bleach or a peroxy-based or peroxy-generating bleach system. The wash additive provides improved or broader stain profile bleaching.

Description

The bleaching method of stained fabrics

Invention field

The present invention relates to a kind of method that is used to bleach stained fabrics, more specifically, described method is a kind of in the presence of the detergent additive that comprises organic ligand (forming the transition metal complex as bleaching catalyst), the method for washing stained fabrics in aqueous cleaning solution.The invention still further relates to described part or complex compound as detergent additive, add in the aqueous cleaning solution purposes to spot on the bleached woven fabric.

Background of invention

EP-A-0909809 discloses the iron complex compound that a class can be used as the bleach activating catalyzer of peralcohol, comprise the various part N that comprise, two (pyridines-2-base-methyl)-1 of N-, the iron complex of two (pyridine-2-the yl)-1-ethylamines (being also referred to as MeN4Py) of 1-.It is said that these catalyzer can be used for comprising in the bleach system of peralcohol or its precursor, as be used for the washing of various dirt-carrying bodies and bleaching (comprise laundry, wash dish and hard surface cleans), or in textiles, paper and wood pulp industry and in wastewater treatment, be used for bleaching.

In our copending application PCT/GB99/02876, described and in water-bearing media, adopted metal coordination complex, with the method for the various dirt-carrying bodies of atmosphericoxygen catalytically bleaching as the catalytically bleaching agent.It is said that these methods specifically can be applicable to the bleaching of laundering of textile fabrics, are applicable to detergent formulations, the association with pulp bleaching, process hides, dyestuff transmission inhibition, food processing, the starch that also can be used for simultaneously in hard surface cleaning, wastewater treatment, the papermaking are bleached, sterilize, are brightened in oral hygiene composition and/or contact lens disinfection.

Yet, still need various bleachings the improving one's methods of laundering of textile fabrics of getting dirty.Therefore wish and to implement improved bleaching to the spot of various particular types.Also wish simultaneously and can implement more effective bleaching the outward appearance of the spot kind of wider scope.

Brief summary of the invention

We have now found that: according to the present invention, by using specified part or transition metal complex bleaching catalyst, add the spot outward appearance bleaching that the aqueous cleaning solution that is used for the spot on the bleached woven fabric can be realized improved or wider scope to as detergent additive.

Therefore, in first aspect, the invention provides a kind of method of bleached woven fabric spot, this method is included under the existence of detergent additive, washs stained fabrics in aqueous cleaning solution, wherein:

Described detergent additive comprises the part that forms complex compound with transition metal, and described complex compound is by atmosphericoxygen catalytically bleaching spot; With

In described detergent additive and the described washings one or both are substantially free of peroxygen bleach or peroxy or produce the bleach system of peroxide.

In second aspect, the invention provides the purposes that forms the part of complex compound with transition metal, described complex compound is by atmosphericoxygen, catalytically bleaching spot add in order to the carrier in the aqueous cleaning solution of the spot on the bleached woven fabric as detergent additive on.

Preferred described part is N, two (pyridines-2-base-methyl)-1 of N-, and two (pyridine-2-the yl)-1-ethylamines of 1-, and described complex compound is an iron complex.

We find: can make in the washings by described part or complex compound are joined as detergent additive that the spot of some type obtains more effective bleaching on the stained fabrics.Therefore, by being joined, described detergent additive can improve the bleaching that various oil-dirts (as the tomato spot) are carried out in the described washings.Spot for the type, can have maybe in described detergent additive not to have, and can have maybe at described washings and can not have bleach system (but not having in the preferred described washings) peroxygen bleach (as hydrogen peroxide) or peroxy or that produce peroxide.Also can improve the bleaching that the tea spot is carried out by adding described detergent additive.For the spot of the type, as described in bleach system peroxygen bleach (as hydrogen peroxide) or peroxy or that produce peroxide should be present in detergent additive and as described in the washings one or both, and preferably be present in the described detergent additive.

In order to provide more effective bleachability, preferably in described detergent additive, there is the bleach system of peroxygen bleach or peroxy or generation peroxide, but do not have these materials in the described washings various dissimilar spots.We should recognize that in case described detergent additive is joined in the described washings, then various substance (part or complex compound as described) and peroxygen bleach (if present) will migrate in the described washings medium.

Can use be easy to carry out the spot bleaching or people wish any suitable fabric bleached.Preferred described fabric is laundering of textile fabrics or clothes.In a preferred embodiment, method of the present invention is carried out on laundering of textile fabrics, and described detergent additive joined in the washings in a conventional wash(ing)cycle.

Described detergent additive comprises the combination of described at least part or complex compound and any appropriate carrier.The effect of described carrier only is carrying or comprises described additive active material, part or complex compound as described, and peroxygen bleach (if present), and when the described detergent additive of adding, the additive active material can be sent in the washings.The method according to this invention should be recognized, any carrier that is applicable to this purpose can be used.

Can be deposited on described part or complex compound on the described carrier easily or be impregnated in the carrier by any suitable mode, as liquid (the optional then drying of carrying out), or as the form of dry powder.Comprising the solvent that is used for described part or complex compound or the composition of mounting medium, preferred described part or complex compound appendix are in described carrier or on it.Described composition can be any suitable form, as can be the form of solid, powder, paste, gel or liquid.Preferred described composition is the form of liquid.

In an especially preferred embodiment, the method according to this invention adopts aqueous cleaning solution to implement on the laundry fabric.The adding of especially described detergent additive can be finished in the wash(ing)cycle of basic conventional cleaning clothes, or as the accessory constituent in this cycle.More preferably described detergent additive is joined in the aqueous detergent washings.Described part or complex compound can be sent to from carrier in the washings, and described carrier can or comprise three-dimensional body for particulate state, sheet.Described carrier can be scattered in or be dissolved in the described washings, maybe can keep complete substantially form.

The detergent additive for example form of dough (body) exists, and described complex compound slowly releases from described dough during whole process of doing washing or part process.This release can take place in the process of one way washing, also can take place in the process of multipass washing.In the later case, imagining described complex compound can discharge from the used carrier dirt-carrying body of washing process, as can be from placing the washing machine supply package, or discharges in the delivery system of washing machine or the dough in the cylinder.When using in washing machine drum, described carrier can free movement for cylinder, also can maintain static.By various mechanical means, as the barb by cooperating with cylinder wall, or it is this fixing to use other power (as magnetic force) to realize.Consider that the improvement washing machine is similar to provide fixing and to keep the method and the method in the known water closet production similar techniques of this carrier.Free-moving carrier, as be used for the container that surfactant material and/or other detergent ingredients join washings can comprise with as described in complex compound be discharged into various devices in the washings.

In as the scheme of selecting, described detergent additive can the dispersive form exist, and preferably dissolves in the washings.Described additive can adopt any various physical form that are used for detergent additive, comprises Powdered, granular, coccoid, sheet, bulk, bulk, strip or other solid forms, or adopts the form of paste, gel or liquid.The dosage of described additive can be consistent, also can add by the quantity that the user needs.Can be used in main wash(ing)cycle though consider these additives, do not get rid of them and can be used in conditioning or drying cycle.

The present invention is not limited to the situation of using washing machine, in the situation that also can be applicable to wash in some other alternate container.In these situations, consider by from employed rotating cylinder, well-bucket or other containers the described complex compound in the detergent additive, perhaps from the apparatus of any use (as brush, stub or smash the clothing pestle), or the method that slowly discharges from any suitable applicator transmits.

The present invention also extend to comprise part or complex compound commodity package together with its working instructions.

The present invention also extends to part or the purposes of complex compound in detergent additive is produced.The present invention describes in detail

Described catalyzer can comprise the preformed complex of part and transition metal.Perhaps described catalyzer can comprise and be present in the transition metal in the water or be present in the free ligand of the transition metal complex in the dirt-carrying body.Described catalyzer also can comprise the form of the composition of free ligand or transition metal-replaceable metal-ligand complex and transition metal source, takes this that original position generates described complex compound in medium.

Described part and one or more transition metal have formed complex compound, form for example a kind of binuclear complex in the latter's situation.Suitable transition metal comprises that for example oxidation state is manganese, iron II-V, copper I-III, cobalt I-III, titanium II-IV, tungsten IV-VI, vanadium II-V and the molybdenum II-VI of II-V.

Preferred described transition metal complex has following general formula:

[M _aL _kX _n] Y _mIn the formula:

The M representative is selected from following metal: Mn (II)-(III)-(IV)-(V), Cu (I)-(II)-(III), Fe (II)-(III)-(IV)-(V), Co (I)-(II)-(III), Ti (II)-(III)-(IV), V (II)-(III)-(IV)-(V), Mo (II)-(III)-(IV)-(V)-(VI) and W (IV)-(V)-(VI), is preferably selected from Fe (II)-(III)-(IV)-(V);

L represents part, is preferably N, two (pyridines-2-base-methyl)-1 of N-, two (pyridine-2-the yl)-1-ethylamines of 1-, or its protonated or deprotonation analogue;

X representative be selected from the anionic coordination species of any monovalence, divalence or trivalent and any can with described metal with a tooth, bidentate or three tooth pattern coordinate neutral molecules;

Y represents any non-coordinate counter ion;

A represents 1 to 10 integer;

K represents 1 to 10 integer;

N represents 0 or 1 to 10 integer;

M represents 0 or 1 to 20 integer.

Preferred described complex compound is for comprising described part N, two (pyridines-2-base-methyl)-1 of N-, two (pyridine-2-the yl)-1-ethylamines of 1-iron complex.Yet, should recognize that pretreatment process of the present invention is alternative or use other part and transition metal complex in addition that condition is that the complex compound that is generated can be by the bleaching of atmosphericoxygen catalysis spot.The suitable following description of ligand species:

(A) part of general formula (IA): In the formula:

The Z1 group is represented independently of one another and is selected from following coordinating group: hydroxyl, amino ,-NHR or-N (R) ₂(R=C wherein _1-6Alkyl), carboxylate radical, amide group ,-NH-C (NH) NH ₂, hydroxy phenyl, optional heterocycle or the optional aromatic heterocycle that replaces by one or more E of functional group that replaces by one or more E of functional group, described aromatic heterocycle is selected from: pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, oxazole and thiazole;

Q1 and Q3 represent the group of following formula independently of one another:

In the formula:

5 〉=a+b+c 〉=1; A=0-5; B=0-5; C=0-5; N=0 or 1 (preferred n=0);

Y represent independently of one another be selected from following group :-O-,-S-,-SO-,-SO ₂-,-C (O)-, arylidene, alkylidene group, heteroarylidene, heterocycle alkylidene group ,-(G) P-,-P (O)-and-(G) N-, wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, more than each (dehydrogenation outer) is optional is replaced by one or more E of functional group;

R5, R6, R7 and R8 represent independently of one another and are selected from following group: hydrogen, hydroxyl, halogen ,-R and-OR, wherein R represents alkyl, alkenyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl or carbonyl deriveding group, and R is optional to be replaced by one or more E of functional group;

Or R5 is with R6, or R7 is with R8, or both all represent oxygen;

Or R5 with R7 and/or separately R6 with R8, or R5 with R8 and/or separately R6 represent optional by C with R7 _1-4Alkyl ,-F ,-Cl ,-Br or-C that I replaced _1-6Alkylidene group;

T representative is selected from following non-coordinating group: hydrogen, hydroxyl, halogen ,-R and-OR, wherein R represents alkyl, alkenyl, cycloalkyl, Heterocyclylalkyl, aryl, arylalkyl, heteroaryl or carbonyl deriveding group, R is optional to be replaced by one or more E of functional group (preferred T=-H ,-OH, methyl, methoxyl group or benzyl);

U representative is the non-coordinating group T of the independent definition of institute as above, or represents following general formula (IIA), (IIIA) or coordinating group (IVA): In the formula:

Q2 and Q4 are independently of one another as the definition to Q1 and Q3;

Q representative-N (T)-(wherein N independently of one another as defined above), or the optional heterocycle that replaces or be selected from the aromatic heterocycle of following optional replacement: pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, oxazole and thiazole;

Z2 is independently of one another as the definition to Z1;

The Z3 group is represented-N (T)-(wherein T independently of one another as defined above) independently of one another;

Z4 representative is selected from following coordination or non-coordinating group: hydrogen, hydroxyl, halogen ,-NH-C (NH) NH ₂,-R and-OR, wherein R=alkyl, alkenyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl or carbonyl deriveding group, R is optional to be replaced by one or more E of functional group, or the group of the Z4 following general formula of representative (IIAa):

With

1≤j≤4 preferred Z1, Z2 and Z4 represent the optional heterocycle that replaces independently of one another or are selected from the aromatic heterocycle of following optional replacement: pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, oxazole and thiazole.More preferably Z1, Z2 and Z4 independently represent separately and are selected from following group: quinoline-2-base of choosing pyridine-2-base, the optional imidazoles-2-base that replaces that replaces, the imidazol-4 yl of choosing replacement wantonly, the optional pyrazol-1-yl that replaces and optional replacement wantonly.Most preferably Z1, Z2 and Z4 represent the optional pyridine-2-base that replaces separately.

If group Z1, Z2 and Z4 are substituted, then preferably are selected from following group and are replaced: C _1-4Alkyl, aryl, arylalkyl, heteroaryl, methoxyl group, hydroxyl, nitro, amino, carboxyl, halogen and carbonyl.Preferred Z1, Z2 and Z4 are separately by methyl substituted.The identical group of our also preferred each Z1 group representative.

Preferred Q1 represents covalent linkage or C1-C4-alkylidene group, more preferably covalent linkage, methylene radical or ethylidene, most preferably covalent linkage separately.

Preferred group Q represents covalent linkage or C1-C4 alkylidene group, more preferably covalent linkage.

Preferred group R5, R6, R7, R8 independently represent separately and are selected from following group :-H, hydroxyl-C ₀-C ₂₀-alkyl, halo-C ₀-C ₂₀-alkyl, nitroso-group, formyl radical-C ₀-C ₂₀-alkyl, carboxyl-C ₀-C ₂₀-alkyl and various ester thereof and salt, formamyl-C ₀-C ₂₀-alkyl, sulfo group-C ₀-C ₂₀-alkyl and various ester thereof and salt, sulfamyl-C ₀-C ₂₀-alkyl, amino-C ₀-C ₂₀-alkyl, aryl-C ₀-C ₂₀-alkyl, C ₀-C ₂₀-alkyl, alkoxy-C ₀-C ₈-alkyl, carbonyl-C ₀-C ₆-alkoxyl group and C ₀-C ₂₀-alkylamidoalkyl.None links together among the preferred R5-R8.

Preferred non-dentate T represents hydrogen, hydroxyl, methyl, ethyl, benzyl or methoxyl group.

At it on the one hand, the dentate of the following general formula of representative of the group U in the formula (IA) (IIA):

According to this aspect, preferred Z2 representative is chosen the heterocycle that replaces wantonly or is selected from the aromatic heterocycle of following optional replacement: pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, oxazole and thiazole, and more preferably choose the pyridine-2-base that replaces wantonly or choose the benzimidazolyl-2 radicals-Ji that replaces wantonly.

Also preferred Z4 represents the aromatic heterocycle of choosing the heterocycle that replaces wantonly or being selected from following optional replacement at this aspect: pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, oxazole and thiazole, the more preferably optional pyridine-2-base that replaces, or be selected from following non-dentate: hydrogen, hydroxyl, alkoxyl group, alkyl, alkenyl, cycloalkyl, aryl or benzyl.

In the preferred embodiment of this aspect, described part is selected from:

1, two (pyridine-2-yl)-N-methyl-N-(pyridine-2-ylmethyl) methylamines of 1-;

1, two (pyridine-2-the yl)-N of 1-, two (6-methyl-pyridine-2-ylmethyl) methylamines of N-;

1, two (pyridine-2-the yl)-N of 1-, two (5-carboxymethyl-pyridine-2-ylmethyl) methylamines of N-;

1, two (pyridine-2-the yl)-1-benzyl-N of 1-, two (pyridine-2-ylmethyl) methylamines of N-; With

1, two (pyridine-2-the yl)-N of 1-, two (benzimidazolyl-2 radicals-ylmethyl) methylamines of N-.

In a variant of this aspect, the group of the group Z4 following general formula of representative (IIAa) in the formula (IIA):

In this variant, the optional alkylidene group that replaces of preferred Q4 representative, preferred-CH ₂-CHOH-CH ₂-or-CH ₂-CH ₂-CH ₂-.In a preferred embodiment of this variant, described part is: In the formula-Py represents pyridine-2-base.

On the other hand, the dentate of the following general formula of representative of the group U in the formula (IA) (IIIA):

J is 1 or 2 in the formula, is preferably 1.

According to this aspect, preferred Q2 represents (CH separately ₂) _n-(n=2-4), preferred Z3 represents separately-N (R)-, wherein R=-H or-C _1-4Alkyl, preferable methyl.

In the preferred embodiment of this aspect, described part is selected from:

In the formula-Py represents pyridine-2-base.

More on the one hand, the dentate of the group U following general formula of representative (IVA) in the formula (IA):

In this aspect, preferred Q representative-N (T)-(wherein T=-H, methyl or benzyl) or pyridine-two base.

In the preferred embodiment of this aspect, described part is selected from: In the formula-and Py represents pyridine-2-base, and-Q-represents pyridine-2,6-two bases.(B) part of general formula (IB):

In the formula:

N=1 or 2, if n=2, then-Q ₃-R ₃Group will define independently of one another;

R ₁, R ₂, R ₃, R ₄Representative independently of one another is selected from following group: hydrogen, hydroxyl, halogen ,-NH-C (NH) NH ₂,-R and-OR, wherein R=alkyl, alkenyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl or carbonyl deriveding group, R is optional to be replaced by one or more E of functional group;

Q ₁, Q ₂, Q ₃, Q ₄Represent the group of following formula independently of one another with Q:

In the formula:

5 〉=a+b+c 〉=1; A=0-5; B=0-5; C=0-5; N=1 or 2;

Y separately independently the representative be selected from following group :-O-,-S-,-SO-,-SO ₂-,-C (O)-, arylidene, alkylidene group, heteroarylidene, heterocycle alkylidene group ,-(G) P-,-P (O)-and-(G) N-, wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, more than each (dehydrogenation outer) is optional is replaced by one or more E of functional group;

R5, R6, R7, R8 separately independently representative be selected from following group: hydrogen, hydroxyl, halogen ,-R and-OR, wherein R represents alkyl, alkenyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl or carbonyl deriveding group, and R is optional to be replaced by one or more E of functional group;

Or R5 is with R6, or R7 is with R8, or the both represents oxygen;

Or R5 with R7 and/or separately R6 with R8, or R5 with R8 and/or separately R6 represent optional by C with R7 _1-4Alkylidene group ,-F ,-Cl ,-Br or-C that I replaced _1-6Alkylidene group;

Condition is R ₁, R ₂, R ₃And R ₄In at least two comprise the coordination heteroatoms, and be no more than 6 heteroatomss and be coordinated on the identical transition metal atoms.

R ₁, R ₂, R ₃And R ₄In at least two, preferred at least three independent separately representatives be selected from following group: carboxylate radical, amide group ,-NH-C (NH) NH ₂, hydroxy phenyl, the optional heterocycle that replaces or be selected from the aromatic heterocycle of following optional replacement: pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, oxazole and thiazole.

Work as radicals R ₁, R ₂, R ₃And R ₄Substituting group when representing heterocycle or aromatic heterocycle, be preferably selected from C _1-4Alkyl, aryl, arylalkyl, heteroaryl, methoxyl group, hydroxyl, nitro, amino, carboxyl, halogen and carbonyl.

Preferred group Q ₁, Q ₂, Q ₃And Q ₄Independent separately representative is selected from-CH ₂-and-CH ₂CH ₂-group.

Group Q is preferably and is selected from-(CH ₂) _2-4-,-CH ₂CH (OH) CH ₂-group. Optional by methyl or ethyl, With

Replace wherein R representative-H or CH _1-4Alkyl.

Preferred definition Q ₁, Q ₂, Q ₃And Q ₄, make a=b=0, c=1 and n=1, and definition Q makes a=b=0, c=2 and n=1.

Preferred group R5, R6, R7, R8 independently represent separately and are selected from following group :-H, hydroxyl-C ₀-C ₂₀-alkyl, halogen-C ₀-C ₂₀-alkyl, nitroso-group, formyl radical-C ₀-C ₂₀-alkyl, carboxyl-C ₀-C ₂₀-alkyl and various ester thereof and salt, formamyl-C ₀-C ₂₀-alkyl, sulfo group-C ₀-C ₂₀-alkyl and various ester thereof and salt, sulfamyl-C ₀-C ₂₀-alkyl, amino-C ₀-C ₂₀-alkyl, aryl-C ₀-C ₂₀-alkyl, C ₀-C ₂₀-alkyl, alkoxy-C ₀-C ₈-alkyl, carbonyl-C ₀-C ₆-alkoxyl group and C ₀-C ₂₀-alkylamidoalkyl.None links together among the preferred R5-R8.

One preferred aspect, described part has following general formula (IIB): In the formula:

Definition Q ₁, Q ₂, Q ₃And Q ₄Make a=b=0, c=1 or 2 and n=1;

Definition Q makes a=b=0, c=2,3 or 4 and n=1; With

R ₁, R ₂, R ₃, R ₄, R ₇, R ₈Independently of one another as definition to formula (I).

Shown in following formula (IIB), as follows according to the preferred ligand species of this aspect:

(i) part of general formula (IIB), wherein:

R ₁, R ₂, R ₃And R ₄Independent separately representative is selected from following dentate: carboxylate radical, amide group ,-NH-C (NH) NH ₂, hydroxy phenyl, the optional heterocycle that replaces or be selected from the aromatic heterocycle of following optional replacement: pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, oxazole and thiazole.

In such, we are preferred:

Definition Q makes a=b=0, c=2 or 3 and n=1;

R ₁, R ₂, R ₃And R ₄Independent separately representative is selected from following dentate: the optional pyridine-2-base that replaces, the optional imidazoles-2-base that replaces, the optional imidazol-4 yl that replaces, the optional pyrazol-1-yl that replaces and the optional quinoline-2-base that replaces.

The (ii) part of general formula (IIB), wherein:

R ₁, R ₂, R ₃Independent separately representative is selected from following dentate: carboxylate radical, amide group ,-NH-C (NH) NH ₂, hydroxy phenyl, the optional heterocycle that replaces or be selected from the aromatic heterocycle of following optional replacement: pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, oxazole and thiazole; With

The R4 representative is selected from following group: hydrogen, C _1-20Optional alkyl, the C that replaces _1-20Optional arylalkyl, aryl and the C that replaces _1-20The optional NR that replaces ₃ ⁺(R=C wherein _1-8Alkyl).

In such, we are preferred:

Definition Q makes a=b=0, c=2 or 3 and n=1;

R ₁, R ₂, R ₃Independent separately representative is selected from following dentate: the optional pyridine-2-base that replaces, the optional imidazoles-2-base that replaces, the optional imidazol-4 yl that replaces, the optional pyrazol-1-yl that replaces and the optional quinoline-2-base that replaces; With

R ₄Representative is selected from following group: hydrogen, C _1-10Optional alkyl, the C that replaces _1-5Furyl, C _1-5Optional benzyl alkyl, benzyl, the C that replaces _1-5Optional alkoxyl group and the C that replaces _1-20The optional N that replaces ⁺Me ₃

The (iii) part of general formula (IIB), wherein:

R ₁, R ₄Independent separately representative is selected from following dentate: carboxylate radical, amide group ,-NH-C (NH) NH ₂, hydroxy phenyl, the optional heterocycle that replaces or be selected from the aromatic heterocycle of following optional replacement: pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, oxazole and thiazole; With

R ₂, R ₃Independent separately representative is selected from following group: hydrogen, C _1-20Optional alkyl, the C that replaces _1-20Optional arylalkyl, aryl and the C that replaces _1-20The optional NR that replaces ₃ ⁺(R=C wherein _1-8Alkyl).

In such, we are preferred:

Definition Q makes a=b=0, c=2 or 3 and n=1;

R ₁, R ₄Independent separately representative is selected from following dentate: the optional pyridine-2-base that replaces, the optional imidazoles-2-base that replaces, the optional imidazol-4 yl that replaces, the optional pyrazol-1-yl that replaces and the optional quinoline-2-base that replaces; With

R ₂, R ₃Independent separately representative is selected from following group: hydrogen, C _1-10Optional alkyl, the C that replaces _1-5Furyl, C _1-5Optional benzyl alkyl, benzyl, the C that replaces _1-5Optional alkoxyl group and the C that replaces _1-20The optional N that replaces ⁺Me ₃

The example of its simple form of preferred part has:

N, N ', N '-three (3-methyl-pyridine-2-ylmethyl)-quadrol;

N-trimethyl ammonium propyl group-N, N ', N '-three (pyridine-2-ylmethyl)-quadrol;

N-(2-hydroxy ethylene)-N, N ', N '-three (pyridine-2-ylmethyl)-quadrol;

N, N, N ', N '-four (3-methyl-pyridine-2-ylmethyl)-quadrol;

N, N '-dimethyl-N, N '-two (pyridine-2-ylmethyl)-hexanaphthene-1,2-diamines;

N-(2-hydroxy ethylene)-N, N ', N '-three (3-methyl-pyridine-2-ylmethyl)-quadrol;

N-methyl-N, N ', N '-three (pyridine-2-ylmethyl)-quadrol;

N-methyl-N, N ', N '-three (5-ethyl-pyridine-2-ylmethyl)-quadrol;

N-methyl-N, N ', N '-three (5-methyl-pyridine-2-ylmethyl)-quadrol;

N-methyl-N, N ', N '-three (3-methyl-pyridine-2-ylmethyl)-quadrol;

N-benzyl-N, N ', N '-three (3-methyl-pyridine-2-ylmethyl)-quadrol;

N-ethyl-N, N ', N '-three (3-methyl-pyridine-2-ylmethyl)-quadrol;

N, N ', N '-three (3-methyl-pyridine-2-ylmethyl)-N ' (2 '-methoxyl group-ethyl-1)-quadrol;

N, N, N '-three (1-methyl-benzimidazolyl-2 radicals-yl)-N '-methyl-quadrol;

N-(furans-2-yl)-N, N ', N '-three (3-methyl-pyridine-2-ylmethyl)-quadrol;

N-(2-hydroxy ethylene)-N, N ', N '-three (3-ethyl-pyridine-2-ylmethyl)-quadrol;

N-methyl-N, N ', N '-three (3-methyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-ethyl-N, N ', N '-three (3-methyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-benzyl-N, N ', N '-three (3-methyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-(2-hydroxyethyl)-N, N ', N '-three (3-methyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-(2-methoxy ethyl)-N, N ', N '-three (3-methyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-methyl-N, N ', N '-three (5-methyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-ethyl-N, N ', N '-three (5-methyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-benzyl-N, N ', N '-three (5-methyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-(2-hydroxyethyl)-N, N ', N '-three (5-methyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-(2-methoxy ethyl)-N, N ', N '-three (5-methyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-methyl-N, N ', N '-three (3-ethyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-ethyl-N, N ', N '-three (3-ethyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-benzyl-N, N ', N '-three (3-ethyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-(2-hydroxyethyl)-N, N ', N '-three (3-ethyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-(2-methoxy ethyl)-N, N ', N '-three (3-ethyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-methyl-N, N ', N '-three (5-ethyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-ethyl-N, N ', N '-three (5-ethyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines;

N-benzyl-N, N ', N '-three (5-ethyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines; With

N-(2-methoxy ethyl)-N, N ', N '-three (5-ethyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines.

Preferred part is:

N-(2-hydroxyethyl)-N, N ', N '-three (3-methyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines; With

N-(2-methoxy ethyl)-N, N ', N '-three (3-methyl-pyridine-2-ylmethyl) ethylidene-1,2-diamines.

(C) part of general formula (IC):

In the formula:

Z ₁, Z ₂And Z ₃Independent separately representative is selected from following dentate: carboxylate radical, amide group ,-NH-C (NH) NH ₂, hydroxy phenyl, the optional heterocycle that replaces or be selected from the aromatic heterocycle of following optional replacement: pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, oxazole and thiazole;

Q ₁, Q ₂And Q ₃Represent the group of following formula independently of one another: In the formula:

5 〉=a+b+c 〉=1; A=0-5; B=0-5; C=0-5; N=1 or 2;

Y separately independently the representative be selected from following group :-O-,-S-,-SO-,-SO ₂-,-C (O)-, arylidene, alkylidene group, heteroarylidene, heterocycle alkylidene group ,-(G) P-,-P (O)-and-(G) N-, wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, more than each (dehydrogenation outer) is optional is replaced by one or more E of functional group; With

Or R5 is with R6, or R7 is with R8, or the both represents oxygen;

Or R5 with R7 and/or separately R6 with R8, or R5 with R8 and/or separately R6 represent optional by C with R7 _1-4-alkyl ,-F ,-Cl ,-Br or-C that I replaced _1-6Alkylidene group.

Z ₁, Z ₂And Z ₃Independent separately representative is preferably selected from following dentate: the optional pyridine-2-base that replaces, the optional imidazoles-2-base that replaces, the optional imidazol-4 yl that replaces, the optional pyrazol-1-yl that replaces and the optional quinoline-2-base that replaces.Preferred Z ₁, Z ₂And Z ₃Optional pyridine-2-the base that replaces of independent separately representative.

Group Z ₁, Z ₂And Z ₃Optional substituting group be preferably selected from C _1-4-alkyl, aryl, arylalkyl, heteroaryl, methoxyl group, hydroxyl, nitro, amino, carboxyl, halogen and carbonyl, preferable methyl.

Also preferred definition Q ₁, Q ₂And Q ₃Make a=b=0, c=1 or 2 and n=1.

Preferred Q ₁, Q ₂And Q ₃The independent separately C that represents _1-4-alkylidene group more preferably is selected from-CH ₂-and-CH ₂CH ₂-group.

Preferred described part is selected from three (pyridine-2-ylmethyl) amine, three (3-methyl-pyridine-2-ylmethyl) amine, three (5-methyl-pyridine-2-ylmethyl) amine and three (6-methyl-pyridine-2-ylmethyl) amine.

(D) part of general formula (ID): In the formula:

R ₁, R ₂And R ₃Representative independently of one another is selected from following group: hydrogen, hydroxyl, halogen ,-NH-C (NH) NH ₂,-R and-OR, wherein R=alkyl, alkenyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl or carbonyl deriveding group, R is optional to be replaced by one or more E of functional group;

Q independently represents to be selected from separately and chooses wantonly by H, benzyl or C _1-8The C that-alkyl replaces _2-3The group of-alkylidene group.

5 〉=a+b+c 〉=1; A=0-5; B=0-5; C=0-5; N=1 or 2;

Or R5 is with R6, or R7 is with R8, or the both represents oxygen;

Or R5 with R7 and/or separately R6 with R8, or R5 with R8 and/or separately R6 represent optional by C with R7 _1-4-alkyl ,-F ,-Cl ,-Br or-C that I replaces _1-6-alkylidene group.

Condition is R ₁, R ₂And R ₃In at least one, preferably at least two be dentate.

R ₁, R ₂And R ₃In at least two, preferred at least three independent separately representatives be selected from following group: carboxylate radical, amide group ,-NH-C (NH) NH ₂, hydroxy phenyl, the optional heterocycle that replaces or be selected from the aromatic heterocycle of following optional replacement: pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, oxazole and thiazole.Preferred R ₁, R ₂And R ₃In have two independent separately representatives at least preferably from following dentate: the optional pyridine-2-base that replaces, the optional imidazoles-2-base that replaces, the optional imidazol-4 yl that replaces, the optional pyrazol-1-yl that replaces and the optional quinoline-2-base that replaces.

Work as radicals R ₁, R ₂And R ₃Substituting group when representing heterocycle or aromatic heterocycle, be preferably selected from C _1-4-alkyl, aryl, arylalkyl, heteroaryl, methoxyl group, hydroxyl, nitro, amino, carboxyl, halogen and carbonyl.

Preferred definition Q ₁, Q ₂And Q ₃Make a=b=0, c=1,2,3 or 4 and n=1.Preferred group Q ₁, Q ₂And Q ₃Independent separately representative is selected from-CH ₂-and-CH ₂CH ₂-group.

Preferred group Q is for being selected from-CH ₂CH ₂-and-CH ₂CH ₂CH ₂-group.

One preferred aspect, described part has following general formula (IID):

Wherein R1, R2 and R3 are as before this to R ₁, R ₂And R ₃Definition, and Q ₁, Q ₂And Q ₃Also such as before this definition.

Shown in following formula (IID), as follows according to the preferred ligand species of this preferred aspect:

(i) part of general formula (IID), wherein:

R1, R2 and R3 separately independently representative be selected from following dentate: carboxylate radical, amide group ,-NH-C (NH) NH ₂, hydroxy phenyl, the optional heterocycle that replaces or be selected from the aromatic heterocycle of following optional replacement: pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, oxazole and thiazole.

In such, we are preferred:

R1, R2 and R3 independently represent separately and are selected from following dentate: quinoline-2-base of choosing pyridine-2-base, the optional imidazoles-2-base that replaces that replaces, the imidazol-4 yl of choosing replacement wantonly, the optional pyrazol-1-yl that replaces and optional replacement wantonly.

The (ii) part of general formula (IID), wherein:

Among R1, R2 and the R3 two independent separately representatives are selected from following dentate: carboxylate radical, amide group ,-NH-C (NH) NH ₂, hydroxy phenyl, the optional heterocycle that replaces or be selected from the aromatic heterocycle of following optional replacement: pyridine, pyrimidine, pyrazine, pyrazoles, imidazoles, benzoglyoxaline, quinoline, quinoxaline, triazole, isoquinoline 99.9, carbazole, indoles, isoindole, oxazole and thiazole; With

A representative among R1, R2 and the R3 is selected from following group: hydrogen, C _1-20Optional alkyl, the C that replaces _1-20Optional arylalkyl, aryl and the C that replaces _1-20The optional NR that replaces ₃ ⁺(R=C wherein _1-8-alkyl).

In such, we are preferred:

Two independent separately representatives among R1, R2 and the R3 are selected from following dentate: the optional pyridine-2-base that replaces, the optional imidazoles-2-base that replaces, the optional imidazol-4 yl that replaces, the optional pyrazol-1-yl that replaces and the optional quinoline-2-base that replaces; With

A representative among R1, R2 and the R3 is selected from following group: hydrogen, C _1-10Optional alkyl, the C that replaces _1-5Furyl, C _1-5Optional benzyl alkyl, benzyl, the C that replaces _1-5Optional alkoxyl group and the C that replaces _1-20The optional N that replaces ⁺Me ₃

In particularly preferred embodiments, described part is selected from:

Wherein-and Et represents ethyl, and-Py represents pyridine-2-base, and Pz3 represents pyrazole-3-yl, and Pz1 represents pyrazol-1-yl, and Qu represents quinoline-2-base.

(E) part of general formula (IE): In the formula:

G represents 0 or 1 to 6 integer;

R represents 1 to 6 integer;

S represents 0 or 1 to 6 integer;

Q1 and Q2 independently represent the group of following formula separately:

In the formula:

5≥d+e+f≥1；d＝0-5；e＝0-5；f＝0-5；

Y1 separately independently the representative be selected from following group :-O-,-S-,-SO-,-SO ₂-,-C (O)-, arylidene, alkylidene group, heteroarylidene, heterocycle alkylidene group ,-(G) P-,-P (O)-and-(G) N-, wherein G is selected from hydrogen, alkyl, aryl, arylalkyl, cycloalkyl, more than each (dehydrogenation outer) is optional is replaced by one or more E of functional group;

If s＞1, then-[N (R1)-(Q1) _r-]-group defines independently of one another;

R1, R2, R6, R7, R8, R9 separately independently representative be selected from following group: hydrogen, hydroxyl, halogen ,-R and-OR, wherein R represents alkyl, alkenyl, cycloalkyl, Heterocyclylalkyl, aryl, heteroaryl or carbonyl deriveding group, and R is optional to be replaced by one or more E of functional group;

Or R6 is with R7, or R8 is with R9, or the both represents oxygen;

Or R6 with R8 and/or separately R7 with R9, or R6 with R9 and/or separately R7 represent optional by C with R8 _1-4-alkyl ,-F ,-Cl ,-Br or-C that I replaces _1-6-alkylidene group;

Or among the R1-R9 one bridging group for another part of being incorporated into same general formula;

T1 and T2 independently represent radicals R 4 and R5 separately, and wherein R4 and R5 be as the definition to R1-R9, and if g=0 and s＞1, then R1 can choose independent separately representative=CH-R10 with R4 and/or R2 wantonly with R5, and wherein R10 is as the definition to R1-R9, or

When s＞1 and g＞0, T1 and T2 can (T2-T1-) represent a covalent linkage together;

If T1 and T2 represent a singly-bound together, then Q1 and/or Q2 can independently represent the group of following formula :=CH-[-Y1-separately] _e-CH=(condition is not have R1 and/or R2), and R1 and/or R2 can not exist (condition is the group that Q1 and/or Q2 independently represent following formula separately :=CH-[-Y1-] _e-CH=).

Preferred group R1-9 independently represents separately and is selected from following group :-H, hydroxyl-C ₀-C ₂₀-alkyl, halogen-C ₀-C ₂₀-alkyl, nitroso-group, formyl radical-C ₀-C ₂₀-alkyl, carboxyl-C ₀-C ₂₀-alkyl and various ester thereof and salt, formamyl-C ₀-C ₂₀-alkyl, sulfo group-C ₀-C ₂₀-alkyl and various ester thereof and salt, sulfamyl-C ₀-C ₂₀-alkyl, amino-C ₀-C ₂₀-alkyl, aryl-C ₀-C ₂₀-alkyl, heteroaryl-C ₀-C ₂₀-alkyl, C ₀-C ₂₀-alkyl, alkoxy-C ₀-C ₈-alkyl, carbonyl-C ₀-C ₆-alkoxyl group and aryl-C ₀-C ₆-alkyl and C ₀-C ₂₀-alkylamidoalkyl.

Among the R1-R9 one can be described ligand moiety is connected in bridging group on second ligand moiety of preferred same structure.In this case, described bridging group defines according to the general formula of described Q1, Q2 independently of one another, is preferably alkylidene group or hydroxyl-alkylidene group or comprises the bridging group of heteroaryl, and is more preferably optional by C _1-4-alkyl ,-F ,-Cl ,-Br or-C that I replaces _1-6-alkylidene group.

In first kind of variant according to formula (IE), group T1 and T2 form a singly-bound and s＞1 together, according to following general formula (IIE): Wherein R3 independently representative as separately to the group of the definition of R1-R9; Q3 is independently representative as to the group of the definition of Q1 and Q2 separately; H represents 0 or 1 to 6 integer; And s=s-1.

In first embodiment of described first kind of variant, s=1,2 or 3 in the general formula (IIE); R=g=h=1; D=2 or 3; E=f=0; R6=R7=H preferably makes described part have and is selected from following general formula:

In these preferred embodiments, preferred R1, R2, R3 and R4 independently be selected from separately-H, alkyl, aryl, heteroaryl, and/or a representative among the R1-R4 is incorporated into the bridging group on another part of same general formula, and/or among the R1-R4 two or more are represented a bridging group on the N atom that is connected in same section together, described bridging group is alkylidene group or hydroxyl-alkylidene group or the bridging group that comprises heteroaryl, is preferably heteroarylidene.More preferably R1, R2, R3 and R4 independently are selected from-H, methyl, ethyl, sec.-propyl, nitrogenous heteroaryl separately, or be connected in bridging group on same general formula another part, or be connected on the N atom of same section for the bridging group of alkylidene group or hydroxyl-alkylidene group.

In second embodiment of first kind of variant, s=2 and r=g=h=1 in the general formula (IIE) meet following general formula:

In this second embodiment, preferably there is not R1-R4; Q1 and Q2 represent=CH-[-Y1-] _e-CH=; And Q2 and Q4 represent-CH ₂-[Y1-] _n-CH ₂-.

Therefore, preferred described part has following general formula: Wherein A representative optional by heteroatoms the alkylidene group of optional replacement at interval; With n be 0 or 1 to 5 integer.

Preferred R1-R6 represents hydrogen, n=1 and A=-CH ₂-,-CHOH-,-CH ₂N (R) CH ₂-or-CH ₂CH ₂N (R) CH ₂CH ₂-, wherein R represents hydrogen or alkyl, more preferably A=-CH ₂-,-CHOH-or-CH ₂CH ₂NHCH ₂CH ₂-.

In second variant according to general formula (IE), T1 and T2 independently represent separately as to the radicals R in the definition of R1-R9 4, R5, meet following general formula (IIIE):

In first embodiment of described second variant, s=1 in the general formula (IIIE); R=1; G=0; D=f=1; E=0-4; Y1=-CH ₂-; With R1 with R4, and/or R2 is with the independent separately representative=CH-R10 of R5, wherein R10 is as the definition to R1-R9.In one embodiment, R2 represents=CH-R10 with R5, and R1 and R4 are two groups that separate.Perhaps R1 is with R4, and R2 can independent separately representative=CH-R10 with R5.Therefore, preferred part for example can have and is selected from following structure: N=0-4 in the formula.

Preferred described part is selected from:

Wherein R1 and R2 are selected from: optional phenols, the heteroaryl-C that replaces ₀-C ₂₀-alkyl, R3 and R4 be selected from-H, alkyl, aryl, optional phenols, the heteroaryl-C that replaces ₀-C ₂₀-alkyl, alkylaryl, aminoalkyl group, alkoxyl group, more preferably R1 and R2 are selected from optional phenols, the heteroaryl-C that replaces ₀-C ₂-alkyl, R3 and R4 be selected from-H, alkyl, aryl, optional phenols, the nitrogen-heteroaryl-C that replaces ₀-C ₂-alkyl.

In second embodiment of described second variant, s=1 in the general formula (IIIE); R=1; G=0; D=f=1; E=1-4; Y1=-C (R ') (R "), wherein R ' and R " independent separately as to the definition of R1-R9.Preferred described part has following general formula:

Radicals R 1, R2, R3, R4 and R5 in preferred this formula are-H or C ₀-C ₂₀-alkyl, n=0 or 1, R6 be-H, alkyl ,-OH or-SH and preferred R7, R8, R9 and R10 be selected from-H, C independently of one another ₀-C ₂₀-alkyl, heteroaryl-C ₀-C ₂₀-alkyl, alkoxy-C ₀-C ₈-alkyl and amino-C ₀-C ₂₀-alkyl.

In the 3rd embodiment of described second kind of variant, s=0 in the general formula (IIIE); G=1; D=e=0; F=1-4.Preferred described part has following general formula:

According to the present invention, preferred especially such part.More preferably described part has following general formula: Wherein R1, R2 and R3 are as the definition to R2, R4 and R5.

In the 4th embodiment of described second kind of variant, described part is five tooth parts of following general formula (IVE):

In the formula:

R ¹, R ²Independent separately representative-R ⁴-R ⁵

R ³Represent hydrogen, optional alkyl, aryl or the arylalkyl that replaces, or-R ⁴-R ⁵

R ⁴Independent separately singly-bound or optional alkylidene group, alkylene group, oxygen base alkylidene group (oxyalkylene), amino alkylidenyl, alkylene ether, carboxylicesters or the carboxylic acid amide that replaces represented; With

R ⁵Aminoalkyl group that the optional N-of independent separately representative replaces or the heteroaryl that is selected from following optional replacement: pyridyl, pyrazinyl, pyrazolyl, pyrryl, imidazolyl, benzimidazolyl-, pyrimidyl, triazolyl and thiazolyl.

The present invention is especially preferably by the represented ligand species of general formula (IVE).As defined above, the part with general formula (IVE) is a kind of five tooth parts." five teeth " herein be meant in metal complex five heteroatomss can with described metal M ion coordination.

In formula (IVE), a coordination heteroatoms is provided by the nitrogen-atoms in the methylamine main chain, and a preferred coordination heteroatoms is included in four R ¹And R ²Each of side group in.Preferred all coordination heteroatomss are nitrogen-atoms.

The part of preferred formula (IVE) comprises at least two replacements or unsubstituted heteroaryl in described four side groups.Preferred described heteroaryl is pyridine-2-base, as is substituted, and then is preferably methyl-or the pyridine-2-base of ethyl-replacement.More preferably described heteroaryl is unsubstituted pyridine-2-base.Preferred described heteroaryl is connected on the methylamine by methylene radical, and preferably is connected on its N atom.The part of preferred formula (IVE) comprises at least one optional amino-pendent alkyl groups that replaces, and more preferably comprises two amino-ethyl side groups, particularly 2-(N-alkyl) amino-ethyl or 2-(N, N-dialkyl group) amino-ethyl.

Therefore, preferred R in general formula (IVE) ¹Represent pyridine-2-base or R ²Represent pyridine-2-base-methyl.Preferred R ²Or R ¹Represent 2-amino-ethyl, 2-(N-(first) ethyl) amino-ethyl or 2-(N, N-two (first) ethyl) amino-ethyl.As be substituted R then ⁵The preferred 3-picoline-2-base of representing.R ³Preferred hydrogen, benzyl or the methyl represented.

The example of its simple form of the preferred part of general formula (IVE) has:

(i) contain the part of pyridine-2-base, as:

N, two (pyridine-2-base-methyl)-two (pyridine-2-yl) methylamines of N-;

N, two (pyrazol-1-yl-methyl)-two (pyridine-2-yl) methylamines of N-;

N, two (imidazoles-2-base-methyl)-two (pyridine-2-yl) methylamines of N-;

N, two (1,2,4-triazoles-1-base-methyl)-two (pyridine-2-yl) methylamines of N-;

N, two (pyridine-2-base-methyl)-two (pyrazol-1-yl) methylamines of N-;

N, two (pyridine-2-base-methyl)-two (imidazoles-2-yl) methylamines of N-;

N, two (pyridine-2-base-methyl)-two (1,2, the 4-triazol-1-yl) of N-methylamine;

N, two (pyridines-2-base-methyl)-1 of N-, two (pyrazoles-2-the yl)-1-ethylamines of 1-;

N, two (pyridines-2-base-methyl)-1 of N-, two (pyridine-2-the yl)-2-phenyl-1-ethylamines of 1-;

N, two (pyrazol-1-yl-methyl)-1 of N-, two (pyridine-2-the yl)-1-ethylamines of 1-;

N, two (pyrazol-1-yl-methyl)-1 of N-, two (pyridine-2-the yl)-2-phenyl-1-ethylamines of 1-;

N, two (imidazoles-2-base-methyl)-1 of N-, two (pyridine-2-the yl)-1-ethylamines of 1-;

N, two (imidazoles-2-base-methyl)-1 of N-, two (pyridine-2-the yl)-2-phenyl-1-ethylamines of 1-;

N, two (1,2,4-triazol-1-yl-methyl)-1 of N-, two (pyridine-2-the yl)-1-ethylamines of 1-;

N, two (1,2,4-triazol-1-yl-methyl)-1 of N-, two (pyridine-2-the yl)-2-phenyl-1-ethylamines of 1-;

N, two (pyridines-2-base-methyl)-1 of N-, two (the pyrazol-1-yl)-1-ethylamines of 1-;

N, two (pyridines-2-base-methyl)-1 of N-, two (the pyrazol-1-yl)-2-phenyl of 1--1-ethylamine;

N, two (pyridines-2-base-methyl)-1 of N-, two (imidazoles-2-the yl)-1-ethylamines of 1-;

N, two (pyridines-2-base-methyl)-1 of N-, two (imidazoles-2-the yl)-2-phenyl-1-ethylamines of 1-;

N, two (pyridines-2-base-methyl)-1 of N-, two (1,2, the 4-the triazol-1-yl)-1-ethylamines of 1-;

N, two (pyridines-2-base-methyl)-1 of N-, two (pyridine-2-the yl)-1-ethylamines of 1-;

N, two (pyridines-2-base-methyl)-1 of N-, two (pyridine-2-the yl)-1-aminohexanes of 1-;

N, two (pyridines-2-base-methyl)-1 of N-, two (pyridine-2-the yl)-2-(4-sulfonic acid-phenyl) of 1--1-ethylamine;

N, two (pyridines-2-base-methyl)-1 of N-, two (pyridine-2-the yl)-2-(pyridine-2-yl) of 1--1-ethylamine;

N, two (pyridines-2-base-methyl)-1 of N-, two (pyridine-2-yl)-2-(the pyridin-3-yl)-1-ethylamines of 1-;

N, two (pyridines-2-base-methyl)-1 of N-, two (pyridine-2-yl)-2-(the pyridin-4-yl)-1-ethylamines of 1-;

N, two (pyridines-2-base-methyl)-1 of N-, two (pyridine-2-the yl)-2-(1-alkyl-pyridin-4-yl) of 1--1-ethylamine;

N, two (pyridines-2-base-methyl)-1 of N-, two (pyridine-2-the yl)-2-(1-alkyl-pyridin-3-yl) of 1--1-ethylamine;

N, two (pyridines-2-base-methyl)-1 of N-, two (pyridine-2-the yl)-2-(1-alkyl-pyridine-2-yl) of 1--1-ethylamine;

The part that (ii) contains the 2-amino-ethyl, as:

N, two (2-(N-alkyl) amino-ethyl)-two (pyridine-2-yl) methylamines of N-;

N, two (2-(N-alkyl) amino-ethyl)-two (pyrazol-1-yl) methylamines of N-;

N, two (2-(N-alkyl) amino-ethyl)-two (imidazoles-2-yl) methylamines of N-;

N, two (2-(N-alkyl) amino-ethyl)-two (1,2, the 4-triazol-1-yl) of N-methylamine;

N, two (2-(N, the two alkyl of N-) amino-ethyl)-two (pyridine-2-yl) methylamines of N-;

N, two (2-(N, the two alkyl of N-) amino-ethyl)-two (pyrazol-1-yl) methylamines of N-;

N, two (2-(N, the two alkyl of N-) amino-ethyl)-two (imidazoles-2-yl) methylamines of N-;

N, two (2-(N, the two alkyl of N-) amino-ethyl)-two (1,2, the 4-triazol-1-yl) methylamines of N-;

N, two (pyridine-2-base-methyl)-two (2-amino-ethyl) methylamines of N-;

N, two (pyrazol-1-yl-methyl)-two (2-amino-ethyl) methylamines of N-;

N, two (imidazoles-2-base-methyl)-two (2-amino-ethyl) methylamines of N-;

N, two (1,2,4-triazol-1-yl-methyl)-two (2-amino-ethyl) methylamines of N-.

Preferred part is:

N, after this two (pyridine-2-base-methyl)-two (pyridine-2-yl) methylamines of N-are referred to as N4Py;

N, two (pyridines-2-base-methyl)-1 of N-, after this two (pyridine-2-the yl)-1-ethylamines of 1-are referred to as MeN4Py;

N, two (pyridines-2-base-methyl)-1 of N-, after this two (pyridine-2-the yl)-2-phenyl-1-ethylamines of 1-are referred to as BzN4Py.

In the 5th embodiment of described second kind of variant, five teeth or the sexadentate ligand of the described part following general formula of representative (VE):

R ¹R ¹N-W-NR ¹R ²(VE) in the formula:

R ¹Independent separately representative-R ³-V, wherein R ³Optional alkylidene group, alkylene group, oxygen base alkylidene group, amino alkylidenyl or the alkylene ether that replaces of representative, and the V representative is selected from the heteroaryl groups of following optional replacement: pyridyl, pyrazinyl, pyrazolyl, pyrryl, imidazolyl, benzimidazolyl-, pyrimidyl, triazolyl and thiazolyl;

The W representative is selected from the alkylidene group bridging base of following optional replacement :-CH ₂CH ₂-,-CH ₂CH ₂CH ₂-,-CH ₂CH ₂CH ₂CH ₂-,-CH ₂-C ₆H ₄-CH ₂-,-CH ₂-C ₆H ₁₀-CH ₂-and-CH ₂-C ₁₀H ₆-CH ₂-; With

R ²Representative is selected from following group: R ¹, and optional hydroxyl, alkoxyl group, phenoxy group, carboxylate radical, amide group, carboxylicesters, sulfonate radical, amine, alkylamine and the N of being selected from ⁺(R ⁴) ₃(R wherein ⁴Be selected from hydrogen, alkyl group (alkanyl), alkenyl, aryl alkyl group, aromatic yl alkenyl, oxygen base alkyl group, oxygen base alkenyl (oxyalkenyl), amino-alkane base, amino alkenyl, alkyl group ether and alkenyl ether) the alkyl that substituting group replaced, aryl and arylalkyl.

As defined above, the part with general formula (VE) is five tooth parts, if perhaps R ¹=R ², then it can be a sexadentate ligand.As mentioned above, " five teeth " be meant in metal-complex compound five heteroatomss can with described metal M ion coordination.Similarly, " six teeth " be meant six heteroatomss in principle can with described metal M ion coordination.Yet we believe that bonding will not take place a heteroatoms in described complex compound in this case, thereby sexadentate ligand will become five tooth coordinations.

In general formula (VE), two heteroatomss link together by described bridging group W, and a coordination heteroatoms is included in three R ¹In each of group.Preferred described coordination heteroatoms is a nitrogen-atoms.

The part of general formula (VE) is at three R ¹Comprise at least one optional heteroaryl that replaces in each of group.Preferred described heteroaryl is pyridine-2-base group, particularly methyl-or the pyridine-2-base of ethyl-replacement.Preferred described heteroaryl is by alkylidene group, more preferably be connected on the N atom in the general formula (VE) by methylene radical.Most preferably described heteroaryl is for being connected in the 3-methyl-pyridine-2-base on the N atom by methylene radical.

Radicals R in the general formula (VE) ²Be replacement or unsubstituted alkyl, aryl or arylalkyl, or radicals R ¹But preferred R ²Be different from each R in the following formula ¹Group.Preferred R ²Be methyl, ethyl, benzyl, 2-hydroxyethyl or 2-methoxy ethyl.More preferably R ²Be methyl or ethyl.

Described bridging group W is selected from following replacement or unsubstituted alkylidene group :-CH ₂CH ₂-,-CH ₂CH ₂CH ₂-,-CH ₂CH ₂CH ₂CH ₂-,-CH ₂-C ₆H ₄-CH ₂-,-CH ₂-C ₆H ₁₀-CH ₂-and-CH ₂-C ₁₀H ₆-CH ₂-(wherein-C ₆H ₄-,-C ₆H ₁₀-and-C ₁₀H ₆-can be the ortho position-, contraposition-or position-C ₆H ₄-,-C ₆H ₁₀-and-C ₁₀H ₆-).Preferred described bridging group W is ethylidene or tetramethylene, more preferably ethylidene.

Pyridine pyridine-2-base, especially methyl-replacement or ethyl-replacement-2-base that preferred V representative replaces, most preferably V represents 3-picoline-2-base.

(F) be disclosed in ligand species among WO-A-98/39098 and the WO-A-98/39406

In by ligand L, metal M and the formed complex compound of coordination species X, the counter ion Y balance in the general formula (A1) electric charge z.Therefore, if electric charge z is a positive charge, then Y can be negatively charged ion, as RCOO ^-, BPh ₄ ^-, ClO ₄ ^-, BF ₄ ^-, PF ₆ ^-, RSO ₃ ^-, RSO ₄ ^-, SO ₄ ^2-, NO ₃ ^-, F ^-, Cl ^-, Br ^-Or I ^-, and R can be hydrogen, the optional alkyl that replaces or the optional aryl that replaces.If z is a negative charge, then Y can be common positively charged ion, as basic metal, alkaline-earth metal or (alkyl) ammonium cation.

Suitable counter ion Y comprises those ions of solid that cause generating the energy stably stored.Preferred counter ion are selected from R for preferred metal complex ⁷COO ^-, ClO ₄ ^-, BF ₄ ^-, PF ₆ ^-, RSO ₃ ^-(CF particularly ₃SO ₃ ^-), RSO ₄ ^-, SO ₄ ^2-, NO ₃ ^-, F ^-, Cl ^-, Br ^-And I ^-, wherein R represents hydrogen or optional phenyl, naphthyl or the C that replaces ₁-C ₄Alkyl.

Should recognize by suitable mode, comprise that original position method of formation (wherein the precursor conversion of described complex compound is the activated complex of general formula (A1) under the condition that stores or use) can form described complex compound (A1).The preferred complex compound that is generated is univocal complex compound or maybe can produces in the solvent mixture of species of ligand L in the salt that comprises metal M and ligand L.Perhaps described catalyzer can be generated by suitable complex compound precursor original position, generates as original position in solution that contains precursor substance or dispersion.In such embodiment, described active catalyst can the salt that comprises metal M and ligand L maybe can produce ligand L species mixture and in The suitable solvent original position generate.Therefore, for example if M is an iron, then molysite such as FeSO ₄Can in solution, mix the formation activated complex with the species that described ligand L maybe can produce ligand L.Therefore, for example can be from ligand L and metal-salt MX _nForm described composition in the mixture of (wherein preferred n=1-5, more preferably 1-3 in solution).In another such embodiment, described ligand L maybe can produce ligand L species can be present in metal M ion in dirt-carrying body or the washings and be mixed together with original position and form described active catalyst.The suitable species that can produce ligand L comprise metal-free compound or comprise the metal coordination complex that described ligand L also can be formed the activated complex of general formula (A1) by the metal M ionic replacement.

Amount at catalyzer described in the typical cleaning composition makes that usage quantity is 1 μ M to 50mM, makes that preferably the usage quantity of home laundry operation is the level of 10-100 μ M.

The pH of preferred washings is 6 to 13, more preferably 6 to 11, still more preferably 8 to 11, most preferably 8 to 10, particularly 9 to 10.

In the context of the present invention " bleaching " be interpreted as relating generally to spot or adhere to or other materials relevant with the dirt-carrying body decolour.Yet the present invention can consider to be applied to need to remove and/or by in the oxidation bleaching reaction and foul smell or other adhere to dirt-carrying body or other associated undesirable component parts.In addition, in the context of the present invention " bleaching " be interpreted as being confined to not need to exist light or carry out any bleaching mechanism of activatory or method by light.Therefore the present invention does not comprise based on various photo bleach compositions and the method using photobleaching catalyzer or photobleaching activator and have light.

According to the present invention, bleach systems one or both be substantially free of peroxygen bleachs in described detergent additive and the washings or peroxy or that produce peroxide takes this will play a major role by the catalytically bleaching of atmosphericoxygen or air.Yet, it will be appreciated that in this case as need as described in can comprise system a spot of hydrogen peroxide or peroxy or that produce peroxide in the composition.Therefore, " be substantially free of bleach systems peroxygen bleach or peroxy or that produce peroxide " and mean described composition and comprise based on oxygen molal weight meter 0 to 50%, preferred 0 to 10%, more preferably 0 to 5%, best 0 to 2% peroxygen bleach or bleach systems peroxy or that produce peroxide.But preferred described composition does not contain bleach systems peroxygen bleach or peroxy or that produce peroxide fully.

Thereby the bleaching of any dirt-carrying body of at least 10%, preferably at least 50%, best at least 90% realizes by being derived from airborne oxygen.

According to the present invention, preferred described detergent additive contains bleach systems peroxygen bleach or peroxy or that produce peroxide.Described peroxygen bleach can be a kind of compound that can produce hydrogen peroxide in the aqueous solution.Hydrogen peroxide cource is well-known in the art.It comprises alkali metal peroxide, various organo-peroxide (as urea peroxide) and various inorganic persalt (as alkali-metal perborate, percarbonate, superphosphate, persilicate and persulphate).The mixture of two or more of these compounds also suits.

Particularly preferably be four hydrated sodium perborates, especially sodium perborate monohydrate.Because sodium perborate monohydrate has higher active o content, thus preferred.For the also preferred SPC-D of the reason of environment aspect.Its amount in the present composition is usually in the scope of about 5 to 35% weight, preferred 10 to 25% weight.

The system of the generation hydrogen peroxide that another is suitable is C ₁-C ₄Alkanol oxydase and C ₁-C ₄The combination of alkanol, especially methanol oxidase (MOX) and alcoholic acid combination.These combinations are disclosed among the WO-A-9507972, by reference it are incorporated into herein herein.

The alkyl hydroxy superoxide is another kind of peroxy bleaching compound.These examples of material comprise cumene hydroperoxide and t-butyl hydroperoxide.

Organic peroxide acid is also suitable to described peroxy bleaching compound.These materials have following general formula usually:

Wherein R contains 1 alkyl to about 20 carbon atoms-or alkylidene group-or alkylidene group of replacing, and optional have a lactam bond; Or the phenylene of phenylene or replacement; With Y be hydrogen, halogen, alkyl, aryl, imino--aromatic group or non-aromatic group ,-COOH or-COOOH group or quaternary ammonium group.

The single peroxy acid of available typical case comprises herein, for example:

(i) peroxybenzoic acid and cyclosubstituted various peroxybenzoic acid are as peroxide-a-naphthoic acid;

The aliphatic series of (ii) various aliphatic series, replacement and arylalkyl list peroxy acid, as peroxide lauric acid, peroxide stearic acid and N, N-O-phthalic amido peroxide caproic acid (PAP); With

(iii) 6-octyl group amino-6-oxo-mistake oxy hexanoic acid.

Available typical case diperoxy acid herein comprises, for example:

(iv) 1,12-diperoxy dodecanedioic acid (DPDA);

(v) 1, the 9-diperoxyazelaic acid;

(vi) diperoxy brassylic acid, diperoxy sebacic acid and two peroxide m-phthalic acid;

(vii) 2-decyl diperoxy fourth-1,4-diacid; With

(viii) 4,4 '-alkylsulfonyl diperoxy phenylformic acid.

Various inorganic peroxy acid compounds, for example single potassium peroxide (MPS) also suits.If the organic or inorganic peroxy acid is as described peralcohol, then its amount is usually in the scope of about 2-10% weight, preferred 4-8% weight.

All these peralcohol can use separately, also can be with peroxyacid bleach precursor and/or organic bleaching catalyst of not containing transition metal unite use.

Generally described laundry additive composition can be mixed with aptly the peroxygen bleach that contains 2-35% weight, preferred 5-25% weight.

Various peroxyacid bleach precursors are known and are described in detail in the document, as see and be set forth in GB-A-836988, GB-A-864,798, GB-A-907,356, GB-A-1,003,310 and GB-A-1,519,351, DE-A-3,337,921, EP-A-0,185,522, EP-A-0,174,132, EP-A-0,120,591 and US-A-1,246,339, US-A-3,332,882, US-A-4,128,494, US-A-4,412,934 and US-A-4,675,393.

Another kind of available peroxyacid bleach precursor is cationic peroxyacid precursor, promptly as be disclosed in US-A-4,751,015 and US-A-4,397,757, EP-A-0,284,292 and EP-A-331, the peroxyacid precursor of 229 quaternary ammonium-substituted.The example of the peroxyacid bleach precursor of this type has:

Chlorination 2-(N, N, N-TMA (TriMethylAmine)) ethyl-4-sodium sulfonate benzol carbonate (SPCC);

The N-octyl group, N, N-dimethyl-N10-carbonization phenoxy group decyl ammonium chloride (ODC);

3-(N, N, N-TMA (TriMethylAmine)) propyl group-4-sodium sulfonate phenyl carboxylicesters; With

N, N, N-TMA (TriMethylAmine) toluyl oxygen base benzene sulfonate.

Another kind of special bleach precursor forms by various positively charged ion nitriles, as at EP-A-303, and disclosing in 520, EP-A-458,396 and EP-A-464,880.

Any of these peroxyacid bleach precursors all can be used among the present invention, though some of them are more more preferred than other.

In above-mentioned various bleach precursors, preferred kind has various esters (comprising Acylphenol sulphonate and acyl group alkylphenol sulphonate), various acid amides, and the peroxyacid precursor of various quaternary ammonium-substituted (comprising the positively charged ion nitrile).

The example of described preferred peroxyacid bleach precursor or activator has: 4 benzoic acid base benzene sulfonic acid sodium salt (SBOBS), N; N; N ' N '-tetra acetyl ethylene diamine (TAED), 1-methyl-2-benzoyloxy benzene-4-sodium sulfonate, 4-methyl-3-benzoyloxy Sodium Benzoate, chlorination 2-(N; N; the N-TMA (TriMethylAmine)) ethyl-4-sodium sulfonate benzol carbonate (SPCC), TMA (TriMethylAmine) toluene acyloxy-benzene sulfonate, acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (SNOBS), 3; 5, the positively charged ion nitrile of 5-trimethyl acetyl-phenolsulfonic acid sodium (STHOBS) and various replacements.

The consumption of described precursor can be at most described laundry additive composition weight 12%, be preferably 2-10%.

Method of the present invention specifically can be applicable to detergent bleaching, in cleaning in particular for laundry.Therefore, preferred described method is used the washings that contains surfactant, chooses wantonly and uses with washing assistant.

Optional described detergent additive also can comprise surfactant, and is optional with washing assistant.Described detergent additive can comprise its amount and be for example surfactant of 10-50% weight.

Described surfactant can be from natural (as soap), also can be from following synthetic: negatively charged ion, nonionic, both sexes, zwitter-ion, cation activity thing and various mixture thereof.Many suitable activess can be buied from the market, and detailed description is arranged in the literature, for example as seen are set forth in " the SurfaceActive Agents and Detergents " that shown by Schwartz, Perry and Berch, volume I and II.

An alkali metal salt of typical normally water miscible organic sulfuric acid of synthetic anionic surface-active substance and sulfonic acid (having about 8 alkyl to about 22 carbon atoms), term " alkyl " is used for comprising the moieties of senior aryl.The example of suitable synthetic anionic detergent compound has sodium alkyl sulfate and alkylsurfuric acid ammonium, especially by the senior (C to making from for example butter or Oleum Cocois ₈-C ₁₈) alcohol carries out those that sulfation obtains; Alkyl (C ₉-C ₂₀) benzene sulfonic acid sodium salt and alkyl (C ₉-C ₂₀) ammonium benzene sulfonate, particularly linear secondary alkyl (C ₁₀-C ₁₅) benzene sulfonic acid sodium salt; The alkyl glycerol ether sodium sulfate is especially derived from the ether of the higher alcohols of butter or coco-nut oil fatty acid monoglyceride sulfate and glycerine monosulfonic acid ester salt; Senior (C ₉-C ₁₈) sodium salt and the ammonium salt of sulfuric ester of Fatty Alcohol(C12-C14 and C12-C18) alkylene oxide (particularly oxyethane); Lipid acid such as coconut fatty acid employing isethionic acid carry out esterification and carry out the neutral reaction product with sodium hydroxide again; The sodium salt of the fatty acid amide of N-methyltaurine and ammonium salt; The alkane monosulfonate is as from alpha-olefin (C ₈-C ₂₀) react the product that obtains with sodium bisulfite; And from paraffin and SO ₂And Cl ₂React, being hydrolyzed with alkali then obtains those products of random sulphonate; (C ₇-C ₁₂) dialkyl sodium sulfosuccinate and (C ₇-C ₁₂) the dialkyl sulfosuccinate Succinic acid ammonium salt; And ethylenic sulfonate, this term is used for describing by making alkene, particularly (C ₁₀-C ₂₀) alpha-olefin and SO ₃React, then neutralization and the prepared material of hydrolysis reaction product.The preferred anionic surfactants detergent compound is (C ₁₀-C ₁₅) sodium alkyl benzene sulfonate and (C ₁₆-C ₁₈) sodium alkylether sulphate.

The example of available and the suitable non-ionic surface active compound that preferably uses with described anionic surfactant compound specifically comprises alkylene oxide (normally oxyethane) and alkyl (C ₆-C ₂₂) reaction product (being generally 5-25 EO, also is every mole of 5-25 ethylene oxide unit(s)) of phenol; And aliphatic series (C ₈-C ₁₈) condensation product (being generally 2-30 EO) of uncle or secondary straight or branched alcohol and oxyethane.Other so-called non-ionic surface active things comprise alkyl polyglycoside sugar ester, long-chain tertiary amine oxide, long-chain oxidation tertiary phosphine and dialkyl sulphoxide.

Both sexes or zwitterionic surface active cpd also can be used in the composition of the present invention, but because its cost is higher, so do not consider usually.If use any both sexes or zwitterionic detergent compounds, then the amount of the synthetic anionic of its more normal use of amount in composition and nonionic actives will be lacked.

Preferred described detergent additive comprises the anion surfactant of 1-15% weight and the nonionogenic tenside of 10-40% weight.In a preferred embodiment, described washing composition reactive systems does not contain C ₁₆-C ₁₂Fatty acid soaps.

Described detergent additive also can contain washing assistant, as containing the 5-80% weight of having an appointment, the preferred washing assistant of about 10-60% weight.

The washing assistant material can be selected from 1) the calcium sequestrant material; 2) deposited material; 3) calcium ion-exchanged material; With 4) above various mixtures.

Calcium sequestrant washing assistant examples of material comprises alkali metal polyphosphates (as tripoly phosphate sodium STPP); Nitrilotriacetic acid(NTA) and various water-soluble salt thereof; Below an alkali metal salt of various acid: carboxy methoxy-succinic acid, oxalic acid tetraacethyl, oxygen di-succsinic acid, mellitic acid, benzene polycarboxylic acid, citric acid; And as US-A-4, disclosed polyacetal carboxylic acid ester in 144,226 and US-A-4,146,495.

Precipitation washing assistant examples of material comprises sodium orthophosphate and yellow soda ash.

Calcium ion-exchanged washing assistant examples of material comprises various types of water-insoluble crystalline state or amorphous silicon aluminate, its mesolite is the best representative in known, as zeolite A, zeolite B (being also referred to as zeolite P), zeolite C, X zeolite, zeolite Y and P-type zeolite (as EP-A-0, described in 384,070).

Particularly, described detergent additive or washings can contain any of described organic and inorganic builders material, preferably need not or only use very a spot of phosphate builders for the reason of environment certainly.The typical washing assistant that can be used among the present invention is, the for example sodium salt of yellow soda ash, calcite/carbonate, nitrilotriacetic acid(NTA), Trisodium Citrate, carboxymethyloxymalo,ates, carboxy methoxy-succinic acid salt and water-insoluble crystalline state or amorphous silicon aluminate washing assistant material, its each all can be used as main washing assistant, can use separately, also can use as complementary washing assistant fusion with a spot of other washing assistants or polymkeric substance.

Preferred described detergent additive contain be no more than 5% weight, more preferably no more than 2.5% weight to the carbonate builders that is substantially zero (representing) with yellow soda ash, condition be described composition pH be up to 10 than the low alkalinity scope in.

Except the various components of having mentioned, described detergent additive or washings also can contain the additive of any routine, and its consumption is generally used for the amount in the detergent composition of fabric washing for these materials.The example of these additives comprises that buffer reagent (as carbonate), suds booster are (as alkanolamide, particularly derived from the single ethanol amide of palm kernel fatty acid and coconut fatty acid), froth suppressor (as alkyl phosphate and siloxanes), anti redeposition agent (as the alkyl cellulose ether of Xylo-Mucine and alkyl or replacement), stablizer (as various phosphoric acid derivatives, also be Dequest ^Type), fabric softener, inorganic salt and ealkaline buffer (as sodium sulfate and water glass), and amount white dyes, spices, enzyme (as proteolytic enzyme, cellulase, lipase, amylase and oxydase), sterilant and tinting material seldom usually.

Except the specific catalyst part, various transition metal chelators (as EDTA) and various phosphonate derivative are (as EDTMP, be ethylenediamine tetraacetic (phosphonic acids methylene ester)) also can be included, so that for example improve the responsive composition (as enzyme, white dyes and spices) of various stability, still keep bleaching validity but condition is described composition.Yet the preferred described detergent additive that contains catalyzer basically, does not more preferably contain transition metal chelator (except the described catalyst ligand) fully.

Various generic groups in entire description and claims, have been used, as alkyl, alkoxyl group, aryl.Except as otherwise noted, otherwise below be preferred group range, promptly can be applicable to the generic groups in the compound disclosed herein:

Alkyl: C1-C6-alkyl;

Alkenyl: C2-C6-alkenyl;

Cycloalkyl: C3-C8-cycloalkyl;

Alkoxyl group: C1-C6-alkoxyl group;

Alkylidene group: be selected from following group: methylene radical, 1,1-ethylidene, ethylene, 1,1-propylidene, propylene, trimethylene, 2,2-propylidene, fourth-2-alcohol-1,4-two bases, propan-2-ol-1,3-two bases and tetramethylene;

Aryl: be selected from molecular weight less than 300 same aromatic compound;

Arylidene: be selected from following group: 1,2-benzene, 1,3-benzene, 1,4-benzene, 1,2-naphthalene, 1,3-naphthalene, 1,4-naphthalene, 2,3-naphthalene, phenol-2,3-two bases, phenol-2,4-two bases, phenol-2,5-two base and phenol-2,6-two bases;

Heteroaryl: be selected from following group: pyridyl, pyrimidyl, pyrazinyl, triazolyl, pyridazinyl, 1,3,5-triazinyl, quinolyl, isoquinolyl, quinoxalinyl, imidazolyl, pyrazolyl, benzimidazolyl-, thiazolyl, oxazolidinyl, pyrryl, carbazyl, indyl and isoindolyl;

Heteroarylidene: be selected from following group: pyridine-2,3-two bases, pyridine-2,4-two bases, pyridine-2,5-two bases, pyridine-2,6-two bases, pyridine-3,4-two bases, pyridine-3,5-two bases, quinoline-2,3-two bases, quinoline-2,4-two bases, quinoline-2,8-two bases, isoquinoline 99.9-1,3-two bases, isoquinoline 99.9-1,4-two bases, pyrazoles-1,3-two bases, pyrazoles-3,5-two bases, triazole-3,5-two bases, triazole-1,3-two bases, pyrazine-2,5-two base and imidazoles-2,4-two bases;

Heterocyclylalkyl: be selected from following group: pyrrolinyl, pyrrolidyl, morpholinyl, piperidyl, piperazinyl, hexamethylene imine He oxazolidinyl;

Amine: group-N (R) ₂Wherein R independently is selected from following group separately: hydrogen, C1-C6-alkyl, C1-C6-alkyl-C6H5 and phenyl, wherein when two R are the C1-C6-alkyl two R can form together-NC3 is to-NC5 heterocycle, any remaining alkyl chain forms described heterocyclic alkyl substituent;

Halogen: be selected from F, Cl, Br and I;

Sulfonate radical: group-S (O) ₂OR, wherein R is selected from: hydrogen, C1-C6-alkyl, phenyl, C1-C6-alkyl-C6H5, Li, Na, K, Cs, Mg and Ca;

Sulfate radical: group-OS (O) ₂OR, wherein R is selected from: hydrogen, C1-C6-alkyl, phenyl, C1-C6-alkyl-C6H5, Li, Na, K, Cs, Mg and Ca;

Sulfone: group-S (O) ₂R, wherein R is selected from: hydrogen, C1-C6-alkyl, phenyl, C1-C6-alkyl-C6H5 and be selected from the amine (so that obtaining sulphonamide) of group-NR ' 2, wherein R ' independently is selected from hydrogen, C1-C6-alkyl, C1-C6-alkyl-C6H5 and phenyl separately, wherein when two R ' are the C1-C6-alkyl, two R ' can form together-and NC3 is to the heterocycle of-NC5, and any remaining alkyl chain forms described heterocyclic alkyl substituent;

Carboxylate derivatives: group-C (O) OR, wherein R is selected from: hydrogen, C1-C6-alkyl, phenyl, C1-C6-alkyl-C6H5, Li, Na, K, Cs, Mg and Ca;

Carbonyl derivative: group-C (O) R, wherein R is selected from: hydrogen, C1-C6-alkyl, phenyl, C1-C6-alkyl-C6H5 and be selected from the amine (so that obtaining acid amides) of group-NR ' 2, wherein R ' independently is selected from hydrogen, C1-C6-alkyl, C1-C6-alkyl-C6H5 and phenyl separately, wherein when two R ' are the C1-C6-alkyl two R ' can form together-NC3 is to the heterocycle of-NC5, any remaining alkyl chain forms described heterocyclic alkyl substituent;

Phosphonate radical: group-P (O) (OR) ₂, wherein R independently is selected from separately: hydrogen, C1-C6-alkyl, phenyl, C1-C6-alkyl-C6H5, Li, Na, K, Cs, Mg and Ca;

Phosphate radical: group-OP (O) (OR) ₂, wherein R independently is selected from separately: hydrogen, C1-C6-alkyl, phenyl, C1-C6-alkyl-C6H5, Li, Na, K, Cs, Mg and Ca;

Phosphine: group-P (R) ₂, wherein R independently is selected from separately: hydrogen, C1-C6-alkyl, phenyl and C1-C6-alkyl-C6H5;

Phosphine oxide: group-P (O) R ₂Wherein R independently is selected from separately: hydrogen, C1-C6-alkyl, phenyl and C1-C6-alkyl-C6H5, and the amine (so that obtaining aminophosphonic acid root (phosphonamidate)) that is selected from group-NR ' 2, wherein R ' independently is selected from hydrogen, C1-C6-alkyl, C1-C6-alkyl-C6H5 and phenyl separately, wherein when two R ' are the C1-C6-alkyl two R ' can form together-NC3 is to the heterocycle of-NC5, any remaining alkyl chain forms described heterocyclic alkyl substituent.

Except as otherwise noted, otherwise below be the group range that is more preferably, promptly can be applicable to the group in the compound disclosed herein:

Alkyl: C1-C4-alkyl;

Alkenyl: C3-C6-alkenyl;

Cycloalkyl: C6-C8-cycloalkyl;

Alkoxyl group: C1-C4-alkoxyl group;

Alkylidene group: be selected from following group: methylene radical, ethylene, trimethylene, fourth-2-alcohol-1,4-two bases and tetramethylene;

Aryl: be selected from following group: phenyl, xenyl, naphthyl, anthryl and phenanthryl;

Arylidene: be selected from following group: 1,2-benzene, 1,3-benzene, 1,4-benzene, 1,2-naphthalene, 1,4-naphthalene, 2,3-naphthalene and phenol-2,6-two bases;

Heteroaryl: be selected from following group: pyridyl, pyrimidyl, quinolyl, pyrazolyl, triazolyl, isoquinolyl, imidazolyl He oxazolidinyl;

Heteroarylidene: be selected from following group: pyridine-2,3-two bases, pyridine-2,4-two bases, pyridine-2,6-two bases, pyridine-3,5-two bases, quinoline-2,3-two bases, quinoline-2,4-two bases, isoquinoline 99.9-1,3-two bases, isoquinoline 99.9-1,4-two bases, pyrazoles-3,5-two base and imidazoles-2,4-two bases;

Heterocyclylalkyl: be selected from following group: pyrrolidyl, morpholinyl, piperidyl and piperazinyl;

Amine: group-N (R) ₂, wherein R independently is selected from following group separately: hydrogen, C1-C6-alkyl and benzyl;

Halogen: be selected from F and Cl;

Sulfonate radical: group-S (O) ₂OR, wherein R is selected from: hydrogen, C1-C6-alkyl, Na, K, Mg and Ca;

Sulfate radical: group-OS (O) ₂OR, wherein R is selected from: hydrogen, C1-C6-alkyl, Na, K, Mg and Ca;

Sulfone: group-S (O) ₂R, wherein R is selected from: hydrogen, C1-C6-alkyl, benzyl and be selected from the amine of group-NR ' 2, wherein R ' independently is selected from hydrogen, C1-C6-alkyl and benzyl separately;

Carboxylate radical derivative: group-C (O) OR, wherein R is selected from: hydrogen, Na, K, Mg, Ca, C1-C6-alkyl and benzyl;

Carbonyl derivative: group-C (O) R, wherein R is selected from: hydrogen, C1-C6-alkyl, benzyl and be selected from the amine of group-NR ' 2, wherein R ' independently is selected from hydrogen, C1-C6-alkyl and benzyl separately;

Phosphonate radical: group-P (O) (OR) ₂, wherein R independently is selected from separately: hydrogen, C1-C6-alkyl, benzyl, Na, K, Mg and Ca;

Phosphate radical: group-OP (O) (OR) ₂, wherein R independently is selected from separately: hydrogen, C1-C6-alkyl, benzyl, Na, K, Mg and Ca;

Phosphine: group-P (R) ₂, wherein R independently is selected from separately: hydrogen, C1-C6-alkyl and benzyl;

Phosphine oxide: group-P (O) R ₂, wherein R independently is selected from separately: hydrogen, C1-C6-alkyl, benzyl and be selected from the amine of group-NR ' 2, wherein R ' independently is selected from hydrogen, C1-C6-alkyl and benzyl separately.

The present invention now is further described by following non-restrictive example.

Embodiment

Following according to the acquisition of the method among EP-A-0909809 A FeMeN4Py.

Following on tea spot and tomato spot, the test by adopting iron complex FeMeN4Py to be blended into the effect of leading in washing as catalyst soakage cloth and with described catalyzer.

Be applied to the aqueous solution of catalyzer on the cotton sheet and make its dried overnight.Concentration is for making a slice cotton during be added to described master washes that the peak concentration of 10 μ M can be provided in washings.Adopt 3.5 g/l detergent bases (with 0.5%Dequest 2047 and 10%Na ₂CO ₃Back dosing) at 4 H (Ca ²⁺: Mg ⁺=2: 1) water (25 ℃) washs in stirring formula detersive power determinator (80opm).The cotton and the superoxide (feeding intake) that add painting catalyst on request by the calculating of 15% 1 hydration perborate.

The detergent base powder constituent is as follows:

Component	Umber (weight)
Component	Umber (weight)	LAS (linear alkylbenzene sulfonate)	?28
Sodium sulfate	?10.258	LAS (linear alkylbenzene sulfonate)	?28
Sodium sulfate	?10.258	STP	?28
Alkaline silicate	?9.9778	STP	?28
Alkaline silicate	?9.9778	White dyes	?0.24
EDTA	?0.009	White dyes	?0.24
EDTA	?0.009	SCMC (Xylo-Mucine)	?1.12
Water	?10.222	SCMC (Xylo-Mucine)	?1.12
Water	?10.222	Amount to	?87.627

Following measurement Δ E _Aw(aw=washs the back) value:

The washing back is with the described cotton of water rinse and subsequently at room temperature in the dark place drying, and described cotton is in the dark measured colour-change with Ultrascan Xe spectrophotometer (deriving from Hunterlab) behind the 24h.Colour-change (comprising bleaching) is by the Δ E that compares with the white cotton of cleaning _AwValue characterizes.Aberration (Δ E after the measured washing between cotton and the clean white cotton _Aw) be defined as follows:

Δ E _Aw=[(Δ L) ²+ (Δ is a) ²+ (Δ b) ²] ^1/2In the dark observed value poor between the white cotton of the cotton of Δ L after and cleaning wherein for washing; Δ a and Δ b are the two kinds of cottons observed value under redness and yellow poor respectively.About the measuring technology of this color, with reference to Commission International del ' Eclairage (CIE); Recommendation on Uniform Colour Spaces, aberration equation, mental measurement colour terminology, 2, the 15 phases of CIE Publication appendix, Colormetry, Bureau Central de la CIE, Paris 1978.

The results are shown in following table.

The mixed effect of iron complex FeMeN4Py in main washing that table 1. obtains by adopting the catalyst soakage cotton.

	E _aw
	E _aw		Tea	Pomarola
	Blank	20.9	Tea	Pomarola	?14.4
Superoxide	Blank	20.9	19.9	?14.6	?14.4
Superoxide	Catalyzer	21.1	19.9	?14.6	?3.1
Catalyzer/superoxide	Catalyzer	21.1	18.2	?1.7	?3.1

Claims

1. the method for a bleached woven fabric spot, described method is included under the existence of detergent additive, washs stained fabrics in aqueous cleaning solution, wherein:

Described detergent additive comprises the part that forms complex compound with transition metal, and described complex compound carries out catalytically bleaching by atmosphericoxygen to spot; With

In described detergent additive and the described washings one or both are substantially free of bleach system peroxygen bleach or peroxy or that produce peroxide.

2. the method for claim 1, a kind of in wherein said detergent additive and the described washings comprises bleach system peroxygen bleach or peroxy or that produce peroxide, be preferably hydrogen peroxide, and the another kind in described pre-treatment liquid and the described washings is substantially free of bleach system peroxygen bleach or peroxy or that produce peroxide.

3. the method for claim 2, wherein said detergent additive comprise bleach system described peroxygen bleach or peroxy or that produce peroxide.

4. claim 1 or 2 method, wherein said detergent additive is substantially free of bleach system peroxygen bleach or peroxy or that produce peroxide.

5. each method in the aforementioned claim, wherein said detergent additive comprises described complex compound on carrier.

6. according to the method for claim 5, wherein said carrier is for adopting the cloth of described complex compound dipping.

7. each method in the aforementioned claim, wherein said part forms the complex compound of following general formula:

[M _aL _kX _n] Y _mIn the formula:

L represents described part, or its protonated or deprotonation analogue;

X representative be selected from the anionic coordination species of any monovalence, divalence or trivalent and can with described metal with a tooth, bidentate or any neutral molecule of three tooth mode coordinate;

Y represents any non-coordinate counter ion;

A represents 1 to 10 integer;

K represents 1 to 10 integer;

N represents 0 or 1 to 10 integer;

M represents 0 or 1 to 20 integer.

8. each method in the aforementioned claim, wherein said part are five tooth parts of following general formula (IVE):

In the formula:

R ¹, R ²Independent separately representative-R ⁴-R ⁵

R ⁴Independent separately singly-bound or optional alkylidene group, alkylene group, oxygen base alkylidene group, amino alkylidenyl, alkylene ether, carboxylicesters or the carboxylic acid amide that replaces represented; With

9. each method in the aforementioned claim, wherein said part is N, two (pyridines-2-base-methyl)-1 of N-, two (pyridine-2-the yl)-1-ethylamines of 1-.

10. each method in the claim 1 to 9, wherein said pretreatment compositions comprises the preformed complex of described part and described transition metal.

11. each method in the claim 1 to 10, wherein said pretreatment compositions comprise and the free ligand that is present in the transition metal complex in the described washings.

12. each method in the claim 1 to 10, wherein said pretreatment compositions comprise and the free ligand that is present in the transition metal complex in the described spot.

13. each method in the claim 1 to 10, wherein said pretreatment compositions comprise free ligand or commutable metal-ligand complex of transition metal and transition metal source.