CN1073714A

CN1073714A - Detergent bleach compositions

Info

Publication number: CN1073714A
Application number: CN92111815A
Authority: CN
Inventors: R·J·马滕斯; T·施瓦特霍夫
Original assignee: Unilever NV
Current assignee: Unilever NV
Priority date: 1991-11-26
Filing date: 1992-11-25
Publication date: 1993-06-30
Anticipated expiration: 2007-11-25
Also published as: TW234144B; CA2083661A1; JPH0641586A; KR960000205B1; AU2962092A; AU661522B2; MX9206779A; ZA928188B; JPH0768543B2; KR930010171A; BR9204549A; CN1031647C; EP0544490A1; TR27075A

Abstract

The invention discloses detergent bleach compositions, it contains surfactant, peroxide bleaching agent and as the double-core manganese complex of bleaching catalyst, it is characterized in that said composition contains by weight 0-25% anion surfactant and 7.5-55% nonionogenic tenside by weight, if containing, said composition is not more than 7.5% carbonate by weight, represent with yellow soda ash, the weight ratio at least 0.75 of nonionogenic tenside and anion surfactant, if and said composition is when containing by weight greater than 7.5% carbonate, its ratio is at least 2.2.

Description

Detergent bleach compositions

The present invention relates to detergent bleach compositions.More particularly, relate to the improvement detergent bleach compositions, especially, but not only be applicable to fabric washing and cleaning, it contains surfactant materials, peroxide bleaching agent and as the manganese complex of bleaching catalyst.

The used manganese complex of the present invention is the double-core manganese complex, and its general formula is:

Mn is the manganese that can independently exist with III or IV valency oxidation state in the formula; X ₁, X ₂And X ₃Represent a coordination or bridging group separately arbitrarily, they are selected from H ₂O, O ^2- ₂, O ^2-, OH ^-, HO ^- ₂, SH ^-, S ^2-,＞SO, CI ^-, N ^3-, SCN ^-, RCOO ^-, RSO ^- ₃, NH ^- ₂, NR ₃Its R is H, alkyl, aryl, and both randomly are substituted, or R ' COO ^-, wherein R ' is alkyl, aryl, both randomly are substituted; L is the ligand of organic molecule, and this molecule contains 3 nitrogen-atoms at least, by all or some nitrogen-atoms wherein and the coordination of manganese center; Z represents the electric charge of title complex and is a positive integer or negative integer; Y is monovalence or polyvalent counter ion, and in its energy and electric charge, counter ion depends on the electric charge Z of title complex; Q=Z/[electric charge Y].

Preferred manganese complex is those wherein X ₁, X ₂And X ₃Perhaps be CH ₃COO ^-Or O ^2-, perhaps be its blended title complex, preferably manganese wherein be the IV oxidation state and X ₁, X ₂And X ₃Be O ^2-

Good especially title complex is that those ligand general formulas wherein are

Ligand, wherein t is the integer of 2-3; S is the integer of 3-4; U is zero or 1; R ¹, R ²And R ³Independently be selected from H, alkyl, aryl respectively, both are randomly substituted.

Other preferred complexes is those title complexs that comprise two ligands, and its ligand general formula is

Wherein t is the integer of 2-3; S is the integer of 3-4; U is zero or 1;

R ¹And R ²Independently be selected from H, alkyl, aryl respectively, both are randomly substituted; And R ³Independently be selected from hydrogen, alkyl, aryl, both are randomly substituted, but the R of bridging unit ⁴Must be by 1 R in each ligand ³Unit generates, R ⁴Be group CnR ⁵R ⁶-(D) p-CmR ⁵R ⁶, wherein p is zero or 1; D is selected from heteroatoms such as oxygen and NR ⁷, or partly be aromatics or saturated with nuclear or heteronuclear ring,

N is the integer of 1-4;

M is the integer of 1-4;

If but must P be zero or P be 1 and D partly be aromatic or saturated same nuclear or heteronuclear ring, then n+m=＜4; If P is 1 and D is heteroatoms such as oxygen or NR ⁷, n+m=＜3 then; R ⁵And R ⁶Independently be selected from H, NR respectively ⁸And OR ⁹, alkyl, aryl, they are randomly substituted, and R ⁷, R ⁸, R ⁹Independently be selected from H, alkyl, aryl respectively, both are randomly substituted.

The suitable ligand example of simple form is:

(I) 1,4, the 7-7-triazacyclononane;

1,4,7-three nitrogen heterocyclic decane;

1,4,8-three nitrogen heterocyclic undecanes;

1,5, the 9-triazododecane;

1,4,7-trimethylammonium-1,4,7-7-triazacyclononane;

1,4,7-trimethylammonium-1,4,7-three nitrogen heterocyclic decane;

1,4,8-trimethylammonium-1,4,8-three nitrogen heterocyclic undecanes;

1,5,9-trimethylammonium-1,5,9-triazododecane;

1,2-pair-(4,7-dimethyl-1,4,7-three azepines-1 ,-ring nonyl) ethane.

(II) three (pyridine-2-yl) methane;

Three (pyrazol-1-yl) methane;

Three (imidazoles-2-yl) methane;

Three (triazol-1-yl) methane.

(III) three (pyridine-2-yl) boric acid ester;

Three (triazol-1-yl) boric acid ester;

Three (pyrazol-1-yl) boric acid ester;

Three (imidazoles-2-yl) boric acid ester;

Three (imidazoles-2-yl) phosphine;

Three (imidazoles-2-yl) boric acid ester.

(IV) 1,3,5-triamino-hexanaphthene;

1,1,1-three (methylamino-) ethane.

(V) two (pyridine-2-base-methyl) amine;

Two (pyrazol-1-yl-methyl) amine;

Two (triazol-1-yl-methyl) amine;

Two (imidazoles-2-base-methyl) amine,

All at the N-of amine atom and/or CH ₂Randomly replace on carbon atom and/or the aromatic ring.

Those ligands of the derivative that group (I) and carbon thereof replace are particularly preferred, especially:

(1) 1,4,7-trimethylammonium-1,4,7-three nitrogen heterocyclic alkane (Me in the ninth of the ten Heavenly Stems 3 ₃TACN) and

(2) 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane (Me ₄TACN)

(3) 1,2,2,4,7-pentamethyl--1,4,7-7-triazacyclononane (Me ₅TACN)

(4) 2-benzyl-1,4,7-trimethylammonium-1,4,7-7-triazacyclononane

(5) 1,2-are two, and (4,7-dimethyl-1,4,7-three azepines-1-encircle nonyl the ethane ((Me of Et-bridging ₂TACN) ₂)

Be used for and active unimportant for title complex of the type of the counter ion y of electric charge, and can be selected from for example following any counter ion: chlorion; Sulfate radical; Nitrate radical; Methylsulfate; Anion surfactant, for example alkyl sulfate of long-chain, alkyl azochlorosulfonate, benzene sulfonamide acid group, tosylate; The trifluoromethane sulfonic acid root; Perchlorate (ClO ^- ₄), Bph ^- ₄And PF ^- ₆Although some counter ions are more much better than other, because product property and security former thereby be restricted.

Yet be used for best manganese complex of the present invention be:

（Ⅰ）[（Me ₃TACN）Mn ^Ⅳ（μ-O） ₃Mn ^Ⅳ（Me ₃TACN）] ²⁺（PF6 ^-） ₂

（Ⅱ）[（Me ₄TACN）Mn ^Ⅳ（μ-O） ₃Mn ^Ⅳ（Me ₄TACN）] ²⁺（PF6 ^-） ₂

（Ⅲ）[（Me ₃TACN）Mn ^Ⅲ（μ-O）（μ-OAC） ₂Mn ^Ⅲ（Me ₃TACN）] ²⁺（PF ^- ₆） ₂

（Ⅳ）[（Me ₄TACN）Mn ^Ⅲ（μ-O）（μ-OAC） ₂Mn ^Ⅲ（Me ₄TACN）] ²⁺（PF ^- ₆） ₂

(V) [((Me of Et-bridging ₂TACN) ₂) Mn ^IIIMn ^IV(μ-O) ₂(μ-OAC)] ²⁺(ClO ^- ₄) ₂

These also can be abbreviated as hereinafter:

（Ⅰ）[Mn ^Ⅳ ₂（μ-O） ₃（Me ₃TACN） ₂]（PF ₆） ₂

（Ⅱ）[Mn ^Ⅳ ₂（μ-O） ₃（Me ₄TACN） ₂]（PF ₆） ₂

（Ⅲ）[Mn ^Ⅲ ₂（μ-O）（μ-OAC） ₂（Me ₃TACN） ₂]（PF ₆） ₂

（Ⅳ）[Mn ^Ⅲ ₂（μ-O）（μ-OAC） ₂（Me ₄TACN） ₂]（PF ₆） ₂

Think that the structural formula of title complex I is as described below:

In applicant's await the reply European patent specification 458397 and 458398, report these manganese complexes and had significantly effectively bleaching and oxide catalyst effect.In of the present invention further describing, above-mentioned cooperation 7 things also can be described as " bleaching catalyst " or are referred to as " catalyzer " simply.

The detergent bleach compositions that the present invention relates at present comprises surfactant, peroxide bleaching agent and above-mentioned double-core manganese complex as bleaching catalyst.

Peroxide bleaching agent

A peroxide bleaching agent normally class can produce the compound of hydrogen peroxide in the aqueous solution.Hydrogen peroxide cource is known in the prior art.They comprise alkali metal peroxide, and organism superoxide such as urea peroxide, and inorganic persalt are as alkali metal perborate, percarbonate, superphosphate, persilicate and persulphate.The mixture of two or more this compounds also is suitable for.Good especially is four water sodium perborate, especially monohydrate sodium stannate.Monohydrate sodium stannate is preferred, because its active o content height.In view of environmental factors, SPC-D also is preferred.Their consumptions in the present composition are general by weight in the scope of about 5-35%, are preferably 10-25%.

The alkyl hydroxy superoxide is another kind of peroxide bleaching agent.The example of these materials comprises cumene hydroperoxide and uncle's monobutyl hydroperoxide.

Organic peroxide acid also can be used as peroxide bleaching agent.The general formula that this class material has usually is:

R contains the alkylidene group of about 20 carbon atoms of 1-or the alkylidene group of replacement in the formula, preferably has lactam bond; Or the phenylene group of phenylene or replacement; Y be hydrogen, halogen, alkyl, aryl, imido-aromatics or non-aromatic group,

Can be used for the single peroxy acid of typical case of the present invention for example comprises:

(I) peroxybenzoic acid and nuclear substituted peroxybenzoic acid, for example peroxide-α-Nai Jiasuan;

(II) aliphatic series, the aliphatic series and the aralkyl list peroxy acid that replace are for example crossed lauric acid, perstearic acid and N, and N-O-phthalic amido is crossed caproic acid (PAP); With

The hot amino of (III) 6--6-oxo-mistake caproic acid.

Being used for typical diperoxy acid of the present invention for example comprises:

(IV) 1,12-diperoxy dodecandioic acid (DPDA);

(V) 1, the 9-diperoxyazelaic acid;

(VI) diperoxy brassylic acid; Diperoxy sebacic acid (sebasic acid) and diperoxy m-phthalic acid;

(VII) 2-decyl diperoxy butane-1, the 4-bisgallic acid; With

(VIII) 4, the two benzoyl hydroperoxides of 4 '-sulphonyl.

The inorganic peroxy acid compound also is suitable for, for example a Potassium Persulphate (MPS).If use the organic or inorganic peroxy acid as peralcohol, its consumption generally is about 2-10% by weight, is preferably 4-8%.

All these superoxide all can use separately or be used in combination with peroxy acid bleach precursor and/or organic bleaching catalyst.

The peroxy acid bleach precursor is known, and detailed description is arranged in the literature, and for example English Patent 836,988; 864,798; 907,356; 1,003,310 and 1,519,351; German Patent 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591 US1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.

An other class peroxy acid bleach precursor is cationic peroxy acid bleach precursor, i.e. the peroxy acid precursor of quaternary ammonium-substituted, and as US4,751,015 and 4,397,757; EP-A-284,292 and EP-A-331, described in 229.The example of this peroxy acid bleach precursor is:

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

The N-octyl group, N, N-dimethyl-N10-benzene oxygen formyl radical (carbophenoxy) decyl ammonium chloride-(ODC);

3-(N, N, N-trimethyl ammonium) propyl group sodium-4-sulfophenyl carboxylicesters; And N, N, N-trimethyl ammonium toluyl oxygen base benzene sulfonate.

Another special positively charged ion peroxy acid bleach precursor is generated by the positively charged ion nitrile, and EP-A-0303520, European patent specification 458396 and 464880 are described it.

Any of these peroxy acid bleach precursors can both use in the present invention, although some may be better than other are arranged.

In above-mentioned bleaching precursor, best is ester, comprises Acylphenol sulphonate and acyl group alkyl (benzene) sulfocarbolate; The acyl group monoamide; With the quaternary ammonium-substituted peroxy acid precursor that comprises the positively charged ion nitrile.

The example of described best peroxy acid bleach precursor or activator is sodium-4-phenoxy group benzene sulfonate (SBOBS); N, N, N ', N '-tetra-acetylated ethylene diamine (TAED); Sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; Sodium-4-methyl-3-phenoxy group (benzoloxy) benzoic ether; SPCC; Trimethyl ammonium toluyl oxygen base-benzene sulfonate; Sodium nonanoyl oxo benzene sulfonate (SNOBS); Sodium 3,5,5-trimethyl acetyl oxo benzene sulfonate (STHOBS); With the positively charged ion nitrile that replaces.

The precursor consumption can be about the 1-8% of composition weight, is preferably 2-5%.To the only organic bleaching catalyst of the present invention is usually said sulfimide (suphonimide), as EP-A-O, and 453,003 and EP-A-O, 446,982 is described.

Surfactant

The surfactant that is generally used in the detergent bleach compositions can be the crude substance deutero-, soap for example, or be selected from the synthesis material of negatively charged ion, nonionic, amphoteric, zwitterionic, cationic active agent and composition thereof.Many suitable promoting agents can be obtained and Schwartz for example in the literature by commercially available, " tensio-active agent and the washing composition " of Perry and Berch (" Surface Active Agents and Detergents ") done in volume I and the II to describe fully.

Typical synthetic anion surface active agent is water-soluble alkali organic sulfate and the sulfonate with about 8-22 carbon atom alkyl normally, and the term alkyl of use comprises the moieties of senior aryl.

For example, suitable synthetic anionic detergent compound is sodium alkyl sulfate and ammonium, especially through the senior (C of vitriolization ₈-C ₁₈) compound of alcohol (as producing by fat or Oleum Cocois); Alkyl (C ₉-C ₁₀) benzene sulfonic acid sodium salt and ammonium, especially linear secondary alkyl (C ₁₀-C ₁₅) benzene sulfonic acid sodium salt; Alkyl glycerol base ether sodium sulfate, the especially ester of the synthol that produces by the ester of fat or Oleum Cocois deutero-higher alcohols with by oil; Coco-nut oil fatty acid-glyceryl ester sodium sulfate and sodium sulfonate; Senior (C ₉-C ₁₈) the sulfuric ester sodium salt and the ammonium salt of reaction product of Fatty Alcohol(C12-C14 and C12-C18) alkylene oxide (especially oxyethane); With the isethionic acid esterification with the reaction product of sodium hydroxide neutral lipid acid such as coconut fatty acid; The sodium of the fatty acid amide of N-methyltaurine and ammonium salt; Alkane-sulfonate is as by alpha-olefin (C ₈-C ₂₀) produce with sodium bisulfite reaction and by alkane (C ₁₂) and SO ₂Reaction produce then with basic hydrolysis to produce random sulfonate; C ₇-C ₁₂Dialkyl sodium sulfosuccinate and ammonium salt; And alkene sulfonate, this term is used to describe especially C of alkene ₁₀-C ₂₀Alpha-olefin and SO ₃React the material that the hydrolysis reaction product that neutralizes is then again generated.Best anionic detergent immunomodulator compounds is (C _10-15) sodium alkyl benzene sulfonate, (C _16-18) sodium alkylether sulphate.

Employed suitable non-ionic surface active compound preferably uses with anionic surfactant compound, and the example is generally oxyethane and alkyl (C particularly including alkylene oxide ₆-C ₂₂) reaction product of phenol, be generally 5-25EO, promptly per molecule has 5-25 unitary oxyethane; Aliphatic series (C ₈-C ₁₈) condensation product of uncle or secondary straight or branched alcohol and oxyethane, be generally 2-30EO, and product can be the condenses of oxyethane and propylene oxide and reacting ethylenediamine product.Other so-called ionic surfactant pack is drawn together APG, sugar ester, long-chain oxidation quaternary amine, long-chain oxidation season phosphine and dialkyl sulphoxide.

A certain amount of both sexes or zwitter-ion surface active cpd also can be used for composition of the present invention, but because their price is higher, so unsatisfactory usually.If use any both sexes or zwitterionic detergent compounds, according to the synthetic anionic and the tween of the most common use, it can be used for composition on a small quantity so.

Yet if having now found that the above-mentioned catalyzer of use in detergent bleach compositions, its performance depends on the builder system of activated detergent system and composition to a great extent.Experiment shows common anion surfactant and specific long-chain C ₁₆-C ₂₂The fatty acid soaps class has very big negative interaction to catalyst activity, therefore reduced performance significantly, but not ion-cleaning tensio-active agent and catalyzer does not act on mutually.The highest about 10%(is by weight) the short chain C of low concentration ₁₂-C ₁₄The fatty acid soaps class has active effect to catalyst activity, but when height is dense, for example＞20%(by weight), they also begin to become harmful.

Produce the mechanism of these effects and imperfectly understand, but can suppose, can think that the part catalyzer disappears under the condition that anion surfactant exists from solution by some mechanism.For instance, this may be because the catalyst molecule of positive charge precipitates the promoting agent of negative charge, or only because form the result of the ion pair that can cause the catalysis inactivation.Other a kind of possibility may be that catalyzer is wrapped in the micelle of anion surfactant.

No matter be what reason, if be noted that when activated detergent has comprised anionic surface active substances, contain the double-core manganese complex the bleachability of detergent bleach compositions of catalytic peroxide bleaching system be not good.

Therefore the purpose of this invention is to provide a kind of detergent bleach compositions, it contains surfactant, peroxide bleaching agent and a kind of aforesaid double-core manganese complex with best bleaching action.

Now found to comprise the nonionogenic tenside of q.s unusually, can improve bleaching action to optimum extent.

There is no need to be bound by any theory, can think provides the nonionogenic tenside of sufficient amount to compensate because the maximum negative interaction of the anion surfactant that the resolubilization of catalyzer causes.

The invention provides a kind of detergent bleach compositions, said composition contains surfactant materials, peroxide bleaching agent and as the double-core manganese complex of bleaching catalyst, said composition is characterised in that it contains 0-25%(wt) anion surfactant and 7.5-55%(wt) nonionogenic tenside, if composition contains 0-7.5%(wt) carbonate builders (representing) with yellow soda ash, the weight ratio of nonionogenic tenside and anion surfactant is 0.75, if composition contains 7.5%(wt) during above carbonate builders, its weight ratio is at least 2.2.

Composition preferably contains 0-15%(wt) anion surfactant and 10-40%(wt) nonionogenic tenside.

In the another one preferred embodiment, do not contain C in the washing composition reactive systems ₁₆-C ₂₂Fat soap.Detergent bleach compositions has been removed any anion surfactant based on prescription in another preferred embodiment, so all be nonionogenic tenside.

The present composition preferably also contains 5-80%(wt usually) the de-sludging washing assistant, be preferably 10-60%.

The de-sludging washing assistant

The washing assistant raw material can be selected from 1) sequestrant, 2 of calcium) sedimentable matter, 3) calcium ion-exchanged material and 4) their mixture.

The example of calcium chelating washing assistant comprises alkali metal polysilicate phosphoric acid salt, for example tripoly phosphate sodium STPP; Nitrilotriacetic acid(NTA) and water-soluble salt thereof; An alkali metal salt of carboxymethoxyl Succinic Acid, ethylenediamine tetraacetic acid (EDTA), oxo two Succinic Acid, mellitic acid, benzene polycarboxylic acid, citric acid and as US4,144,226 and 4,146,495 described polyacetal carboxylic acid esters.

The example of precipitation washing assistant comprises sodium orthophosphate and yellow soda ash.

The example of calcium ion-exchanged washing assistant comprises various types of non-water-soluble crystal or unbodied aluminosilicate, wherein known most representative be zeolite, for example zeolite A, zeolite B(are also referred to as zeolite P), zeolite C, X zeolite, zeolite Y and EP-A-O, 384,070 described zeolite P types.

Particularly, composition of the present invention can contain any organic or inorganic washing assistant, yet considers environmental factors, preferably without phosphate builders or only use on a small quantity.

Be used for typical washing assistant of the present invention and be for example yellow soda ash, calcite/carbonate, sodium nitrilo triacetate salt, Trisodium Citrate, carboxymethoxyl malonic ester, carboxymethoxyl succinate and water-insoluble crystal or amorphous aluminosilicate washing assistant, wherein each can both be used as main washing assistant, or uses separately or use with other washing assistant or as the mixed with polymers that is total to washing assistant.

With regard to builder system, alkali-metal carbonate and phosphoric acid salt have been observed, especially yellow soda ash, sodium bicarbonate and tripoly phosphate sodium STPP, also the catalytically bleaching performance to the hydroperoxide SYNTHETIC OPTICAL WHITNER has negative interaction, unexpectedly, then much smaller to the catalytically bleaching performance impact degree of peroxyacid bleach.Yet the influence of carbonate is relevant with PH, and when PH is increased to 10 when above, particularly 10.5 and 10.5 when above, and this negative interaction is weakened greatly.

Therefore, when using hydroperoxide such as Sodium peroxoborate or SPC-D as SYNTHETIC OPTICAL WHITNER, preferred compositions contains 5%(wt) following carbonate builders (representing) with yellow soda ash, if the PH of composition up to 10 than the low alkalinity zone in the time, most preferably its content is not more than 2.5% to being zero basically.

Except the above-mentioned composition of pointing out already, detergent composition of the present invention can contain typical additives arbitrarily, and it is measured by being generally used for the detergent composition that fabric washing is used.The example of these additives comprises buffer reagent, carbonate for example, and profoamer, alkanolamide for example is especially by palm kernel fatty acid and coconut fatty acid deutero-single ethanol amide; Froth suppressor, for example alkyl phosphate and siloxanes; Anti redeposition agent, for example alkyl cellulose ether of sodium carboxymethyl-cellulose and alkyl or replacement; Stablizer, for example ethylenediamine tetraacetic acid (EDTA) (EDTA) and phosphonate derivative (are Dequest

Type); Fabric softener; Inorganic salt and ealkaline buffer, for example sodium sulfate, water glass etc.; And the common very little fluorescent agent of consumption; Spices; Enzyme, for example proteolytic enzyme, cellulase, fat plum, amylase and oxydase; Sterilant and dyestuff.

When using hydroperoxide, when making SYNTHETIC OPTICAL WHITNER as Sodium peroxoborate or SPC-D, preferred composition contains and is not more than 5% carbonate buffer agent (representing with yellow soda ash) by weight, if the pH of composition be in up to 10 than in the low alkalinity zone time, be not more than 2.5% to being zero to be reasonable basically by its consumption.

In its additive, transition metal chelator, for example EDTA and phosphonate derivative, for example ethylenediamine tetraacetic (methene phosphonate ester)-EDTMP-is a particularly important, because they have not only improved catalyzer/H ₂O ₂The stability of system and sensitive composition (as enzyme, fluorescent agent, spices etc.), but also improved bleachability is especially in the higher pH zone more than 10, particularly at PH10.5 and 10.5 when above.

Therefore, when detergent bleach compositions comprises surfactant, peroxide bleaching agent, manganese complex bleaching catalyst, carbonate builders and transition metal chelator, the PH that makes solution is more than 10, particularly 10.5 and 10.5 when above, then falls within the scope of the present invention.

Falling in addition within the scope of the invention is that detergent bleach compositions contains surfactant, peroxyacid bleach, DPDA for example, PAP and MPS, bleaching catalyst and phosphate builders, preferably Tri sodium Phosphate.

Optional in addition but additive component that very have multi-functional characteristic in the ideal cleaning composition, its consumption is the about 3%(wt of 0.1%-) polymer materials, its molecular weight is 1000-2,000,000, it can be the homopolymer or the multipolymer of vinylformic acid, toxilic acid or salt or its acid anhydride, vinyl pyrrolidone, methyl or ethyl vinyl ether and other polymerisable vinyl monomer.

The best example of this polymeric material is polyacrylic acid or polyacrylic ester; Polymaleic acid/acrylic copolymer; 70: 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; Polyvinylpyrrolidone and vinyl pyrrolidone/maleic acid.

Detergent bleach compositions of the present invention, when by non-current particle formulation, for example Powdered or particulate state, can produce by any routine techniques that is used to produce cleaning composition, for example by slurrying, the subsequent spray drying to be forming the detergent based powder, and this powder heat-sensitive ingredients comprises other adult and bleaching catalyst of peroxide bleaching agent and optional on demand some, can be used as to do the matter state and add.

Yet, the detergent based powder composition itself that has added bleaching catalyst according to estimates to it, can make with various alternate manners, for example alleged merological approach (part-part processing), non-tower route method (non-tower route processing), dry mix, agglomeration technique, comminution granulation, extrusion process, press closely method etc., these methods are known and do not constitute essential part of the present invention the those skilled in the art of affiliated technical field.

The present invention will be illustrated by following limiting examples.

Embodiment 1

Following experiment is finished in Glass Containers, and heating spiral silica tube, magnetic stirring, thermopair and the PH electrode of controllable temperature is housed.

Under 40 ℃ of isothermals, in the softening water of PH10, measure soap class, primary alconol sulfuric ester (PAS), alkylbenzene sulfonate (ABS) and nonionogenic tenside (NI) for sodium perborate monohydrate (PBM) and [Mn as bleaching catalyst ^IV ₂(μ-O) ₃(Me-TACN) ₂] (PF ₆) ₂, i.e. the effect of the bleachability of title complex (I) is on the test cloth that Standard China Green Tea pollutes.

If press the dosage preparation detergent bleach agent of 6g/l, the concentration that adds SYNTHETIC OPTICAL WHITNER in the washing soln then is 2.5 μ mol/l catalyzer and 8.6mmol/l PBM, is 0.03% catalyzer and 14.3% PBM corresponding to weight.

Soak test cloth is 30 minutes in each composition of embodiment, and is dry in rotary drum dryer after the tap water rinsing, measures the contrast (R460*) of washing front and back on zeiss Elrephometer.Value difference (△ R460*) provides measuring of washing effect.

The results are shown in down in the tabulation 1

1)=Empicol LXV, available from Albright ﹠amp; Wilson

2)=and Synperonic A7, available from ICI

The result shows, works as C ₁₈The consumption of-soap is very low as 1: in the time of 6%(weight), can detect catalyst performance and descend.Work as C ₁₈-soap is 9%(wt) time, performance is reduced to about 9 units from 25 △ R units significantly.Be 9% C astoundingly ₁₂-soap can be brought up to the catalytically bleaching performance 29 units.Two kinds of synthetic anion surfactant PAS(9%) and ABS(9%) also have very strong negative interaction for activity of such catalysts, the catalytically bleaching performance is reduced to about 16 units by 25 units.

On the other hand, 4% NI is almost to not influence of activity of such catalysts.

Embodiment 2

This example shows adds nonionogenic tenside to containing 9%C ₁₈The influence of the bleachability of-soap prescription.This experiment with embodiment 1 used conditionally complete same case under finish.

The results are shown in Table 2

These results clearly illustrate that the NI of interpolation 4% is not enough to improve fully bleachability, and adding 16%(NI on the contrary is 1: 8 with the anion surfactant ratio), the catalytically bleaching performance can be increased to about best 25 △ R units.

Embodiment 3

This example shows adds nonionogenic tenside to containing the influence of 9% ABS prescription bleachability.This experiment is to finish under the situation identical with the used conditionally complete of routine II, and the results are shown in Table 3.

These results clearly illustrate that, add 4% NI and are not enough to fully improve bleachability, add 8%(NI on the contrary: the ratio 0.9 of anion surfactant), improved the catalytically bleaching performance, its as a result when not having promoting agent the contrast experiment more better.

The embodiment IV

This example shows increases C ₁₂The consumption of-soap is to the catalytically bleaching Effect on Performance of catalyzer/PBM bleach system on the test cloth that tea pollutes.Experiment is to finish under the situation identical with embodiment 1 conditionally complete.The results are shown in table 4

The embodiment V

This example shows Na ₂CO ₃To the influence of the bleachability of the detergent bleach compositions of following demarcation prescription, described prescription:

Prescription	% by weight
		Alkylbenzene sulfonate (ABS)	3.0
C ₁₈-soap	1.7
		Non-ionic (Synperonic A 3/A 7)	9.8
Zeolite	24.0
		Polymkeric substance (Sokalan cp5 purchases BASF)	4.0
Xylo-Mucine	0.6
		-hydrated sodium perborate	14.3
Mn-title complex (I) catalyzer	0.03

The washing experiment is under 40 ℃ of isothermals, and the tap water of 16 H of employing is finished under the condition of PH10 and PH10.5.Only in containing the washing soln of bleaching composition that dosage is 6g/l, the test cloth that tea is polluted soaked 30 minutes.

By contrast difference △ R ₄₆₀* expression the results are shown in the following table.

Last table clearly illustrates that content reaches 5.0% yellow soda ash the catalytically bleaching performance is had slight negative interaction, adds high level, i.e. 10% and 20% yellow soda ash and the catalytically bleaching performance is significantly reduced.

Result according to table 6 shows the active effect that improves PH and increase EDTA.

The embodiment VI

Repeat the step of example 1, the bleaching catalyst that only is to use is Mn ^IIIMn ^IV(μ-O) ₂(((the Me of Et-bridging of μ-OAC) ₂TACN) ₂) ^#Handle (softening water that is further purified) with the water of millipore filtration (promptly by Milli-Qplus water purification System(available from Millipore Corporation).

If detergent bleach prescription dosage is 6g/l, the content of catalyzer is corresponding to by weight 0.037% and the content of PBM by weight 14.3%.

[ ^#-press the preparation of the described method of prof Wieghardt (1991 ICBIC meetings, the Oxford, UK)].

Institute obtains and the results are shown in table 7.

^*Synperonic A7 is available from ICI.

The result shows relevant Mn ^(IV) ₂(μ-O) ₃(Me ₃TACN) ₂The SYNTHETIC OPTICAL WHITNER of bridging material energy catalysis perborate.Owing to uses ABS rather than use nonionogenic tenside, so bleach catalyst reduces significantly.Yet when ABS and nonionogenic tenside all existed, the consumption the when demand of nonionogenic tenside is made bleaching catalyst than the title complex that uses not bridging was big, with the undesirable action of compensation ABS.

Claims

1, a kind of detergent bleach compositions comprises surfactant, and peroxide bleaching agent and as the double-core manganese complex of bleaching catalyst has general formula

Mn is the manganese that can exist with III or IV oxidation state separately in the formula; X ₁, X ₂And X ₃Can represent to be selected from H respectively arbitrarily ₂O, O ₂ ^2-, O ^2-, OH ^-, HO ₂ ^-, SH ^-, S ^2-,＞SO, Cl ^-, N ^3-, SCN ^-, RCOO ^-, RSO ₃ ^-, NH ₂ ^-And NR ₃Coordination or bridged group, the R that is had is H, alkyl, aryl, both are randomly substituted, or R ' COO ^-, its R ' is alkyl, aryl, both are randomly substituted; L is a kind of ligand, and it contains the organic molecule of 3 nitrogen-atoms at least, by whole or some nitrogen-atoms and the coordination of manganese center; Z represents the electric charge of title complex and can be the integer of plus or minus; Y is monovalence or polyvalent counter ion, can make charge neutralization, and this depends on the electric charge Z of title complex; And q=Z/[electric charge y], it is characterized in that composition comprises the anion surfactant of 0-25% by weight and the nonionogenic tenside of 7.5-55% by weight, if composition contains the carbonate of 0-7.5% (representing with yellow soda ash) by weight, the weight ratio of nonionogenic tenside and anion surfactant is at least 0.75, if when composition contained by weight the carbonate more than 7.5%, its ratio was at least 2.2.

2,, it is characterized in that it comprises the anion surfactant of 0-15% by weight and the nonionogenic tenside of 10-40% by weight by the composition of claim 1.

3, by the composition of claim 1 or 2, it is characterized in that the washing composition active system does not contain C ₁₆-C ₂₂Fatty acid soaps.

4, by claim 1,2 or 3 composition, it is characterized in that glass or plastic containers.

5, by each the composition among the aforesaid right requirement 1-4, it is characterized in that SYNTHETIC OPTICAL WHITNER is a hydroperoxide compound.

6,, it is characterized in that PH that it has is up to 10 and contain and be not more than 5% carbonate by weight, represents with yellow soda ash by the composition of claim 5.

7, by the composition of claim 6, it is characterized in that being substantially free of carbonate.

8, by each composition among the claim 1-4, it is characterized in that SYNTHETIC OPTICAL WHITNER is a peracetic acid compound.

9, by the composition of claim 1, wherein bleaching catalyst comprises that its general formula of ligand is

T is the integer of 2-3 in the formula; S is the integer of 3-4; U is zero or 1; R ¹, R ²And R ³Be selected from H, alkyl, aryl respectively, both are randomly substituted.

10, by the composition of claim 1, wherein bleaching catalyst comprises two ligands, its general formula

T is the integer of 2-3 in the formula;

S is the integer of 3-4;

U is zero or 1;

R ¹And R ²Be selected from H, alkyl, aryl respectively, both are randomly substituted; And R ³Be selected from hydrogen, alkyl, aryl respectively, both are randomly substituted, but must the R of bridging unit ⁴Be to generate R by 1 R3 unit in each ligand ⁴Be CnR ⁵R ⁶-(D) p-CmR ⁵R ⁶Group, middle p are zero or 1;

D is selected from as oxygen and NR ⁷Heteroatoms or aromatics or saturated with the nuclear or the part of heteronuclear ring,

N is the integer of 1-4;

M is the integer of 1-4;

If p be zero or p be 1 and D is aromatics or saturated same nuclear or the part of heteronuclear ring, then n+m ≤=4; If p is 1 D is as the heteroatoms of oxygen or NR7 then n+m ≤=3; R ⁵And R ⁶Be selected from H, NR respectively ⁸And OR ⁹, alkyl, aryl, randomly substituted, and R ⁷, R ⁸, R ⁹Be selected from H, alkyl, aryl respectively, both are randomly substituted.

11, by the composition of claim 1-8, it is characterized in that bleaching catalyst is selected from title complex:

（Ⅰ）[Mn ^Ⅳ ₂（μ-O） ₃（Me ₃TACN）]（PF ₆） ₂

（Ⅱ）[Mn ^Ⅳ ₂（μ-O） ₃（Me ₄TACN）]（PF ₆） ₂

(V) [(Et-bridging (Me ₂TACN) ₂) Mn ^IIIMn ^IV(μ-O) ₂(μ-OAC)] ²⁺(ClO ^- ₄) ₂

12, by the composition of claim 11, it is characterized in that described bleaching catalyst is title complex (I).