CN1074237A

CN1074237A - Bleach activation

Info

Publication number: CN1074237A
Application number: CN92115249A
Authority: CN
Inventors: R·海格
Original assignee: Unilever NV
Current assignee: Unilever NV
Priority date: 1991-12-20
Filing date: 1992-12-19
Publication date: 1993-07-14
Also published as: MX9207471A; KR930012103A; EP0549272A1; GB9127060D0; NO924895L; JPH05263098A; CA2085720A1; AU3029792A; BR9205100A; ZA929851B; KR960002630B1; KR930013079A; ZA929850B; TW232706B; GB9204706D0; NO924895D0

Abstract

The bleaching catalyst that comprises the complex compound of molecular formula (I),

[LMnX _p] ²Y _q(I)

Wherein: Mn is II, the manganese of III or IV oxidation state, and X represents coordination or bridging atom; P is 1-3 integer, and Y is a counterion, and its form depends on the electric charge Z of complex compound, can be positive number, zero or negative; Q=Z[electric charge Y]; And L encircles organic molecule coordination body greatly.

Description

Bleach activation

The present invention relates to use superoxide, comprise hydrogen peroxide or can in the aqueous solution, discharge the hydrogen peroxide adduct of hydrogen peroxide, and the activation of the SYNTHETIC OPTICAL WHITNER of peroxy acid; The compound of relevant activation or catalysis peralcohol; The relevant detergent bleach compositions that comprises the catalyzer that contains the catalysis superoxide; And the above-mentioned various forms composition of mentioning of relevant use is bleached and/or the method for detergent.Particularly, the present invention relates to of the new application of the manganese complex of particular variety as the effective catalyst of the bleach activation of peroxide bleaching agent

The general formula of complex compound is as follows:

Wherein Mn can be an II, III, the manganese of IV or V oxidation state, or their mixture; N and m are respectively the integers of 1-4, and X represents coordination or bridging atom; P is the integer of 0-12, and Y is a counterion, and its type depends on the electric charge Z of complex compound; Z is the electric charge of complex compound, be just, zero or negative integer; Q= ^Z/ [electric charge Y]; L is the following macrocycle molecule ligand of molecular formula:

R wherein ¹And R ²Each is zero, H, the alkyl that can replace arbitrarily; Each D is respectively N, NR, and PR, O or S, wherein R is H, any aryl that replaces, alkyl; Be described in EP-A-O, in 458,397, as effective catalyst with the peralcohol bleaching.Though this definition has promptly covered monokaryon and has covered polynuclear complex again, do not mention the monokaryon manganese complex in the specification sheets and point out that clearly preferred material is that multinuclear manganese complex, particularly general formula are the two nuclear manganese complexs of (A), wherein n and m are 〉=2.

The following monokaryon manganese of structural formula has been described in U.S.'s pending application application 798396.

Wherein Mn is+manganese of 4 oxidation state; R is the C that is selected from alkyl, cycloalkyl, aryl, benzyl ₁-C ₂₀Group and their groups of combining;

At least two R bases also can link mutually.So that the bridge unit between formation and two Sauerstoffatoms of manganese coordinate; L is selected from the C that has three and manganese coordinate nitrogen-atoms at least ₃-C ₆₀The ligand of group; Y is the stable counterion of oxidation state; They all are used as bleaching catalyst.

Now be surprised to find other monokaryon manganese co-ordination complex that general formula is following:

Wherein Mn can be II, III or IV oxidation state; X represents coordinating group, for example Cl ^-, Br ^-, I ^-, F ^-, NCS ^-, N ^- ₃, I ^- ₃, NH ₃, NR ₃, RCOO ^-, RO ^-,

; RSO ^- ₃, RSO ^- ₄, wherein R is hydrogen, alkyl, aryl, they all are to replace arbitrarily, or R ' COO ^-, wherein R ' is an alkyl or aryl, they all can replace arbitrarily, OH ^-, O ^2- ₂, O ^2-, HOO ^-, H ₂O, SH, CN ^-, OCN ^-, S ^2- ₄With their mixture; P is the integer of 1-3; Z represents the electric charge of complex compound, can be positive number, and zero or the integer of negative; Y is a counterion, and its type depends on the electric charge z of complex compound; Q= ^Z/ [electric charge Y]; Reaching L is ligand,

Be the following big ring organic molecule of structural formula:

Wherein t is the integer of 2-3, and S is the integer of 3-4, and u is 0 or 1, and R ¹, R ²And R ³Each is respectively from H, alkyl, and aryl, the two all can replace arbitrarily, middle selection, but when p was 3, Mn was the manganese of IV oxidation state; X can not be RO ^-; This complex compound also can be used as the bleaching catalyst of superoxide, and EP-A-O, and two nuclear manganese complexs in 458,397 and EP-A-O, 458,398 are equally effective.

The selection of X is not too crucial to activity of such catalysts, but is important to the physical property of complex compound, for example solvability and stability.

Preferred ligand is t=2, s=3, u=1, R ¹, R ², R ³Each is respectively H or CH ₃, R wherein particularly ¹And R ²All be H, R ³=CH ₃Those.

The example of preferred ligand is 1,4,7-7-triazacyclononane (TACN); 1,4,7-trimethylammonium 1,4, the 7-7-triazacyclononane (1,4,7-Me ₃TACN); The 2-methyl isophthalic acid, 4,7-7-triazacyclononane (2-Me-TACN); With 1,2,4,7-tetramethyl--1,4,7 7-triazacyclononanes (1,2,4,7-Me ₄TACN); With 1,2,2,4,7-pentamethyl--1,4,7 7-triazacyclononanes (1,2,2,4,7-Me ₅TACN); 2-benzyl-1,4,7-trimethylammonium-1,4,7-7-triazacyclononane; With 2-decyl-1,4,7-trimethylammonium-1,4,7-7-triazacyclononane.

The above-mentioned ligand of mentioning can be synthetic with the method for 1982,21 3086 pages of the Inorganic Chemistry that is disclosed in K.Wieghardt etc., quotes at this as a reference.

The example of the complex compound that is suitable for is:

＝[（1，4，7-Me ₃TACN）Mn ^Ⅲ（N ₃） ₃]

（5）

＝[（1，4，7-Me ₃TACN）Mn ^Ⅲ（SCN） ₃]

（6）

＝[（1，4，7-Me ₃TACN）Mn ^ⅡS ₄OH ₂]

(7) [(1,4,7-Me ₃TACN) Mn(AcAc) (Eto)] BPh ₄Wherein AcAc is an acetylacetonate

The preparation and the synthetic method that are applicable to some complex compounds of bleaching catalyst of the present invention are described below:

Synthesizing of complex compound (4) and complexing (5):

At room temperature solid sodiumazide (0.5 gram) or sulphur (generation) Zassol are added to [Mn ^III ₂(μ-and o) (μ-oAc) ₂(1,4,7)-Me ₃TACN) ₂] (ClO ₄) ₂In (0.5 gram is dissolved in 30 milliliters of ethanol), and stir.Small red-brown crystalline material is precipitated out (productive rate 0.3-0.4 gram).

(Inorg.Chim such as K.Wieghardt, Acta, 126,39(1987)).

Synthesizing of complex compound (6):

Be dissolved in the Mn(oAc in the methyl alcohol) ₃2H ₂O(1 restrains) and 1,4,7-Me ₃The TACN(1 gram) solution at room temperature stirs 30 minutes adding (NH afterwards under argon atmospher ₄) ₂The S(2 milliliter, 40%) the aqueous solution.Under the decompression situation, volume is reduced to 15 milliliters, and in refrigerator, placed 24 hours, form the pale yellow crystal, collect, productive rate 0.48 gram with filter method.

(Inorg.Chim.Acta such as K.Wieghardt, 126,39(1987)).

Synthesizing of complex compound (2):

At room temperature 10 concentrated hydrochloric acids are added to [Mn ^III ₂(μ-o) (oAc) ₂(1,4,7)-MeTACN) ₂] (ClO ₄) ₂(1 gram is dissolved in 20 milliliters of CH ₃Among the CN) solution in, productive rate 0.25 gram.

(K.Wieghardt etc., J.Am, Chem, Soc, 170,7398(1988)

Synthesizing of complex compound (3): [MnTACNMn ^II(CH ₃) ₃] (ClO ₄) ₂:

0.5 milliliter of ammoniacal liquor and 0.5 gram 1,4 under argon atmospher, 7-Me ₃TACN is dissolved in 15 ml methanol, is dissolved in 1.0 gram Mn(ClO of 15 ml methanol following of argon atmospher ₄) ₂Be added in this solution, under argon atmospher, isolate white precipitate.

Synthesizing of complex compound (7):

0.5 restrain 1,4,7-Me ₃TACN is dissolved in 25 milliliters of ethanol, after this adds 1.35 gram Mn(AcAc) ₃, the mixture of stirring generation is 30 minutes then.Add the sodium tetraphenylborate of 0.7 gram that is dissolved in 20 ml waters, form yellow-green precipitate, leach precipitation, and dry in a vacuum (productive rate 1.4 grams).

(K Wieghardt etc., Z Naturforsch, 436,1184-1194,1988).

These pure crystalline materials of application of replacing are by Mn salt, as Mn(NO ₃) ₂Be added in the acidic solution of ligand, for example 1,4,7-Me ₃Can obtain monokaryon manganese complex of the present invention in the acid solution of TACN and be the solution shape.This solution that obtains can be added in the liquid lime chloride that contains superoxide, to obtain and the similar product of isolated Mn-complex compound.

Found the special applications of monokaryon manganese complex of the present invention in bleaching composition.

Therefore, another aspect of the present invention has provided the bleaching composition of the complex compound of the molecule formula I that comprises superoxide and aforementioned definitions.The best combination thing also contains surfactant, detergent additive, for example synergistic agent.

The advantage of bleaching catalyst of the present invention is to have hydrolysis and oxidative stability and effective in various detergent formulation.Catalyzer of the present invention has increased hydroperoxide and the organic and bleaching action inorganic peroxide SYNTHETIC OPTICAL WHITNER.

Further surprising characteristics are bleaching catalyst and various detersive enzyme, proteolytic enzyme for example, and cellulase, lipase, amylase, oxydase etc. are common to be used.

Bleaching composition of the present invention comprises that to the staining agent of wide scope hydrophilic and hydrophobic staining agent is effective.

Therefore, further, the invention provides the method for bleaching and dyeing material.This method comprises to be used from comprising hydrogen peroxide, discharges or the generation peroxide compound peroxy acid or their salt, the SYNTHETIC OPTICAL WHITNER of selecting in peroxy acid bleach precursor and their mixture; The manganese complex of the molecule formula I of aforementioned definitions contacts the method for coloring material in aqueous medium, every kind significant quantity that cooperatively interacts each other and the cleaning action that provides material are provided.

Represent that with 1,000,000/(ppm) terms of the manganese in the aqueous bleaching solution the common scope of the significant quantity of complex compound is 0.001ppm～100ppm, preferred 0.01ppm～20ppm, most preferably 0.1ppm～10ppm.Application in industrial bleaching technology may need higher amount, for example weaving and association with pulp bleaching.The low amount of listing is main purpose and uses best in the family expenses laundry operations.

The SYNTHETIC OPTICAL WHITNER that comprise superoxide and the composition of bleaching catalyst of pH scope between 7-13 is effectively, and preferred pH scope is between the 8-11.

As mentioned above, can use peroxy bleaching compound to comprise hydrogen peroxide, discharge the compound of hydrogen peroxide, produce the system of hydrogen peroxide at bleaching composition of the present invention and detergent bleach compositions, peroxy acid and its salt, peroxy acid bleach precursor systems and their mixture.

Hydrogen peroxide cource is known in the prior art, they comprise alkali metal peroxide, the organo-peroxide bleaching compounds, for example urea peroxide reaches inorganic persalt bleaching compounds, for example alkali metal perborate, percarbonate, persulphate, persilicate and superphosphate also can use the mixture of two or more these compounds.Particularly preferably be SPC-D and Sodium peroxoborate, particularly the Sodium peroxoborate monohydrate.The Sodium peroxoborate monohydrate is better than sodium perborate tetrahydrate, and this is because its fabulous storage stability and its characteristic that rapid dissolved ability combines in the SYNTHETIC OPTICAL WHITNER aqueous solution.From the environment viewpoint, Sodium peroxoborate is preferred.

The alkyl hydroxy superoxide is another kind of peroxide bleaching agent.These examples of substances comprise cumene hydroperoxide and t-butyl hydroperoxide.

Organic peroxide acid also is suitable as peroxide bleaching agent.These materials have following general formula usually:

Wherein R is the thiazolinyl or the substituted alkenyl of 1-20 carbon atom, and it selectively has a lactam bond; Or benzene or substituted-phenyl; And Y is hydrogen, halogen, alkyl, aryl, aromatics or non-aromatics imino-, COOH or

Base or quaternary ammonium group.

Comprise at this useful typical single peroxy acid, for example

ⅰ) benzoyl hydroperoxide and cyclosubstituted benzoyl hydroperoxide, for example peroxide-α-Nai Jiasuan;

ⅱ) aliphatic series replaces aliphatic series and aralkyl list peroxy acid, peroxide lauric acid for example, peroxide stearic acid and N, N-phthalamide peroxide sour (PAP) and

ⅲ) 6-octylame-6-oxo-peroxide acid.

Comprise in this typical useful diperoxy acid, for example:

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

ⅴ) 1,9-two ground oxygen nonane diacids;

ⅵ) diperoxy brassylic acid (undecane dicarboxylic acid); Diperoxy sebacic acid and diperoxy m-phthalic acid;

ⅶ) 2-decyl peroxide butane-1, the 4-diacid;

ⅷ) 4,4 '-the two benzoyl hydroperoxides of alkylsulfonyl.

The inorganic peroxy acid compound also is suitable for, for example Potassium peroxysulfate (MPS).

All these superoxide can use separately or and the peroxyacid bleach precursor use that combines.Using the advantage of peroxy acid bleach precursor is to improve the overall whiteness of white fiber.

These materials also can use, and this is because in addition they can make the material of handling meet the health care requirement.

The peroxy acid bleach precursor is known and fully describes in the literature, for example is described in GB836,988, and GB864,798, GB907,356, GB1 is in 003,310 and GB1519,351.DE3,337,921; EP0,185,522; EP0,174,132 and EP0,120,591 and US1246,339, US3,332,882; US4,128,494, US4 is in 412,934 and US4,675,393.

The kind of useful in addition peroxyacid bleach precursor is the peroxyacid precursor of quaternary ammonium-substituted.They are disclosed in US4, and 751,015 and US4397,757, and EP284292, EP331 is in 229 and EP303,520.The example of this class peroxyacid precursor is:

2-(N, N, N-trimethyl ammonium) ethyl-4-sulfophenyl carbonate-(SPCC);

Chlorination N-octyl group N, N-dimethyl-N-10-carbonyl benzene oxygen decyl ammonium (ODS);

3-(N, N, N-Trimethylamine) propyl group sodium-4-sulfonyl-phenyl carboxylate salt and N, N, N-Trimethylamine toluene acyl-oxygen benzene sulfonate.

Another special positively charged ion peroxyacid bleach precursor is formed by the positively charged ion nitrile, and they are disclosed in EP303520, and EP458 is in 396 and EP464,880.

In these peroxyacid bleach precursors any one can be used in the present invention; preferred material is an ester in the above-mentioned bleach precursor; comprise Acylphenol sulphonate and acyl group alkylphenol sulphonate, the acyl group acid amides comprises the peroxyacid precursor of the quaternary ammonium-substituted of positively charged ion nitrile.

The example of preferred peroxyacid bleach precursor or activator is a 4-benzene oxygen 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-benzoylbenzoic acid sodium; SPCC; Trimethylamine benzoyl oxygen benzene sulfonate; Nonanoyl oxygen benzene sulfonic acid sodium salt (SNOBS); 3,5,5-trimethyl acetyl oxygen benzene sulfonic acid sodium salt (STHOBS); With the positively charged ion nitrile that replaces.

The material of particularly suitable is to be described in EP453,003 and EP4461982 in be called the sulfimide material.

Detergent bleach compositions of the present invention can be by the component preparation that mixes significant quantity.Use means when the mixture that produces and water mix at this term " significant quantity " and forms solution medium, and can be used to washing and cleaning cloth, and when fiber and other goods, the amount that each composition exists can reach expection and render a service.

Particularly, detergent bleach compositions can be mixed with and contain for example about 2%～30% weight, preferably the peralcohol of 5-25% weight.

Amount at some situation use peroxy acid can be slightly lower, for example about 1%-15%(weight), be preferably 2%～10%(weight).

Peroxyacid precursor can use together with peralcohol, and its amount is similar to the amount of peroxy acid, i.e. 1%-15%(weight), be preferably 2%-10%(weight).

The amount of the complex compound that exists in SYNTHETIC OPTICAL WHITNER and detergent bleach compositions provides amount required in wash water solution.Usually, manganese content is the about 0.5%(weight of 0.0005%-in prescription), be preferably 0.001%-0.25%(weight).

When using low dosage in detergent bleach compositions, for example the dosage of Japan and U.S. human consumer use is about the 1-2 grams per liter respectively, and manganese content is 0.0025-0.5%(weight in the prescription), be preferably 0.05-0.25%.Use higher product dosage, european consumer for example, manganese content 0.0005-0.1%(weight in the prescription), be preferably 0.001-0.05%.

Bleaching catalyst of the present invention can match with any known and common tensio-active agent and washing synergistic agent basically.

Surfactant can be natural deutero-, soap for example, or from negatively charged ion, nonionic, both sexes, zwitter-ion is selected in cationic active material and their mixture.Many suitable active substances can obtain from commerce and narrate in the literature.For example at Schwartz, in Perry and Berch " Surface Active Agents and Detergente " volume I and the volume II.The total amount of surfactant can be the 0.5%-50%(weight of composition), preferably be about 1%-40%(weight), 4-25%(weight most preferably).

Normally organic vitriolic water-soluble alkali metal salts of synthetic anion surfactant and sulfonate with the alkyl that contains 8～22 carbon atoms.Use is the moieties that comprises senior aryl at this term alkyl.

The example of the synthetic anionic washing compound that is suitable for is the sodium and the ammonium salt of alkylsurfuric acid, and particularly those are by the senior (C of sulfation ₈-C ₁₈) alcohol obtains, for example obtain from fatty oil or Oleum Cocois; Alkyl (C ₉-C ₂₀) benzene sulfonic acid sodium salt and ammonium, particularly linear branched-chain alkyl (C ₁₀-C ₁₅) benzene sulfonic acid sodium salt; Alkyl glycerol base ether sodium sulfate is particularly from the ester of fatty oil or Oleum Cocois deutero-higher alcohols and the synthol that obtains from oil; Coco-nut oil fatty acid list glycerine sodium sulfate and sodium sulfonate; Senior (C ₉-C ₁₆) sodium salt and the ammonium salt of sulfuric ester of reaction product of Fatty Alcohol(C12-C14 and C12-C18) olefinic oxide, particularly oxyethane.The reaction product of lipid acid is for example used isethionic acid esterification lipid acid, as coco-nut oil fatty acid, and with sodium hydroxide neutral reaction product; The sodium of N-methyltaurine fatty acid amide and ammonium salt; Alkane list sulphonate is for example from alpha-olefins (C ₉-C ₂₀) and sodium sulfite reaction obtain with paraffinic hydrocarbons and SO ₂And Cl ₂The sulphonate arbitrarily that reaction produces with basic hydrolysis then obtains; C ₇-C ₁₂The sulfo-sodium succinate and the ammonium of dialkyl group; Alkene sulphonate, its term are used for describing by alkene, special C ₁₀-C ₁₂Alpha-olefins and SO ₃Reaction, the material of neutralization then, the preparation of hydrolysis reaction product.The preferred anionic surfactants detergent compound is (C ₁₁-C ₁₅) sodium alkyl benzene sulfonate, (C ₁₆-C ₁₈) sodium alkyl sulfate and (C ₁₆-C ₁₈) sodium alkylether sulphate.

The example of spendable suitable non-ionic surface active compound comprises, particularly oxyalkylene, normally oxyethane and alkyl (C ₆-C ₂₂) reaction product of phenol, 5-25EO is arranged usually, promptly each molecule has the unitary ethylene oxide unit of 5-25.Aliphatic series (C ₈-C ₁₈) primary, the product of secondary linearity or branched-chain alcoho and oxyethane, 3-30EO is arranged usually and by the product of oxyethane and propylene oxide and reacting ethylenediamine product condensation prepared.Other the ionic surfactant pack that is called is drawn together the alkyl polysaccharide glucoside, long chain tertiary amine oxide compound, long chain tertiary phosphine oxide and dialkyl sulphoxide.

A certain amount of both sexes or zwitter-ion surface active cpd also can use in composition of the present invention.But this is unwanted usually, and this is because their cost is higher relatively.If use both sexes or zwitterionic detergent compounds, the synthetic negatively charged ion and the tween of relative more frequent use, its amount in composition is seldom.

As mentioned above, soap also can mix in the composition of the present invention, if but long-chain C ₁₆-C ₂₂The bleachability that the amount of fatty acid soaps maintains minimum bleaching and detergent bleach compositions improves.Can contain short chain C ₁₂-C ₁₄The amount of fatty acid soaps preferably is no more than about 10%(weight).

The content height that has also confirmed anion surfactant can reduce bleachability to being lower than optimum level.

Detergent bleach compositions comprises surfactant preferably, hydroperoxide SYNTHETIC OPTICAL WHITNER, the complex compound of the logical formula I of aforementioned definitions, the nonionogenic tenside of the anion surfactant of 0～25% weight and 7.5-55% weight.Nonionogenic tenside is 0.75 to the weight ratio of anion surfactant at least.

Detergent bleach compositions of the present invention generally also contains the washing synergistic agent.The washing builder material can be from the sequestrant of calcium, and precipitation agent is selected in calcium ion-exchanged agent and their mixture.

The example of calcium chelating synergistic agent comprises the basic metal high phosphate, as is described in US4, the Tri sodium Phosphate in 144,226, and US4,146,495, nitrilotriacetic acid(NTA) and its water-soluble salt; The polycarboxylic an alkali metal salt of ether is as the carboxymethoxyl Succinic Acid; Hydroxyl two Succinic Acid, mellitic acid; Ethylenediamine tetraacetic acid (EDTA); The benzene polycarboxylic acid; Citric acid and polyacetal carboxylation.

The example of precipitation synergistic agent comprises sodium orthophosphate, yellow soda ash, yellow soda ash/calcite.

The example of calcium ion-exchanged synergistic agent comprises crystallization of various forms water-insoluble or unsetting aluminosilicate, and its mesolite is the example of knowing.

Especially, composition of the present invention can contain any organic or inorganic synergistic agent, for example Tri sodium Phosphate or potassium, trisodium phosphate or potassium, sodium orthophosphate or potassium, the mixture of yellow soda ash or yellow soda ash/calcite mixture, sodium nitrilo triacetate salt, Trisodium Citrate, carboxymethyl propanedioic acid, carboxymethyl oxysuccinic acid salt and water-insoluble crystallization or amorphous manosil AS synergistic agent or their mixture.

If the use phosphate builder is a SYNTHETIC OPTICAL WHITNER with peroxy acid preferably.

The amount of spendable synergistic agent for example is 5～80%(weight), preferred 10-60%(weight).

Cleaning composition of the present invention also can contain a regularly habitual additive.These materials are used in the cleaning composition of washing the fibre usually.The example of these additives comprises buffer reagent, as carbonate, profoamer is as alkanolamide, particularly single alcohol amide, they are from palm kernel fatty acid and coconut fatty acid deutero-, froth suppressor, for example alkylphosphonic and siloxanes, anti-redeposition agent, the ether of cellulose of Xylo-Mucine and alkyl or substituted alkyl for example, other stablizer, for example ethylenediamine tetraacetic acid (EDTA) (EDTA) and phosphoric acid derivatives (are Dequst ^RType) softening agent for fibres, inorganic salt, sodium sulfate for example, normally used amount fluorescent agent seldom, spices, enzyme, proteolytic enzyme for example, cellulase, lipase, amylase, and oxydase, sterilant and staining agent.

These additives, transition metal chelator, routine EDTA and phosphoric acid derivatives are particularly importants as quadrol-four-(methylene radical phosphoric acid salt) EDTMP.

Can select in addition be not the additive of normal needs with multi-functional characteristic be the polymkeric substance of molecular weight from 1000-2000000, and can be vinylformic acid, toxilic acid, or their ester or acid anhydride, vinyl pyrrolidone, but methyl-or ethyl-Vinyl Ether and the monomeric neat or multipolymer of other polyvinyl, the preferred example of these polymkeric substance is polyacrylic acid or polyacrylic ester; Polymaleic acid/acrylic copolymer; 7: 30 vinylformic acid/hydroxyethyl maleate copolymers; 1: 1 vinylbenzene/maleic acid; Iso-butylene/toxilic acid and diisobutylene/maleic acid; Methyl and ethyl-vinyl ether/maleic acid; Ethene/maleic acid; Polyvinylpyrolidone (PVP); Vinyl pyrrolidone/maleic acid, the normally used amount of this polymeric additive are about the about 3%(weight of 0.1%-).

When using hydroperoxide, for example Sodium peroxoborate or SPC-D, during as SYNTHETIC OPTICAL WHITNER, if being in, the pH in the composition is lower than alkaline range up to 10 situation, contain in the composition and be no more than 5%(weight) carbonate, if yellow soda ash, more preferably no more than 2.5%(weight) up to being 0 substantially.

Detergent bleach compositions of the present invention, when being mixed with free flowable particle, for example powder or granulated form can be by any preparations in the ordinary skill that uses in the preparing washing composition process.For example first slurrying, spray are subsequently done forming the former powder of washing composition, join in the former powder as dry-matter comprising general additive and these heat-sensitive ingredients of complex compound of peroxide bleaching agent.

The former powder composition itself of washing composition of answering correct understanding to mix complex compound can prepare with various other methods; for example be called the part partition method; non-tower mode is processed, and does and mixes, and is coalescent; briquetting; granulation is extruded, compacting and enrichment technology etc.; these technology are known in the prior art, are not cores of the present invention.

Complex compound can be added to respectively in the washing/Javelle water that contains peroxygen bleach on the other hand.

In this case, complex compound is to be included in the washing affixture, expect that this affixture replenishes and increase the effect of general cleaning composition, and can contain any in those composition components, though they do not comprise component whole of full formula cleaning composition.Affixture by spirit of the present invention is added in the aqueous solution that contains (alkali) source of hydrogen peroxide usually, though under some situation, affixture is handled respectively in prewashing or rinsing and used.

Affixture by spirit of the present invention can comprise complex compound separately, or best and carrier combination, for example compatible water or non-aqueous liquid media, or granulation material or plastic non-particulate material.

The granulation examples of substances that can join comprises inert substance, and for example clay and other aluminosilicate comprise the zeolite of natural and synthetic generation.Other the particulate vector material that can join comprises hydratable inorganic salt, for example carbonate and vitriol.

Complex compound also can be made into the detergent bleach compositions of other product form, thin slice for example, tablet, the liquid detergent compositions of rod and liquid and granular non-aqueous solution.

Those can comprise that the non-aqueous solution liquid detergent compositions of complex compound is known in the prior art, and various prescriptions are suggested; For example at US2,864,770; US3,368,977; US4,772,412; GB1,205,711; GB1,370,377; GB2,914,536; DE-A-2 is in 233,771 and EP0,028,849.

These compositions are to generally include the non-aqueous solution liquid medium, are with or without the composition that solid phase is disperseed thing.The non-aqueous solution liquid medium can be liquid surfactant, preferably liquid nonionic surfactants; Non-polar liquid body medium, i.e. liquid paraffin; Polar solvent, alcohol how for example, as glycerine, sorbyl alcohol, ethylene glycol, lower molecular weight single hydroxyl alcohol arbitrarily, for example ethanol or Virahol, or the use that combines of their mixture.

Solid phase can be a synergistic agent, alkali, abrasive material, polymkeric substance, clay, other solid ion tensio-active agent, SYNTHETIC OPTICAL WHITNER, fluorescent agent and other useful solids wash composition.

The present invention will be illustrated by following embodiment:

Embodiment 1

Following embodiment is being equipped with the quartzy heating of temperature control spiral tube, and magnetic stirring apparatus carries out in the Glass Containers of thermopair and PH electrode.

Under 40 ℃ of isothermals, PH is 10, experimentize in the softening water, measures peroxyboric acid monohydrate (PBM) and as bleach catalysts monocycle complex compound standard is caught dark brown experiment bleaching of cloth performance.

It is 8.6 mmoles/rise PBM that bleach system in the washing soln is added with concentration, if the dosage of detergent bleach prescription is 6 grams per liters, should be the PBM of 14.3% weight mutually.

Experiment cloth soaked 30 minutes in every kind of example composition, used the tap water rinsing, and is dry in rotary drum drier, measures reflectivity (R before and after handling on Zeiss Elrephometer _460*).Difference (the △ R of value _460*) provide the degree of functioning of processing.

Outcome record under tabulate in 1

If the dosage of bleaching composition is 69/L, the amount of monokaryon Mn complex compound is 0.03% with respect to the weight of catalyzer

Experiment (A) (B) and (C) is a thing in contrast, and The above results clearlys show monokaryon manganese co-ordination complex (2), (3), (4), (5) and (7) are at least and be described in EP-A-458, the catalyzer of binuclear complex preferably [Mn in 397 and EP-A-458,398 ^IV ₂(μ-O) ₃(1,4,7-Me ₃TACN) ₂] (PF ₆) ₂Equally effective.

Claims

1, the bleaching catalyst that contains logical formula I:

Wherein:

Mn is an II, the manganese of III or IV oxidation state;

The X representative is from Cl ^-, Br ^-, I ^-, F ^-, NCS ^-, I ₃ ^-,-OH, O ₂ ^2-, O ^2-, HOO ^-, H ₂O, SH, CN ^-, OCN ^-, S ₄ ^2-, NH ₃, NR ₃, RCOO ^-, RO ^-,

RSO ₃ ^-And RSO ₄ ^-The middle coordinating group of selecting, wherein R can replace arbitrarily from hydrogen, alkyl, aryl, both, and R ' COO ^-The middle selection, wherein R ' is from alkyl, aryl, the both can replace arbitrarily, and selects in their mixture;

P is the integer of 1-3;

Z is the electric charge of complex compound, and can be positive and negative integer or zero;

Y is a counterion, and its form depends on z;

Q= ^Z/ [electric charge Y];

L is the following big ring organic molecule coordination body of molecular formula:

Wherein:

T is the integer of 2-3;

S is the integer of 3-4;

U is 0 or 1;

And R ¹, R ²And R ³Each is respectively from hydrogen, alkyl and aryl, and the two all can replace arbitrarily, middle selection;

Suppose that when p is 3 Mn is the manganese of IV oxidation state; X can not be RO ^-

2, according to the bleaching catalyst of claim 1, wherein among the ligand L, t is 2, s=3, u=1 and R ¹, R ²And R ³Each is respectively hydrogen or methyl.

3, bleaching composition comprises:

ⅰ) the superoxide of 2%-30% weight; With

ⅱ) bleaching catalyst as claimed in claim 1, what contain effective dosage is used for the active peralcohol of catalytically bleaching.

4,, comprise that the amount of bleaching catalyst is corresponding to composition 0.0005-0.5%(weight according to the bleaching composition of claim 3) manganese content.

5,, further comprise the surfactant of 0.5-50% weight according to the bleaching composition of claim 3 or 4.

6,, also comprise the washing synergistic agent of 5-80% weight according to any one bleaching composition among the claim 3-5.

7, the bleaching method of coloring material, its method are included in handles the coloring material method in aqueous medium of peralcohol and manganese complex, every kind of composition has the significant quantity that cooperatively interacts, and material is had cleaning effectiveness, and the structural formula of complex compound is as (I)

Wherein:

Mn is an II, the manganese of III or IV oxidation state;

X represents coordinating group from Cl ^-, Br ^-, I ^-, F ^-, NCS ^-, I ₃, OH ^-, O ^2- ₂, O ^2-, HOO ^-, H ₃O, SH, CN ^-, OCN ^-, S ^2- ₄, NH ₃, NR ₃, RCOO ^-, RO ^-, ; RSO ^- ₃And RSO ^- ₄The middle selection, wherein R can replace arbitrarily from hydrogen, alkyl, aryl, both, and R ' COO ^-The middle selection, wherein R ' is selected from alkyl and aryl, and the both can replace arbitrarily, and their mixture;

P is the integer of 1-3;

Z is the electric charge of complex compound, and can be positive number, the integer of negative or zero;

Y is a counterion, and its type depends on z;

Q= ^z/ [electric charge Y]; With

L is the following big ring organic molecule coordination body of molecular formula,

[NR ³-（CR ¹（R ²）u）t]s

Wherein: t is the integer of 2-3;

S is the integer of 3-4;

U is 0 or 1; With

R ¹, R ²And R ³Each is respectively from hydrogen, alkyl and aryl, and the two all can replace arbitrarily; With

Suppose when p is 3 and Mn when being the manganese of IV oxidation state, X can not each be RO ^-