CN1146165A - Metallomacrocycle catalyst composition - Google Patents

Abstract

A metallomacrocycle catalyst composition comprising a complex of: (i) a transition metal catalyst selected from: (a) a transition metal porphin and mixtures thereof; (b) a transition metal phthalocyanine and mixtures thereof; (c) mixtures of transition metal porphin and transition metal phthalocyanine; and (ii) an amphiphilic polymer and mixtures thereof; the complex increasing the half life of the catalyst by a factor of at least 1.1.

Description

Metallomacrocycle catalyst composition

Invention field

The present invention relates to a kind of can be in water-bearing media the Metallomacrocycle catalyst composition of prolong half-life, it contains hydrogen peroxide cource; The invention still further relates to the method that a kind of dye transfer suppresses (DTI) composition and suppress dye transfer between fabric in washing process.

Background of invention

Occur in the modern fabrics washing operation the most obstinate and one of the problem of trouble be that some colored fabrics are easy to dyestuff is released in the washing soln.Dyestuff is transferred on other fabric that is washed together then.

A kind of method that overcomes this problem is to bleach them before these fugitive dyes that are washed down from DYED FABRICS have an opportunity to be adhered on other article the washing.

By using known SYNTHETIC OPTICAL WHITNER, in solution to a certain extent oxidation suspend or the dissolved dyestuff.

European patent 538228 has been described a kind of DTI composition, and it comprises a kind of metal catalyst, a kind of polymkeric substance and a kind of enzyme system that can produce hydrogen peroxide, and wherein said polymkeric substance can reduce the deposition of metal catalyst on fabric.

European patent 553608 has been described a kind of DTI composition, and it comprises a kind of metal catalyst, a kind of amines catalyst stablizer and a kind of enzyme system that can produce hydrogen peroxide, and wherein said amine can connect the 5th ligand of metal catalyst.

The both has introduced provides the DTI of solvability sulfonation group composition a kind of preferably having on metal catalyst, this is expensive.

Have now found that some specific polymers can form a kind of title complex with transition-metal catalyst, increase its solubleness in the aqueous solution.This has been avoided the step of expensive sulfonation transition-metal catalyst.

The adding of the said polymer has reduced the self-destruction speed of transition-metal catalyst, thereby has improved the stability of transition-metal catalyst in the whole washing process and made the application of more kinds of transition metal catalyst compound become possibility.

Thereby, a kind of dye transfer inhibiting composition that shows optimum dye metastasis inhibition performance is provided.

On the other hand, the invention provides a kind of effective ways that include the yarn dyed fabric washing operation.

Summary of the invention

The present invention relates to a kind of Metallomacrocycle catalyst composition, it comprises the title complex of following material:

(i) a kind of transition-metal catalyst, it is selected from:

A. transition metal porphines and composition thereof;

B. transition metal phthalocyanine and composition thereof;

C. the mixture of transition metal porphines and transition metal phthalocyanine;

(ii) a kind of amphiphilic polymer and composition thereof;

This title complex makes the transformation period of catalyzer prolong at least 1.1 times.

The transformation period of catalyzer is defined as in containing the water-bearing media of peroxide source, the transformation period of catalyst oxidation stability.

On the other hand, the invention provides a kind of dye transfer inhibiting composition, its method and epoxidizing method.

According to the present invention, the chemical formula of porphines and phthalocyanine refers to Fig. 1 and/or 2 and Fig. 3 and/or 4.

Fig. 1 represents the general formula of porphines compound, and wherein transition metal is in oxidation state (II).

Fig. 2 represents the general formula of porphines compound, and wherein transition metal is in oxidation state (III).

Fig. 3 represents the corresponding formula of phthalocyanine compound, and wherein transition metal is in oxidation state (II).

Fig. 4 represents the corresponding formula of phthalocyanine compound, and wherein transition metal is in oxidation state (III).

Detailed Description Of The Invention

Well known in the art, metallic catalyst such as porphyran are easy to self-destruction. As said from Ruin the result, the consumption that adds catalyst should make enough active catalysts exist, to wash whole Wash and bleach dyestuff in the circulation.

Have now found that the life-span of metallic catalyst can prolong by adding a kind of polymer in the water-bearing media Long, this polymer and catalyst can form a kind of complex and make this catalyst solubilising. This can be by that Micellar copolymerization thing or the poly-nuclear pseudo-gums bundle that can self make up because of hydrophobic effect a bit provide. By this class two The hydrophobic microcell that parent's polymer produces makes the hydrophobic catalyst solubilising.

The present invention one side of wide model has provided a kind of complex that contains two kinds of key elements:

(i) a kind of transition-metal catalyst, it is selected from:

A. transition metal porphines and composition thereof,

B. transition metal phthalocyanine and composition thereof,

C. the mixture of transition metal porphines and transition metal phthalocyanine,

(ii) a kind of amphipathic polymer and composition thereof; This complex makes the half-life of catalyst prolong at least 1.1 times.

Transition-metal catalyst

But be shown in to the visualization of transition metal porphines basic structure Fig. 1 and/or Fig. 2 on the independent page In. In Fig. 1 and 2, atom site is pressed custom numbering and two key and is pressed custom and mark.

In the literature, porphines and porphyrin are used as synonym, but the porphines representative is the simplest traditionally , no any substituent porphyrin; Its mesoporphyrin is that a kind of subclass of porphines is other. Carry among the application To porphines comprise porphyrin.

Transition metal porphines structure is that those are at 5,10,15 and 20 carbon potentials of formula 1 (centre position) A place or many places be selected from hydrogen, alkyl group such as methyl, ethyl, propyl group, tertiary butyl groups Substituting group and be selected from replacement or unsubstituted pyridine radicals, pyridine radicals-N-oxide, phenyl, A kind of aromatic ring system of naphthyl and anthryl part replaces.

Preferred transition metal porphines structure is that those are at 5,10,15 and of formula 1 (centre position) One place of 20 carbon potentials or many places selected from replace or unsubstituted phenyl, pyridine radicals, pyridine radicals-The transition metal porphines that the aromatic rings system of N-oxide, naphthyl and anthryl replaces.

Preferred porphyran is that wherein molecule replaces at 5,10,15 and 20 carbon potential pyridyl substituting groups, and the pyridine substituting group is selected from:Each X wherein₁Independently be selected from H, F, Cl, Br, NO₂, alkyl, alkoxyl, cycloalkyl, Aralkyl, aryl, alkaryl and heteroaryl; Preferred H, Cl or F; And X₂Be selected from O^-, OH, H, alkyl, alkoxyl, cycloalkyl, aralkyl, aryl, alkaryl and heteroaryl, preferred O^-。

Another kind of porphyran very preferably is that wherein molecule is replaced by a phenyl substituent at 5,10,15 and 20 carbon potentials, and phenyl is selected from: Wherein each X independently be selected from H, F, C1, Br ,-SO ₃H, SO ₂NR ₂, wherein R be selected from H, alkyl and hydroxyalkyl ,-CO ₂H alkyl, alkoxyl group, cycloalkyl, aralkyl, aryl, alkaryl and heteroaryl, preferred H, Cl or F;

By NO ₂It also is suitable that group replaces, but can only be in the position of X.

A kind of particularly preferred transition metal porphines is that molecule is replaced by phenyl substituent at 5,10,15 and 20 carbon potentials therein, and wherein said phenyl is replaced by X=H.Known this preferred compound is the transition metal tetraphenylporphines.

The compound of Fig. 1 and/or Fig. 2 can be selected from F, Cl, Br and C in a place or the many places of residue carbon potential ₁-C ₁₀The substituting group of alkyl replaces.

In addition, the compound of Fig. 1 and/or Fig. 2 substituting group that can be selected from F, Cl, Br, alkyl, alkyl carboxyl, alkyl hydroxy, vinyl, alkenyl and aryl in a place or the many places of 2,3,7,8,12,13,17,18 carbon potentials replaces.

The available transition metal is selected from Cu, Fe, Mn, Co, Cr, Ti, V or other transition metal, preferred Mn.

For the oxidation state of the filtering metal porphines that is higher than (II), the symbol X of Fig. 2 ⁴Represent a kind of negatively charged ion, preferred OH-or Cl-when oxidation state is (III).

Preferred porphines transition metal is in oxidation state (III).

Porphine derivative also comprises chlorophyll, chlorin and bacterium chlorin.

Transition metal phthalocyanine and derivative thereof have the structure shown in Fig. 3 and/or Fig. 4, and wherein the atom site of phthalocyanine structure is by the custom label.

The transition metal phthalocyanine structure is 1-4,6,8-11,13,15-18,20,22-25, a place of 27 atom sites or the structure that many places are substituted the base replacement of those Fig. 3 and/or Fig. 4, and substituting group is selected from hydrogen, alkyl group such as methyl, ethyl, propyl group, the tertiary butyl and aromatic ring system such as pyridyl, phenyl, naphthyl and anthracyl radical.

A kind of preferred transition metal phthalocyanine is unsubstituted phthalocyanine.

The available transition metal is selected from Cu, Fe, Mn, Co, Cr, Ti, V or other transition metal, preferred Mn.For the oxidation state of the transition metal phthalocyanine that is higher than (II), the symbol X of Fig. 4 ⁴Represent a kind of negatively charged ion, preferred OH when oxidation state is (III) ^-Or Cl ^-

Preferred phthalocyanine transition metal is in oxidation state (II).Polymkeric substance

Second key element of the present invention is polymkeric substance, and it comprises at least one hydrophilic radical and at least one hydrophobic grouping, and the ratio of hydrophilic radical and hydrophobic grouping is 1: 10 to 10: 1; Preferred 1: 3 to 3: 1.

Hydrophobic part interacts by hydrophobic interaction such as II-II, and/or charge transfer effect, and/or model ylid bloom action, can interact with insoluble catalyzer at least in part, when the hydrophilic group of polymkeric substance makes the composition solubilising, increased composition like this in the intrafascicular stability of poly-nuclear pseudo-gums.Do the time spent when charge transfer takes place, formed a kind of electron donor-acceptor title complex.

The preferred polymers structure that is suitable for the oxide catalyst solubilising is the following formula structure: Wherein A and B can be selected from :-CH ₂-, NH, O, ketone, ester bond, amido linkage, imine linkage; Wherein n, m, p, r, s, t can independently be any integer, as long as (n+m+p) v+ (r+s+t) v is 1-1000, preferred 1-500 and ratio v/w are 0.1-1; Wherein the value of q and u is independently among 1-10.

Each R can independently be selected from H, alkyl, alkylhalide group, alkenyl, alkynyl; Preferred H or CH ₃

R ₁Being selected from (partly) contains derived from the compound aromatic hydrocarbon ring hydrophobic part of toluene, vinyl toluene, stilbene, pyridine, naphthalene, anthracene, phenanthrene, phenyl, Histidine, tryptophane, phenylalanine, tyrosine, alkylbenzene, dimethylbenzene, carbazole, xanthene, acridine, purine, pyridazine and indoles for example.

Select R ₂Providing water-soluble, so be hydrophilic on these substituent characteristics, as-OH, hydroxyalkyl such as methylol and hydroxyethyl; The N-oxide derivative of polyoxyethylene, hydroxy phenyl and derivative thereof, part, pyridine-N-oxide Histidine, tryptophane, phenylalanine, tyrosine derived from pyrrolidone; Phenylbenzimidazole sulfonic acid salt, naphthalenesulfonate, imidazoles, naphthalene, anthracene, phenanthrene, phenyl, carbazole, xanthene, acridine, purine, pyridazine, indoles ,-COOH ,-COOH ,-SO ₃The water-soluble salt derivative of M, wherein M is an alkalimetal ion;-NR ₂,-NR ₃ ⁺X ^-, wherein X is that halogen ion and R independently are selected from H, alkyl and hydroxyalkyl.

When if A and/or B are not ether, ketone, acid amides, imines or ester bond, R ₁And R ₂It can independently be the substituting group on A and the B part.

Another kind of suitable polymkeric substance of the present invention is the polysaccharide with replacement of lower unit structure: Wherein C and D are the oligose unit, and wherein the oligose unit contains the polycondensation product of monose, carry out neighbour-glycosidic linkage and close and form by containing nearly 10 these class resistatess that are selected from hexose, pentose, deoxyhexamethylose resistates.Wherein the value of q and u is independent of 1 to 10; Wherein substituent R 1 and R2 are with mentioned above identical.

Be suitable for the 3rd base polymer of the present invention and have the lower unit structure:

Wherein E and F are dibasic aromatic portion, as phenylene, naphthalene, phenanthroline, anthracene, thiophene; Wherein the value of q and u is independent of 1 to 10; Wherein substituent R 1 and R2 are with referred to above identical.

Polymericular weight is 500-1000,000 and preferred 1000-500,000.

Described polymerization system can be random, grafting or block polymer.

Polymerization system also can contain two or more different monomers, as long as hydrophilic group and hydrophobic group ratio are between 1: 10 to 10: 1; Preferred 1: 3 to 3: 1.

Preferred polymkeric substance is fragrant amphiphilic polymer, and it is selected from: the multipolymer of sodium polystyrene sulfonate and vinyl naphthalene, Polyvinylpyrolidone (PVP) and vinyl imidazole multipolymer, poly-sulfonic acid naphthalene (TAMOL ^).

A kind of multipolymer that is more preferably is the multipolymer of sodium polystyrene sulfonate and vinyl naphthalene.

In addition, polymerization system is a kind of homopolymer, and it shows amphiphilic nature such as part neutral polymethyl acrylic acid.

The another kind of special glycosyl that is fit to the oxide catalyst solubilising is a cyclic polysaccharide, as natural cyclodextrin and modified cyclodextrin.Wherein polymkeric substance is a kind of cyclodextrin, can form a kind of inclusion complex with transition-metal catalyst.The preparation of title complex with separate, it comprises: i) porphines catalyzer and derivative thereof

A kind of method for preparing Metallomacrocycle catalyst composition, said composition are the transition metal porphines catalyst compositions of solid form, and this method comprises the following steps:

A. said Metallomacrocycle catalyst is dissolved in a kind of water soluble organic substance matter;

B. said polymkeric substance is soluble in water;

C. said pre-insoluble polymer may is added in the pre-molten catalyzer;

D. under agitation slowly add at least 25% distilled water; With

E. remove water soluble organic substance matter by evaporation and remove and anhydrate by lyophilize.

Water soluble organic substance matter can be any material that can be dissolved with organic metal catalyst.A kind of suitable material is a water-miscible organic solvent, and it is selected from methyl alcohol, ethanol, Virahol, n-propyl alcohol, acetone, N-Methyl pyrrolidone and dimethyl formamide, particular methanol, ethanol, Virahol, n-propyl alcohol or acetone.

For the production of liquid catalyst title complex, particularly preferred water-soluble substances is a kind of nonionogenic tenside of following formula

R-(O-CH ₂-CH ₂) _n-OH wherein R is C ₈-C ₂₂Alkyl; N between 2-24, preferred 7.Ii) phthalocyanine catalyst and derivative thereof

The method for preparing Metallomacrocycle catalyst composition promptly prepares solid-state transition metal phthalocyanine catalyst method for compositions, and it comprised for two steps:

(a) by solution or by the polymer melts synthetic compound.

(b) title complex is with pure solid or load on the separation of the title complex particle form on the silicon-dioxide.A) title complex is synthetic

1) may further comprise the steps by the synthetic of solution:

I) with in the water-soluble solubleness organic solvent of transition metal phthalocyanine catalyst, preferred dimethyl sulfoxide (DMSO) (DMSO).

Ii) solid polymer is joined in this solution and

Iii) under this mixture of continuously stirring, add less water.

2) may further comprise the steps by the synthetic of polymer melts:

The transition metal phthalocyanine catalyst is dissolved in the polymkeric substance of fusing and stirs half an hour.B. the separation of title complex

1) title complex with pure solids constituent from

Solution is mixed with excessive acetone.Formed a kind of coloured throw out in 2-4 hour, its available suction filtration separates vacuum-drying subsequently.

2) title complex separates with the title complex particle form that loads on the silicon-dioxide

Colourless with the title complex that non-deutero-silica gel (hydroxyl) extracts in the aqueous solution until solution.After suction filtration and vacuum-drying, collect these silicon-dioxide.

Main application of the present invention relates to a kind of DTI composition and a kind of epoxidizing method.1) DTI composition

Title complex can two kinds of forms use:

A) as a kind of additive

B) with a kind of complete preparation a) as a kind of additive

First kind of form relates to a kind of detergent additives composition, and it is suitable for providing the dye transfer restraining effect, in the time of in being added into a kind of water washings that contains tensio-active agent and active oxygen source, also contains enzyme, washing assistant and other conventional washing agent composition.In this case, this title complex can add separately or with other additive.A kind of method that suppresses dye transfer between fabric in including the washing operation of yarn dyed fabric also is provided, said method comprise with said fabric with contain a kind of detergent additives composition and a kind of a kind of washings that obtains oxygen source contacts.Can obtain oxygen source will be described in more detail below.B) with a kind of complete preparation

Second kind of form relates to a kind of dye transfer inhibiting composition, and it comprises previously described Organometallic composition and a kind of oxygen source that obtains.A kind of method that suppresses dye transfer between fabric in including the washing operation of yarn dyed fabric is provided simultaneously, said method comprise with said fabric with contain a kind of dye transfer inhibiting composition and contact with a kind of a kind of washings that obtains oxygen source.Can obtain oxygen source will be described in more detail below.

A) and b) in, title complex content normally detergent composition heavy 0.0001% to 0.1%, preferred 0.0005% to 0.01%, more preferably 0.002%.

This paper design provides a kind of title complex, and its content in washes is 1 * 10 ^-8Mole is to 1 * 10 ^-3Mole, preferred 1 * 10 ^-7Mole is to 1 * 10 ^-4Mole.

Detergent composition of the present invention also comprises the composition that usually occurs under those general items in Betengent product, it comprises heavy metal ion chelating agent, enzyme, white dyes, photoactivation SYNTHETIC OPTICAL WHITNER, spices and the pigment of detergent builder compound, oxygen bleaching system and the subsidiary material of organic surface active agent, interpolation such as antiredeposition and soil-suspending agent, suds suppressor, interpolation.Some product also comprises fabric softener and static inhibitor.

The oxygen bleaching system can be selected from:

I) Chang Gui SYNTHETIC OPTICAL WHITNER; it comprises: hydrogen peroxide itself; the organic peroxy carboxylic acid; the inorganic peroxy SYNTHETIC OPTICAL WHITNER; it is selected from persulphate; inorganic perhydrate such as perborate; percarbonate; cross polyphosphate; combination with said inorganic peroxy SYNTHETIC OPTICAL WHITNER and organic peroxy acid precursor; wherein bleach-activating agent is selected from N-acyl compounds such as tetraacetyl ethylene diamine (TAED); the O-acyl compounds such as the ninth of the ten Heavenly Stems acyloxy benzene carbonate (NOBS; at US4; 412; described in 934); 3; 5-trimethyl acetyl oxygen base benzene sulfonate (ISONOBS; at EP120, described in 591); benzoyl caprolactam; the sulfophenylate of acyl lpsilon.

The content of SYNTHETIC OPTICAL WHITNER is 100-10 in washes, 000ppm, preferred 100-1000ppm.If use the mixture of said inorganic peroxy SYNTHETIC OPTICAL WHITNER and organic peroxy acid precursor, the ratio of precursor and SYNTHETIC OPTICAL WHITNER is 0.05-0.8, preferred 0.1-0.6.

Ii) a kind of enzyme catalysis hydrogen peroxide produces system, and it produces the hydrogen peroxide of low levels continuously and a kind of practical approach of controlling the low stable state content of hydrogen peroxide is provided.When in washing water, when hydrogen peroxide replenishes with the speed that consumes owing to the dyestuff oxidation, can produce maximum effectiveness.These enzyme systems are disclosed among the EP91202655.6 that submitted on October 9th, 1991.A kind of suitable enzyme is an oxydase, as urate oxydase, galactose oxidase, alcohol oxidase, amine oxidase, amino-acid oxidase, rCO and glucose oxidase, malate oxidase, glycollate oxydase, hexose oxidase, fragrant and mellow oxydase, L-gulose oxydase, pyranose oxidase, L-Sionit oxydase, Vit B6 4-oxydase, 2-2-hydroxy acid oxidase, E.C. 1.1.99.1, ecdysone oxidase.Preferred enzyme system is alcohol oxidase, aldehyde oxidase and glucose oxidase.

The more preferably system that is applicable to granulated detergent has solid alcohol, and as glucose, its oxidation can be passed through the glucose oxidase enzyme catalysis, obtains glucuronic acid and follows the formation of hydrogen peroxide.Use preferred system for liquid detergent and comprise liquid alcohol, it for example also can be used as solvent.Example is ethanol/alcohol oxidase.The enzyme that can commercial buy is Ferm-cozyme for the trade(brand)name of being sold by FINNSUGAR ^, Ovazyme ^Glucose oxidase and be the urate oxydase of Uricase S by the trade(brand)name that NOVO sells.The present composition can add product with washing composition easily and be used for conventional detergent composition.These additive products will replenish or improve conventional detergent composition performance.

The present invention also comprises dye transfer inhibiting composition, and it comprises other detergent ingredients, so it can be used as cleaning composition.Other detergent ingredients

Many tensio-active agents can be used for detergent composition.The typical list of anionic, non-ionic type, amphoteric, zwitterionic classes and their kind are authorized the U.S.P.3 of Laughlin and Heuring on December 30th, 1975, be presented in 929,678.The suitable cationic surfactants inventory is authorized the U.S.P.4 of Murphy on March 31st, 1981, be presented in 259,217.

The mixture of anion surfactant here is suitable, particularly as vitriol, and the mixture of sulfonate and/or carboxylate surface active agent.The mixture of sulfonate and sulfate surfactant is use in 5: 1 to 1: 2 with the weight ratio of sulfonate and vitriol usually, and preferred 3: 1 to 2; 3, more preferably 3: 1 to 1: 1.Preferred sulfonate comprises having 9 to 15 in the alkyl, the particularly alkylbenzene sulfonate of 11 to 13 carbon atoms, and α-Huang Huazhifangsuanjiazhi, and wherein fatty acid derived is from C ₁₂-C ₁₈Fat source, preferred C ₁₆-C ₁₈Fat source.Under any circumstance, positively charged ion is a basic metal, preferred sodium.Preferred sulfate surfactant is the alkyl-sulphate that has 12-22 carbon atom in alkyl in these sulfonate sulfate mixtures, preferred 16 to 18 carbon atoms.

Another kind of useful surfactant system comprises the mixture of two kinds of alkyl-sulphate materials, their mean chain length differences separately.A this system contains C ₁₄-C ₁₅Alkyl-sulphate and C ₁₆-C ₁₈The mixture of alkyl-sulphate, C ₁₄-C ₁₅: C ₁₆-C ₁₈Weight ratio be 3: 1 to 1: 1.Alkyl-sulphate also can combine with the alkyl ethoxy sulfate that contains 10-20 carbon atom in alkyl, preferred 10-16 carbon atom, and average degree of ethoxylation is 1 to 6.Under any circumstance, positively charged ion all is a basic metal, preferred sodium.

Another kind of anionic surfactant system very preferably comprises C ₁₂-C ₂₀Alkyl sulfuric ester salt and the per molecule water-soluble C that on average contains 1 to 7 ethoxy group ₁₁-C ₁₈The mixture of AES salt, wherein alkyl sulfuric ester salt and AES salt weight ratio are 2: 1 to 19: 1, more preferably 3: 1 to 12: 1 and most preferably 3.5: 1 to 10: 1.

Alkyl sulfuric ester salt can be derived from natural or synthetic hydrocarbon source.The preferred embodiment of these salt comprises the C of side chain basically ₁₄-C ₁₅Alkyl sulfuric ester salt, i.e. C wherein ₁₄-C ₁₅Alkyl chain collateralization degree greater than about 20%, these are the C of side chain basically ₁₄-C ₁₅Alkyl sulfuric ester salt usually derived from the synthetic resource.Also preferred C ₁₆-C ₂₀Alkyl sulfuric ester salt, it is usually derived from natural resource, as Tallow, beef and signalling oil peculiar to vessel.

C ₁₁-C ₁₈AES salt comprises primary alkyl oxyethyl group sulfuric ester, and it is derived from C ₁₁-C ₁₈The condensed products of pure and average every mole of 1-7 Oxyranyle condensation.The C of preferred every mole of 1 to 5 oxyethyl group ₁₂-C ₁₅Alkyl ethoxy sulfuric acid, most preferably average every mole of 1 to 3 oxyethyl group.This C ₁₁-C ₁₈Alcohol itself can obtain from natural or synthetic resource.From natural fat, derive, or Ziegler olefin is synthetic, or OXO synthetic C ₁₁-C ₁₈Alcohol can both become the appropriate resources of alkyl group.The example of synthesis of derivatives comprises the Dobanol25 (KTM) that is sold by Shell Chemicals (UK) Ltd, and it is a kind of C ₁₂-C ₁₅The adulterant of alcohol is by the Ethyl24 that Ethyl Corporation sells, C ₁₃Be 67%, C ₁₅Be 33% C ₁₃-C ₁₅The adulterant of alcohol, its trade name BASF GmbH sell is Lutensol, ICILtd. sell is into Synperonic (RTM) with by the Lial125 of Liguichimica Italiana sale.The example that can derive to the material of the natural generation of alcohol is Oleum Cocois and palm-kernel oil and corresponding lipid acid.C ₁₁-C ₁₈Alkyl ethoxy sulfate content is preferably the 0.5%-10% of composition weight, more preferably 0.5%-5%, most preferably 1%-3%.

Other anion surfactant that is suitable for purposes of the present invention is the basic metal sarcosinate with following formula

R-CON (R ¹) CH ₂COOM wherein R is C ₅-C ₁₇Straight or branched alkyl or alkenyl group, R ¹Be C ₁-C ₄Alkyl group and M are a kind of alkalimetal ion.Preferred embodiment is lauroyl, the coconut acyl (C of its sodium-salt form ₁₂-C ₁₄) myristyl and oleoyl sarcosine methyl esters.

One class is applicable to that the nonionic surface active agent among the present invention comprises the condenses of oxyethane and a kind of hydrophobic part, and it is 8-17 that the tensio-active agent that provides has hydrophile-lyophile balance mean value, preferred 9.5-13.5, more preferably 10-12.5.Hydrophobic (oleophylic) part can be aliphatics or aromatic in nature, and the length of the polyoxyethylene groups of those and any concrete hydrophobic grouping condensation can easily be regulated to obtain a kind of water-soluble cpds, and it has the quality of balance between the required hydrophilic and hydrophobic part.

Particularly preferred this class nonionogenic tenside is C ₉-C ₁₅The primary alconol b-oxide, it comprises average every mol of alcohol 3-8 moles of ethylene oxide, particularly contains the C of average every mol of alcohol 6-8 moles of ethylene oxide ₁₄-C ₁₅Primary alconol and the C that comprises average every mol of alcohol 3-5 moles of ethylene oxide ₁₂-C ₁₅Primary alconol.

Another kind of ionic surfactant pack is drawn together the alkyl polyglycoside compound with following general formula

RO (C _nH _2nO) _tZ _xWherein Z is the part derived from glucose; R is the saturated hydrophobic alkyl that contains the 6-18 carbon atom; T is that 0-10 and n are 2 or 3; X is 1.1-4, and this compound comprises unreacted Fatty Alcohol(C12-C14 and C12-C18) that is less than 10% and the many glycosides of short-chain alkyl that are less than 50%.This compounds and their application in cleaning composition are disclosed among the EP-B0070074,0070077,0075996 and 0094118.

Another kind of preferred nonionic is the polyhydroxy fatty acid amide surfactant compound with following structural formula:

Wherein: R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, or its mixture, preferred C ₁-C ₄Alkyl, more preferably C ₁Or C ₂Alkyl, most preferably C ₁Alkyl (being methyl); And R ²Be C ₅-C ₃₁Alkyl, preferred straight chain C ₇-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixture; With Z be polyhydroxy alkyl, it has at least 3 straight chain hydroxyl chains of directly linking the hydroxyl on the chain, or the derivative of its alkoxide (preferred ethoxyquin or third oxidation).Z preferably derived from a kind of in the reductive amination reaction reducing sugar; Z is glucosyl more preferably.Suitable reducing sugar comprises glucose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar.High glucose maize treacle, high-fructose corn syrup and high malt sugar maize treacle and top listed single sugar can be used as raw material.These maize treacle can produce the sugar component mixture of a kind of Z.Be to be understood that and never get rid of other proper raw material.Z is preferably selected from-CH ₂-(CHOH) _n-CH ₂OH ,-CH (CH ₂OH)-C (CHOH) _N-1-CH ₂OH ,-CH ₂-(CHOH) ₂(CHOR ') (CHOH)-CH ₂OH, wherein n is the integer of 3-5, comprises 3 and 5, and R ' is H or cyclic or aliphatic monose, and oxidation alkyl derivative.Glucosyl most preferably, wherein n is 4, is in particular-CH ₂-(CHOH) ₄-CH ₂OH.

In formula (I), R ¹Can be, as N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

R ²-CO-N can be, as coconut monoethanolamide, stearylamide, oleylamide, laurylamide, myristic amide, decyl amide, palmitic amide, butter acid amides etc.

Z can be 1-deoxy-glucose base, 2-deoxidation fructosyl, 1-deoxidation malt-base, 1-deoxidation lactose base, 1-deoxy-galactose base, 1-deoxymannose base, 1-deoxidation maltotriose glycosyl etc.Preferred compound is N-methyl N-1-deoxy-glucose base C ₁₄-C ₁₈Fatty acid amide.

The another kind of tensio-active agent that is suitable for purposes of the present invention is two polyhydroxy fatty acid amides, and it is disclosed among the U.S. Patent application No.08/187251 in more detail.

Another kind of tensio-active agent is semi-polarity tensio-active agent such as amine oxide.Suitable amine oxide is selected from single C ₆-C ₂₀, preferred C ₁₀-C ₁₄N-alkyl or alkenyl amine oxide and 1,3-propylene diamine dioxide, wherein Sheng Xia N position is replaced by methyl, hydroxyethyl or hydroxypropyl.

Cats product also can be used in herein the detergent composition, and suitable quaternary ammonium surfactant is selected from single C ₈-C ₁₆, preferred C ₁₀-C ₁₄N-alkyl or alkenyl ammonium surfactant, wherein remain the N position and replaced by methyl, hydroxyethyl or hydroxypropyl.

Laundry detergent composition of the present invention comprises the tensio-active agent that accounts for the heavy 3%-30% of said composition, but more generally contains 5%-20%, more preferably 7%-15%.

Machine dishwashing detergent composition of the present invention comprises the tensio-active agent that accounts for the heavy 0%-10% of said composition, preferred 0.5-10%, most preferably 1%-5%.

Very preferably component is the detergent builders system that comprises one or more other non-phosphate detergent washing assistants in another of detergent composition of the present invention.It can be including, but not limited to alkali metal aluminosilicate zeolite, the amorphous and lamellated water glass of crystal, quadrol-N, N '-disuccinic acid (EDDS), carbonate, borate, monomer multi-carboxylate, poly carboxylic acid homopolymerization or copolymerization or its salt, wherein poly carboxylic acid comprises at least two by the separate carboxyl that is no more than two carbon atoms and the mixture of previously described any material.And quite the aluminosilicate ion exchange material of scope can be used, and preferred sodium silicoaluminate zeolite is as having a unit of following formula structure cell in English Patent 142914.3.

Na _z[(AlO ₂) _z(SiO ₂) _y] xH ₂O wherein z and y is at least 6; The mol ratio of z and y is that 1.0-0.5 and x are at least 5, and is preferred 7.5 to 276, more preferably 10 to 264.The silico-aluminate material is hydrate forms and preferably contains 10%-28%, more preferably the crystal of the combination water of 18%-22%.

The aluminosilicate ion exchange material that enforcement the present invention is suitable for can buy and can be the material of natural generation, but preferably synthetic deutero-material.A kind of method for preparing the silicoaluminate ion-exchange material is in U.S. Patent No. 3,985, comes into question in 669.Being preferred for herein composite crystals shape aluminosilicate ion exchange material can trade mark zeolite A, zeolite B, zeolite P, X zeolite, zeolite HS, zeolite MAP, zeolite MAB and composition thereof and bought.Aluminosilicate ion exchange material is zeolite A and has following formula in a particularly preferred embodiment

Na _L2[(A1O ₂) ₁₂(SiO ₂) ₁₂] xH ₂O wherein x is 20 to 30, preferred 27.Formula Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆] 276H ₂The X zeolite of O and formula Na ₆[(AlO ₂) ₆(SiO ₂) ₆] 7.5H ₂O) zeolite HS also is suitable for.

Preferred nonphosphate builders is the crystal lamina sodium silicate with following general formula

NaMSi _xO _2x+ 1yH ₂O wherein M is sodium or hydrogen, and x is 1.9 to 4 a number and y is 0 to 20 number.This crystalloid lamina sodium silicate is disclosed among the EP-A-0164514 and preparation method thereof and is disclosed among DE-A-3417649 and the DE-A-3742043.For the purposes of the present invention, above in the general formula x value be 2,3 or 4 and preferred 2.M more preferably sodium and y more preferably the preferred embodiment of O and this formula comprise α-, β-, γ-and the Na of δ-form ₂Si ₂O ₅These materials can obtain with NaSKS-5, NaSKS-7, NaSKS-11 and NaSKS-6 respectively from Hoechst AGFRG.Most preferred material is δ-Na ₂Si ₂O ₅, NaSKS-6.

Laundry detergent composition of the present invention preferably contains the crystal lamina sodium silicate, and its content is to account for 1% to 80% of said composition weight, and more preferably 5% to 40% and most preferably 7% to 20%.

Crystal lamina sodium silicate material preferably is present in the granular detergent composition of the present invention with intimately admixing composition granule form with the ionogenic material of a kind of solid, water soluble.Solid, water-soluble ionogenic material are selected from organic acid, organic and inorganic acid salt and composition thereof.

Appropriate organic comprises xitix, citric acid, pentanedioic acid, gluconic acid, oxyacetic acid, oxysuccinic acid, toxilic acid, propanedioic acid, oxalic acid, succsinic acid and tartrate, 1-hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid (EHDP), amino polymethylene phosphonic acids are as NTMP, EDTMP﹠amp; The mixture of DETPMP and aforementioned any material.Suitable acid salt comprises sodium bicarbonate, sodium bioxalate, sodium pyrosulfate, sodium acid pyrophosphate, acid sodium orthophosphate, sodium hydrotartrate and composition thereof.

The pH of the granular mixture of crystal layered silicate and the water-soluble ionizable material of solid is at least 10 (recording) in 1%20 ℃ distilled water solution, be at least 11 more at large, is at least 11.5 usually.

Other composition that mixes interpolation in crystal layered silicate and the ionizable water soluble compounds is particularly useful for particulate processing and increases the stability that contains the particulate detergent composition.Especially, certain class agglomerate need add one or more tackiness agents to help bonding silicate and ionizable water-soluble material, has the particle that can accept physical property thereby produce.The content of tackiness agent accounts for 0% to 20% of said composition weight.Tackiness agent preferably is present in the intimately admixing thing with silicate and ionizable water-soluble substance.The preferred adhesive fusing point is between 30 ℃-70 ℃.Tackiness agent preferably accounts for the 1-10% of said composition weight and 2-5% most preferably.

Preferred adhesive comprises the C that contains every mol of alcohol 5-100 moles of ethylene oxide ₁₀-C ₂₀The alcohol b-oxide more preferably contains the C of every mol of alcohol 20-100 moles of ethylene oxide ₁₅-C ₂₀The primary alconol b-oxide.

Other preferred adhesive comprises some polymeric material.The example of these polymeric materials is that molecular-weight average is that 12,000 to 700,000 Polyvinylpyrolidone (PVP) and molecular-weight average are 600 to 10,000 polyoxyethylene glycol.The multipolymer of maleic anhydride and ethene, methylvinylether or methylacrylic acid, maleic anhydride constitutes at least 20% (molecular fraction) of polymkeric substance, is the further example as the polymeric material of tackiness agent.These polymeric materials can itself or with other solvent such as water, propylene glycol is used in combination with above-mentioned comprise every mole in the C of 5-100 moles of ethylene oxide ₁₀-C ₂₀The alcohol b-oxide.

Other example of tackiness agent of the present invention comprises C ₁₀-C ₂₀List and two glyceryl ethers and C ₁₀-C ₂₀Lipid acid.Some inorganic salt solution comprises that water glass also is used for this purpose.

Derivatived cellulose such as methylcellulose gum, other example that carboxy methyl cellulose and Natvosol and homopolymerization or copolymerization poly carboxylic acid or its salt are tackiness agents of the present invention.

Particle also comprises the conventional component in other detergent composition, as long as they itself are not incompatible and do not hinder the synergism of crystal layer shape silicate.

The suitable multi-carboxylate of containing a kind of carboxyl comprises the water-soluble salt of lactic acid, oxyacetic acid and ether derivant thereof, and they are disclosed in belgian patent 831,368,821,369 and 821,370.

The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of following acid: succsinic acid, propanedioic acid, (ethylidene dioxy base) diacetin, toxilic acid, diethyl alkyd, tartrate, tartronic acid and fumaric acid; and ether carboxylate; as at German Offenlegenschrift 2,446,686 and 2; 446; 687 and United States Patent (USP) 3,935, described in 257 and the sulfinyl carboxylate salt; as described in the belgian patent 840,623.The multi-carboxylate of containing three carboxyls comprises, especially, water-soluble citrate, aconitate and citraconate and succinate derivative, as in English Patent 1,379, the carboxyl methoxy succinate of describing in 241, the newborn oxygen base succinate of in Holland's application 7205873, describing and in English Patent 1,387, the oxygen connection multi-carboxylate's material such as the 2-Evil-1,1 that describe in 447,3-tricarballylic acid salt.

The multi-carboxylate of containing four carboxyls comprises oxygen di-succinate, and it is in English Patent 1,261, be disclosed in 829, and 1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent multi-carboxylate of sulfo group and comprise the sulfo-succinic acid salt derivative, it is in English Patent 1,398, is disclosed in 421 and 1,398,422 and at United States Patent (USP) 1,439,000.

Alicyclic ring and heterocycle multi-carboxylate comprise pentamethylene-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, cyclopentadiene acid amides pentacarboxylic acid salt, 2,3,4,5-tetrahydrofuran (THF)-suitable, suitable, suitable-tetracarboxylic acid hydrochlorate, 2,5-tetrahydrofuran (THF)-suitable-dicarboxylate, 2,2,5,5-tetrahydrofuran (THF)-tetracarboxylic acid hydrochlorate, 1,2,3,4,5, the carboxymethyl derivant of 6-hexane-hexacarboxylic acid salt and polyvalent alcohol such as sorbyl alcohol, mannitol and Xylitol.Aromatic polycarboxylic acids salt is included in English Patent No.1, disclosed mellitic acid, 1,2,4,5-pyromellitic acid and phthalic acid derivative in 425,343.

Above preferred multi-carboxylate is contained the hydroxycarboxylate that per molecule reaches three carboxyls, more specifically is Citrate trianion.

Monomer or oligomeric multi-carboxylate's sequestrant or with the parent acid of the mixture of its salt, also can be considered as the component of the builder system of detergent composition of the present invention as citric acid or Citrate trianion/citric acid mixture.

Other suitable water-soluble organic salt is homopolymerization or copolymerization poly carboxylic acid or its salt, and wherein poly carboxylic acid comprises at least two no more than two carboxyls that carbon atom is spaced-apart of usefulness.Back base polymer is disclosed in GB-A-1, in 596,756.The example of this salt be MWt2000-5000 polyacrylic ester and with the multipolymer of maleic anhydride, it is 20 that these multipolymers have molecular weight, 000-70,000, particularly about 40,000.These materials are usually with the 0.5%-10% of composition weight, more preferably 0.75%-8%, and most preferably the amount of 1%-6% is used.

Detergent composition of the present invention comprises the nonphosphate builders compound, and its content is the 1%-80% of composition weight, more preferably 10%-60%, most preferably 20%-50%.

In preferred laundry detergent composition, sodium silicoaluminate such as zeolite A account for the 20%-60% of washing assistant gross weight, and monomer or oligomeric carboxylate salt account for 5% to 30% and the crystal layered silicate that washing assistant accounts for gross weight and account for 10% to 65% of washing assistant gross weight.In this composition, builder system is preferably also sneaked into a kind of combination of auxiliary inorganic and organic washing-assisting detergent, and as yellow soda ash and maleic anhydride/acrylic copolymer, its content accounts for 35% of total washing assistant.

The sequestrant that contains that is fit to be included in the detergent composition of the present invention is 1-N, N, N ' disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or substituted ammonium salt, or its mixture.Preferred EDDS compound is form and the sodium salt or the magnesium salts of free acid.The example of this preferred EDDS sodium salt comprises Na ₂EDDS and Na ₄EDDS.The example of this preferred EDDS magnesium salts comprises MgEDDS and Mg ₂EDDS.Magnesium salts most preferably is included in the present composition.

Detergent composition can comprise optional sequestrant composition.These optional sequestrants can include organic phosphonates, it comprises that amino alkylidenyl gathers (alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate, nitrilo trimethylene phosphonic salt, 1 tetramethylene phosphonic acid salt and diethylenetriamine pentamethylenophosphonic acid(DTPP) salt.Phosphonate compounds can its sour form or is existed with the complex form of its basic metal or alkaline metal ions; The mol ratio of said metal ion and said phosphonate compounds was at least 1: 1.These title complexs are at US-A-4, are described in 259,200.The organic phospho acid salt compound preferably exists with its magnesium salts form.The content of phosphorated chelating agent is preferably few as far as possible in the composition of the present invention, and the composition that does not contain this thing fully is most preferred.

Amorphous silicate is the useful component of detergent composition.Silicate is to be less than 10% of said composition weight at the content that machine exists in detergent composition, more preferably less than 5%.Though soluble silicate is used as multiple use in routine is done washing with detergent compositions, in the detergent composition that mixes the crystal layered silicate material, they need not exist.Yet, when the crystal layered silicate of a builder system part that forms detergent composition, must add with a kind of exsiccant mixing element fashionable, in spray-dired particle, soluble silicate still can be used as the configuration agent, and it forms the part of laundry detergent composition usually.If do not add the silico-aluminate washing assistant in the spray-dried granules and only contain organism, Here it is especially needs.Suitable silico-aluminate is those SiO ₂: Na ₂The ratio of O is 1.6 to 3.4, preferred 2.0 to 2.8.

The antiredeposition and the soil-suspending agent that are suitable for herein comprise derivatived cellulose, as poly carboxylic acid or its salt and the polyamino compound of methylcellulose gum, carboxymethyl cellulose and Natvosol, homopolymerization or copolymerization.This base polymer comprises the multipolymer of polyacrylate and maleic anhydride and ethene, methylvinylether or methylacrylic acid, and in the multipolymer of describing in detail in EP-A-137669, maleic anhydride accounts for 20% (molar percentage) at least.Polyamino compound such as aspartame are disclosed among EP-A-305282, EP-A-305283 and the EP-A-351629.These materials account for the 0.5%-10% use of composition weight, more preferably 0.75%-8%, most preferably 1%-6% usually with its content.

Other useful polymeric material is a polyoxyethylene glycol, and particularly those molecular weight are 1000-10,000, and more preferably 2000-8000, most preferably from about 4000 polyoxyethylene glycol.Their consumption is 0.20%-5% (weight), more preferably 0.25%-2.5% (weight).The multi-carboxylate of these polymkeric substance and above-mentioned homopolymerization or copolymerization helps improving retention of whiteness, fabric ash deposition and to the cleaning performance of clay, protein and oxidable dirt when transition metal exists.

The preferred optional whitening agent is an anion characteristic, its example is 4,4 ' two-(2-diethanolamino-4-anilino-S-triazine-6-base is amino) Stilbene-2:2 ' disulfonic acid disodium, 4,4 '-the two-(2-morpholino-4-anilino-2-triazine-amino Stilbene-2:2 ' of 6-base-disulfonic acid disodium, 4,4 '-two-(2,4-hexichol amido-S-triazine-6-base is amino) Stilbene-2:2 '-disulfonic acid disodium, 4 ', 4 " two-(2; 4-hexichol amido-S-triazine-6-base is amino) Stilbene-2-sulfonic acid list sodium; 4; 4 '-two-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-2-triazine-6-base is amino) Stilbene-2; 2 '-the disulfonic acid disodium; 4,4 '-two-(4-phenyl-2,1,3-triazine-2-yl) Stilbene-2,2 ' disulfonic acid disodium, 4,4 ' two (2-anilino-4-(1-methyl-2-hydroxyethylamino)-S-triazine-6-base is amino) Stilbene-2,2 ' disulfonic acid disodium and 2 (Stilbene base (stilbyl)-4 " (naphthyl-1 '; 2 ': 4; 5)-1; 2; 3-triazole-2 " sodium sulfonate, 4,4 '-two-(2-sulfo group styryl)-biphenyl disodium.

The stain remover that is used for detergent composition normally terephthalic acid and ethylene glycol and/or propylene diol units with the multipolymer or the ter-polymers of various arrangements.These examples of polymer are disclosed in the United States Patent (USP) 4116885 and 4711730 and the patent application 0272033 of european publishing of common transfer.Particularly preferred polymkeric substance has following formula:

Polyvinylpyrolidone (PVP) typically, its MWt is 5000-20000, and preferred 10000-15000 also can form useful reagent, and it can stop the transfer of unstable dyestuff between fabric in washing process.Also having other useful reagent is polyvinyl imidazol quinoline, Polyvinylpyrolidone (PVP), polyvinyl alcohol, at EP-538, they is had more fully in 228 and describes.

Another kind of optionally washing agent composition components is a suds suppressor, and example is the mixture of siloxanes and silicon-dioxide-siloxanes.Siloxanes can alkylating silicone materials be representative generally, and silicon-dioxide uses with the form of porphyrize usually, and example is silica dioxide gel and xerogel and various types of water drain silica.These materials can particle form mix, and wherein easily mix suds suppressor valuably with discharging, and these suds suppressors are present in and have water-soluble or water dispersible, roughly do not have in surface-active washing composition-impermeability carrier.In addition, suds suppressor can be dissolved or be distributed in the liquid carrier and by being sprayed onto on one or more other components and uses.

As mentioned above, useful silicone foam control agent comprises the mixture of alkylating siloxanes mentioned above and solid silica.This mixture can prepare to the surface of solid silica by adding siloxanes.Preferred silicone foam control agent is that the silicon-dioxide with hydrophobic silanization (most preferably trimethylammonium-silanization) is representative, and its granular size is that 10 nanometers-20 nanometer and specific surface area are greater than 50m ²/ g closely mixes with dimethyl silicone fluids, and the siloxane fluid molecular weight is about 500 to about 200,000, and the weight ratio of the silicon-dioxide of siloxanes and silanization is about 1: 1 to about 1: 2.

Preferred silicone foam control agent is disclosed in people's such as Bartollota the United States Patent (USP) 3,933,672.Other useful especially froth suppressor is a self-emulsifying siloxane foams inhibitor, and it is at disclosed German patent application DTOS2 on April 28th, 1977, is described in 646,126.The example of this compound is DC0544, can buy from Dow Corning, and it is a kind of siloxanes/glycol multipolymer.

Above-mentioned froth suppressor accounts for 0.001% to 5% of composition weight with content usually and uses preferred 0.1% to 3%.

The preferred method of fusion comprises froth suppressor is sprayed onto with liquid form and is applied on one or more main components of composition or froth suppressor is sprayed onto on the individual particles that these particles mix with other solids component of composition then.Foaming regulator mixes as individual particles and also allows to comprise other foam control material such as C ₂₀-C ₂₄Lipid acid, the high MWt multipolymer of Microcrystalline Wax and oxyethane and propylene oxide, it also has secondary influence to the dispersiveness of matrix.Form in the United States Patent (USP) 3,933,672 that these foaming regulator particulate technology are disclosed in people such as above-mentioned Bartolotta.

The another kind of optional member that is useful on detergent composition is one or more enzymes.They can content be that 0.1% to 10% of composition weight mixes, more preferably 0.5% to 5%.

Preferred enzyme material comprises commercial amylase, neutrality and Sumizyme MP, lipase, esterase and the cellulase of selling, and they are incorporated in the composition usually.Suitable enzyme is at United States Patent (USP) 3,519, comes into question in 570 and 3,533,139.

The preferred commercial proteolytic enzyme of selling comprise that those are sold by Novo Industries A/S (Denmark) with trade name Alcalase and Savinase and with trade name Maxatase by InternationalBlo-Synthetics, the proteolytic enzyme that Inc. (The Netherlands) sells.

Preferred amylase comprises that as the α-Dian Fenmei that the lichenoid form bacillus from a kind of special system obtains, it is described among 269,839 (Novo) in more detail at GB-1.Preferred commerce can get amylase and comprise, as Rapidase that is sold by International Bio-Synthetics Inc and the Termamyl that is sold by Novo Industries A/S.

Particularly preferred lipase is produced and is sold by Novo Industries A/S (Denmark), its trade name is Lipolase (Biotechnology Newswatch, on March 7th, 1988, the 6th page) and be mentioned in EP-A-0258068 (Novo) with other suitable lipase.

Also having a kind of optional useful component in detergent composition is sanitas.Its preferred embodiment is C ₁₄-C ₂₀Lipid acid.

Fabric softener also can be incorporated in the detergent composition of laundry usefulness.These reagent can be inorganic or organic types.The example of inorganic softening agent is to be disclosed in GB-A-1, the smectic clays in 400,898.The organic fabric softening agent comprises the water-insoluble tertiary amine that is disclosed among GB-A-1514276 and the EP-B-0011340.

They and single C ₁₂-C ₁₄The combination of quaternary ammonium salt be disclosed in EP-B-0026527﹠amp; In 528.Other useful organic fabric softening agent is the acid amides of two long-chains, and it is disclosed among the EP-B-0242919.Other organic composition of fabric sofetening system comprises the high molecular weight peo material that is disclosed in EP-A-0299575 and 0313146, is disclosed in the cellulase in the U.S. Patent application 08/105422.

The content of smectic clays is 5% to 15% (weight) normally, more preferably 8% to 12% (weight), and these materials join in the remainder of preparation with the composition of dry mixed.Organic fabric softening agent such as water-insoluble tertiary amine or two long-chain acid amides mix with content 0.5% to 5% (weight), usually select 1% to 3% (weight) for use, and high-molecular weight polyoxyethylene material and water-soluble cationic material are that 0.1% to 2% (weight) mixes with content, select 0.15% to 1.5% (weight) usually for use.Wherein a composition part is spray-dired, these materials can add in the water slurries that are added in the spray-drying tower, although in some cases they are sprayed onto on other solids component of composition and can make things convenient for molten state liquid with the adding of dry mixed particulate form or with them.

But according to detergent composition liquid of the present invention, pasty state or particle form.Particulate composition also can be " a closely form " according to the present invention, and promptly they have higher density than conventional granulates washing composition, promptly 550 arrives 950g/l; In this case, granular detergent composition according to the present invention is compared with the conventional granulates washing composition and is contained less " mineral filler salt "; Typical filling salt is the alkaline earth salt of sulfuric acid and hydrochloric acid, preferably sulfuric acid sodium; " closely " washing composition preferably contains and is no more than 10% filling salt.

The invention still further relates to a kind of method, promptly in the fabric washing process, suppress the dyestuff of dissolved or suspension and transfer on another part fabric of running into from a fabric.Present method comprises the washings of fabric with a kind of usefulness of doing washing of above stating is contacted.This method of the present invention can conveniently be carried out in washing process.This washing methods preferably carries out under 5 ℃-90 ℃, and especially at 20 ℃-60 ℃, but catalyzer is effective during up to 95 ℃ in temperature.The pH of treatment soln is preferred 7 to 11, and especially 7.5 to 10.5.

Detergent composition according to the present invention comprises the composition that is used for the cleanup action thing, such as fabric, fiber, crust, skin etc., as hard-surface cleaning composition (containing or do not contain abrasive), laundry detergent composition and automatic and the non-automatic dish composition of washing.2) epoxidizing method

Second kind of purposes of the present invention relates to a kind of epoxidizing method.Therefore, provide a kind of method of carrying out epoxidation reaction when imidazoles exists, wherein Metallomacrocycle catalyst composition comprises a kind of following title complex i) a kind of transition metal, it is selected from:

A. transition metal porphines and composition thereof,

B. transition metal phthalocyanine and composition thereof,

C. the mixture of transition metal porphines and transition metal phthalocyanine and ii) a kind of amphiphilic polymer and composition thereof;

This title complex can make the transformation period of catalyzer increase by 1.1 times at least.

The present invention obtains explanation in the non-limiting example below.Embodiment 1 contains the separation of the title complex of porphines

Following method has been summarized the process of separating the MnTPP title complex, wherein MnTPP is tetraphenylporphyrin Manganous chloride tetrahydrate (III), can Aldrich sequence number 25,4754 obtain with polymer P SSSVN be sodium polystyrene sulfonate vinyl naphthalene multipolymer, its MW is 310, the preparation of 000:1, PSSSVN

The 2-vinyl naphthalene that thermometer, magnetic stirring apparatus, atmospheric condenser being housed and adding in the Erlenmeyer flask of Normag scatterer applying argon gas toward a 150ml: 13.36g can Aldrich lot 0252956 (0.087mo1e) obtains, 20.0g can Aldrich lot 06014KW (0.097mole) obtain the 4-styrene sulfonic acid of its sodium salt, the argon gas that can Alarich obtains of 90ml sprays methyl-sulphoxide.Adding the α that 1.06g can Fluka lot 278989988 obtains, α ' azo isobutyronitrile (6.45mmole, i.e. 3.5mole% monomer) before, stirs the mixture with dissolved solids under room temperature.The dark red solution that obtains is heated to 60 ℃ and kept 21 hours then.Then, with an automatic 10ml transfer pipet (" drop-burette " state) this solution is joined in the 700ml propyl carbinol, and stir with Sprutor.The coloured solid vacuum filtration of paste that forms is also used CaCl in a vacuum with the ether washing ₂Dry.The dry thing in this step heavily is 42.81g.Then the solid sample of the reservation of 1g is dissolved in 1.2 liters of distilled water and with a sintered glass filter funnel filtration (voidage number 4).Use Edwards EF-6 moisture eliminator with the solution lyophilize then.The dry weight of the PSSSVN that obtains is 38.2g.2, the preparation of title complex

Add in a 250ml round-bottomed flask: 0.3gMnTPP, 60ml ethanol, 3.0gPSSSVN under agitation slowly add 100ml distilled water then in this solution.Mixture is added in the flask of a 500ml and under reduced pressure places a rotatory evaporator, this system and 400ml distilled water azeotropic to the last volume are 200ml.Then with the solution lyophilize.The dry weight of the green title complex that obtains is 3.16g and the MnTPP that contains 8% (weight).Embodiment 2

Determine the testing method of MnTPP oxidative stability

Prepare following solution:

1, the catalyst solution (0.5% solution) that contains the Mn-TPP of 10mg in the mixture of 1g ethanol/1g water

2, the catalyzer/polymers soln (1%MnTPP/PSSSVN solution) that contains the 8mg Mn-TPP+92mg PSSSVN in the mixture of 5g ethanol/5g water; This solution is frozen drying then, is formed in 0.5% solution in ethanol and the water (50: 50).

3, the yellow soda ash pH that contains 0.1M is 10 buffered soln.MnTPP oxidative stability method:

Get 50ml buffered soln, wherein add 100 μ l0.5%MnTPP solution (10ppm).Carry out wave spectrum scanning between 350 to 800nm, wherein the main peak of MnTPP is about the 472nm place, and with its (100%MnTPP) for referencial use.Add 0.025g Sodium peroxoborate-hydrate, and carry out length scanning once more.MnTPP/PSSSVN oxidative stability method:

Get 50ml buffered soln, wherein add 1250 μ l0.5%Mn TPP/PSSSVN solution (10ppm Mn TPP/115ppm PSSSVN).Between 350 to 800nm, carry out wave spectrum scanning and with (100%MnTPP/PSSSVN) for referencial use.Add 0.025g Sodium peroxoborate-hydrate and repeatedly carry out length scanning.The amount of peak height and active catalyst is in direct ratio.

The stability of two kinds of catalyst samples is compared as follows:

The transformation period of catalyzer

MnTPP＜30 second

MnTPP/PSSSVN 50 minutes

Conclusion:

By cooperating with PSSSVN, the oxidative stability of MnTPP significantly improves.Embodiment 3a) testing method of DTI prepares following solution

1, the catalyst solution (0.5% solution) that contains the Mn TPP of 10mg in the mixture of 1g ethanol/1g water

2, the catalyzer/polymers soln (solution of 1%MnTPP/PSSSVN) that contains the 8mg Mn TPP+92mg PSSSVN in the mixture of 5g ethanol/5g water

3, detergent solution: 0.7% commercial laundering agent is a solution in 10.5 the municipal water at pH.

For measuring the DTI performance of independent catalyzer, the method below having adopted.

At first, every bottled 200ml detergent solution of going into adds 5 steel balls then and is used for stirring.Add 500 μ l catalyst solutions in this bottle again, and then add a bleeding fabric (sun blue 90).Secondly, prepare a bottle that does not have the bleeding fabric and do not have catalyzer (" target " multifilament) and a bottle that the bleeding fabric is arranged and do not have catalyzer (" reference " multifilament).In each bottle, add multifilament, in Launder-o-meter, rotated these bottles 30 minutes under 30 ℃ then.The reflectance value (L, a, b-value) of measuring dry multifilament with colorimeter (Spectraflash that is made by ICS) is with calculating δ E dyestuff with respect to (maximum value of δ E) oxidation percentage ratio of reference multifilament.

Dyestuff oxidation percentage ratio=100 * (the δ E of 1-δ E/ reference)

Use the same method for measuring the DTI performance of catalyzer/polymkeric substance, can adopting, but at this moment replace catalyst solution with catalyzer/polymers soln.Dyestuff oxidation percentage ratio is relevant with DTI percentage ratio.B) MnTPP/PSSSVN and MnTPP DTI performance in a kind of commercial laundering agent solution compares catalyst content (ppm) %DTI

0.5 19

2 59

MnTPP/PSSSVN

0.5 76

2 91c) performance of the DTI of various MnTPP-polymer complexes in a kind of commercial laundering agent solution

Measure the DTI performance of MnTPP-polymer complexes with different polymerization, the PSSSVN of wherein used polymkeric substance as in embodiment 1, describing, by BASF AG with trade name TAMOL ^NH, TAMOL ^NNOK, TAMOL ^Poly-sodium naphthalene sulfonate that NOC sells and polyvinyl (pyrrolidone and imidazoles multipolymer) (PVPVI), its molecular weight is 100-1000000 and has described said polymkeric substance comprehensively in EP-0372291.MnTPP and MnTPP content in washes that all polymkeric substance contain 8% (weight) are 2ppm.Temperature is 30 ℃.The result is as follows:

The clean percentage ratio of polymkeric substance DTI ^*

Do not have 59

PSSSVN 88

TAMOL?NH 77

TAMOL?NNOC 78

TAMOL?NOC 83

PVPVI 48 ^*The clean percentage ratio implication of DTI is: the DTI percentage ratio of the DTI percentage ratio-polymkeric substance of title complex.Except that PVPVI, there is not other independent polymkeric substance that DTI is provided benefit.Conclusion:

The MnTPP-polymer complexes provides better DTI performance than independent MnTPP, can obtain maximum benefit with PSSSVN.D) dye selection of MnTPP-PSSSVN (2ppm MnTPP) in the commercial laundering agent solution

Select removing of dyestuff as follows:

Dyestuff %DTI

Acid blue 260 30

Sun blue 90 86

Sun blue 218 57

Satin light indigo plant 85

Satin light red 45

Acid red 151 69

Direct brown 30

Directly red 80 4 conclusions: MnTPP-PSSSVN has good DTI performance to various dyestuffs.The separation of the title complex of embodiment 4 implication phthalocyanines

Following method has been summarized the process of separating the MnPc title complex, wherein MnPc is that manganese phthalocyanine (II) and the polymer P VPVI that can Aldrich no 37955-7 obtains is polyvinyl (pyrrolidone and imidazoles multipolymer), and its molecular weight is 100-1000000 and has described said polymkeric substance comprehensively in EP-0372291.

0.0361g MnPc is dissolved in the methyl-sulphoxide (DMSO) of 10ml.Dissolving 0.0509g PVPVI in MnPc solution.In the distilled water with mixture impouring excessive (2ooml).Sapphirine occurs, filtering solution is to remove excessive MnPc.By with 0.4892g not the deutero-hydrophilic silicon dioxide extract to collect blue products in the filtrate, wherein said not deutero-hydrophilic silicon dioxide is with trade name Sipernat by DEGUSSA ^D22LS sells.Silicon-dioxide becomes blueness and solution becomes colorless, and collects then and dried silica.

Utilize atomic absorption proof title complex to be present on the carrier and the title complex that silicon-dioxide contains 0.11% (weight) occurs.Embodiment 5

The epoxidation reaction of utilizing manganese four (p-methoxyphenyl) porphyrin/PSSSVN system is cyclooctene hydrogenated a)

Four (p-methoxyphenyl) porphyrin can obtain by Aldrich No 25-288-3, dissolves manganese four (p-methoxyphenyl) porphyrin (7.4,10 that is blended in the PSSSVN polymkeric substance with distilled water (4ml) ^-3Mmol).Add methylene dichloride (3ml) and form two-phase system, in this mixture, add cyclooctene (1mmol), imidazoles (4.4.10 ^-2Mmol) and last H ₂O ₂(3mmol).Be reflected in the stoppered round-bottomed flask and carry out, open any pressure of stopper once in a while to reduce to form.Follow the tracks of reaction by target vapor-phase chromatography in doing in order to the authentic sample of epoxide, the formation of observation cyclooctene epoxide.This gas phase gas spectrogram is to obtain on the instrument of a Dani3800 that the FFAP30m post is housed.After 24 hours, by the analysis revealed of vapor-phase chromatography to reaction, starting material has generated 48% cyclooctene epoxide relatively.

% cyclooctene epoxide

Blank (no title complex) 8

Manganese four (p-methoxyphenyl) porphyrin/PSSSVN 48b) the 1-tetrahydrotoluene is hydrogenated

Carry out this reaction with carrying out the epoxidised process of cyclooctene, but replace cyclooctene with the 1-tetrahydrotoluene.After 48 hours, show that with the gc analysis reaction starting material has generated 19% 1-tetrahydrotoluene epoxide relatively.

%1-methyl cyclic ethylene epoxide

Blank (no title complex) 2

Manganese four (p-methoxyphenyl)

Porphyrin/PSSSVN 19c) epoxidation of tetramethyl-ethylene

This reaction is undertaken by the epoxidised process of described cyclooctene, but replaces cyclooctene with tetramethyl-ethylene.After 48 hours, show that by the gc analysis reaction starting material has generated 7% tetramethyl-ethylene epoxide relatively.

% tetramethyl-ethylene epoxide

Blank (no title complex) 3

Manganese four (p-methoxyphenyl)

Porphyrin/PSSSVN 7 conclusions: manganese four (p-methoxyphenyl) porphyrin/PSSSVN system compares with independent hydrogen peroxide (blank), increases the productive rate of epoxide in epoxidation reaction.Embodiment 6

In detergent composition, the component definition of writing a Chinese character in simplified form has following meanings:

LAS: straight chain C ₁₂Sodium alkyl benzene sulfonate

TAS: tallow alkyl sodium sulfate

C25EY: with the C of average Y moles of ethylene oxide condensation ₁₂-C ₁₅Based on primary of straight chain

Alcohol

C45EY: with the C of average Y moles of ethylene oxide condensation ₁₄-C ₁₅Based on primary of straight chain

Alcohol

Poly-hydroxy fat

Fat acid acid amides: N-lauroyl N-methylglucosamine

Zeolite A: hydrated sodium aluminosilicate, it has formula Na ₂(A1O ₂SiO ₂) ₁₂27H ₂O,

Its main size of particles is the 1-10 micron.

Citrate trianion: citrate trisodium dihydrate

MA/AA: toxilic acid/acrylic copolymer, by BASF with trade name Sokalan ^

The sodium salt that CP5 sells, its molecular weight is 90,000.

Carbonate: anhydrous sodium carbonate

Perborate: anhydrous sodium perborate-hydrate and tetrahydrate SYNTHETIC OPTICAL WHITNER, empirical formula

NaBO ₂·H ₂O ₂

TAED: tetraacetyl ethylene diamine

DETPMP: diethylenetriamine five (methylene radical phosphine) acid

EDDS: quadrol-N, N '-disuccinic acid (S, S isomer)

CMC: sodium carboxy methyl cellulose

Enzyme: the blended protease of selling by Novo Industries AS and

Lipolytic enzyme

Lipase: by the fat of Novo Industries A/S with trade name Lipolase sale

Enzyme

Proteolytic enzyme: by the egg of Novo Industries A/S with trade name Savinase sale

White lytic enzyme

Silicate: ratio (SiO ₂: Na ₂O) be 2 amorphous sodium silicate

Vitriol: anhydrous magnesium sulfate

Composition catalyst: manganese tetraphenylporphyrin/polyphenyl acetyl sodium sulfonate vinyl naphthalene multipolymer

(MnTPP/PSSSVN)

Detergent composition (umber is represented with weight) below the preparation.Composition A, B, C, D are consistent with the present invention.

A B C DLAS--6.54 6.92TAS--2.94 2.0545AS 6.86 6.86--C25E3S 1.71 1.71 0.16 0.16C45E7--4.0 4.0C25E5 2.21 2.21--C25E3 1.16 1.1 6-- 1.45 1.45-- 10.2 10.2 18.0 20.2---5.5 2.5 2.3 2.35-SKS-6 9.2 8.5 8.64- 5.8 9.8 16.0 15.4--0.56 3.0--4.6--8.0--MA/AA 3.85 3.0 3.92 4.0CMC 0.30 0.30 0.30 0.31SRP 0.20 0.15 0.20 0.30PVP----PVNO 0.02---Savinase 0.41 0.25 0.37 1.4Lipolase 0.11 0.07 0.22 0.36Endo A 0.20 0.12 0.13 0.13PB4---11.64PB1---8.7TAED 4.7 1.6-5.0DETPMP--4.8 0.38MgSO4 0.38 0.38 0.4 0.40 16.9 10.0 17.5-EDDS 0.21 0.21 0.21- 0.22 0.18 0.19 0.19 0.002 0.002 0.002 0.002 2.75 2.75 0.85 0.85 0.35 0.4 0.35 0.43、7 ( )

Zeolite 26.0

Citrate trianion 10.4

Carbonate 11.9

Silicate 2.0

Supercarbonate 6.0

Vitriol 4.8

MA/AA 4.6

CMC 0.31

Title complex 0.002

Catalyzer

Add water, micro-thing and other thing to balance

Claims (27)

1, a kind of Metallomacrocycle catalyst composition, it comprises a kind of following title complex:

(i) a kind of transition-metal catalyst, it is selected from:

A. transition metal porphines and composition thereof;

B. transition metal phthalocyanine and composition thereof;

C. the mixture of transition metal porphines and transition metal phthalocyanine; (ii) a kind of amphiphilic polymer

And composition thereof;

This title complex makes the catalyzer transformation period prolong at least 1.1 times.

2, a kind of Metallomacrocycle catalyst composition according to claim 1, wherein said composition comprises at least one hydrophilic group and at least one hydrophobic group, hydrophilic group and hydrophobic group ratio are between 1: 10 to 10: 1; Preferred 1: 3 to 3: 1.

3, a kind of Metallomacrocycle catalyst composition according to claim 1 or 2, wherein said polymkeric substance are a kind of fragrant amphiphilic polymers.

4, a kind of according to Metallomacrocycle catalyst composition any among the claim 1-3, wherein this polymkeric substance has a polymerization system that is selected from random, grafting, block polymer.

5, a kind of according to Metallomacrocycle catalyst composition any among the claim 1-4, wherein this polymkeric substance has following general formula:

Wherein A and B can be selected from :-CH ₂-, NH, O, ketone, ester bond, amido linkage, imine linkage; Wherein n, m, p, r, s, t can independently be any integer, as long as (n+m+p) v+ (r+s+t) w is 1-1000, in the scope of preferred 1-500; The value of q and u is independently within 1-10; Each R can be independently selected from H, alkyl, alkyl halide, alkylyl; Preferred H, CH ₃R ₁Be selected from the hydrophobic part and the R that contain conjugation aromatic hydrocarbon ring ₂Be selected from hydrophilic segment.

6, a kind of according to Metallomacrocycle catalyst composition any among the claim 1-4, wherein this polymkeric substance has modular construction:

Wherein C and D are the oligose unit; The value of q and u is independent in the 1-10 scope; R ₁Be selected from the hydrophobic part and the R that contain conjugation aromatic hydrocarbon ring ₂Be selected from hydrophilic segment.

7, a kind of according to metal conference catalyst composition any among the claim 1-4, wherein this polymkeric substance has modular construction:

Wherein E and F are dibasic aromatic portion, as phenylene, naphthalene, phenanthroline, anthracene, thiophene; The value of q and u is independent in the 1-10 scope; R ₁Be selected from the hydrophobic part and the R that contain conjugation aromatic hydrocarbon ring ₂Be selected from hydrophilic segment.

8, a kind of according to Metallomacrocycle catalyst composition any among the claim 5-7, wherein R ₁Be selected from toluene, vinyl toluene, stilbene, pyridine, naphthalene, anthracene, phenanthrene, phenyl, Histidine, tryptophane, phenylalanine, tyrosine, alkylbenzene, dimethyl, carbazole, xanthene, acridine, purine, pyridazine and indoles.

9, a kind of according to Metallomacrocycle catalyst composition any among the claim 5-8, wherein R ₂Be selected from hydrophilic segment, as OH, hydroxyalkyl such as methylol and hydroxyethyl; The N-oxide derivative of polyoxyethylene, hydroxy phenyl and derivative thereof, part, pyridine-N-oxide, Histidine, tryptophane, phenylalanine and tyrosine derived from pyrrolidone; Water-soluble salt derivative, anthracene, phenanthrene, phenyl, carbazole, xanthene, acridine, purine, pyridazine and the indoles of phenylbenzimidazole sulfonic acid salt, naphthalenesulfonate, imidazoles, naphthalene ,-COOH ,-COOM ,-SO ₃M, wherein M is a kind of alkalimetal ion;-NR ₂,-NR ₃ ⁺X ^-, wherein X is that a kind of halide-ions and R independently are selected from H, alkyl and hydroxyalkyl.

10, a kind of according to Metallomacrocycle catalyst composition any among the claim 1-9, wherein this polymericular weight is 5 * 10 ²To 1 * 10 ⁶, preferred 1 * 1O ³To 5 * 1O ⁵Between.

11, a kind of basis is quoted any one Metallomacrocycle catalyst composition among the claim 8-10 of claim 5, and wherein said polymkeric substance is a kind of multipolymer such as sodium polystyrene sulfonate and vinyl naphthalene multipolymer.

12, a kind of Metallomacrocycle catalyst composition according to claim 1, wherein said polymkeric substance is cyclodextrin and forms a kind of inclusion complex with transition-metal catalyst.

13, a kind of according to Metallomacrocycle catalyst composition any among the claim 1-12, wherein said porphines comprises a kind of simple porphyrin such as tetraphenylporphyrin.

14, a kind of according to Metallomacrocycle catalyst composition any among the claim 1-12, wherein said transition metal porphines at least one place of position is therebetween replaced by the pyridine group of following formula:

Each X wherein ₁Independently be selected from H, F, Cl, Br, NO ₂, alkyl, alkoxyl group, cycloalkyl, aralkyl, aryl, alkaryl and heteroaryl, preferred H, Cl or F; And X ₂Be selected from O ^-, OH, H, alkyl, alkoxyl group, cycloalkyl, aralkyl, aryl, alkaryl and heteroaryl, preferred O ^-

15, a kind of according to Metallomacrocycle catalyst composition any among the claim 1-12, wherein said transition metal porphines at least one place of position is therebetween replaced by the phenyl of following formula: Wherein each X independently is selected from H, F, Cl, Br, alkyl, alkoxyl group, cycloalkyl, aralkyl, aryl, alkaryl and heteroaryl, preferred H, Cl or F.

16, a kind of according to Metallomacrocycle catalyst composition any among the claim 1-15, wherein said porphines comprises a kind of transition metal, and it is selected from the preferred Mn of Cu, Fe, Mn, Co, Cr, Ti and V..

17, a kind of according to Metallomacrocycle catalyst composition any among the claim 1-12, wherein said phthalocyanine comprises a kind of transition metal, and it is selected from Cu, Fe, Mn, Co, Cr, Ti and V, preferred Mn.

18, a kind of dye transfer inhibiting composition, it comprises a kind of according to a kind of Metallomacrocycle catalyst composition any among the claim 1-17 and a kind of peroxide source.

19, a kind of dye transfer inhibiting composition, it comprises a kind of Metallomacrocycle catalyst composition according to claim 18, wherein said peroxide source is selected from H ₂O ₂, organic peroxy carboxylic acid, inorganic peroxy SYNTHETIC OPTICAL WHITNER and said inorganic peroxy SYNTHETIC OPTICAL WHITNER and organic peroxide acid parent combination.

20, a kind of dye transfer inhibiting composition, it comprises a kind of Metallomacrocycle catalyst composition according to claim 1-18, and wherein said peroxide source is a kind of oxydo-reductase, and it is selected from glucose oxidase and alcohol oxidase.

21, a kind of detergent composition, it comprises a kind of according to metal conference catalyst composition any among the claim 1-17 and a kind of peroxide source, it also comprises enzyme, tensio-active agent, washing assistant and other conventional detergent ingredients.

22, a kind of detergent composition according to claim 21, wherein peroxide source is selected from H ₂O ₂, organic peroxy carboxylic acid, inorganic peroxy SYNTHETIC OPTICAL WHITNER, said inorganic peroxy SYNTHETIC OPTICAL WHITNER and organic peroxide acid parent combination, glucose oxidase and alcohol oxidase.

23, a kind of detergent additives composition, it is in adding a kind of aqueous cleaning solution that contains tensio-active agent and active oxygen source the time, be suitable for providing the dye transfer restraining effect, said composition comprises any one Metallomacrocycle catalyst composition of claim 1-17.

24, a kind of including in washing suppressed the method that dyestuff shifts between fabric in the operating process of yarn dyed fabric, and this method comprises this fabric is contacted with washings with a kind of laundry that contains the washing composition interpolation composition of with good grounds claim 23.

25, a kind of including in washing suppressed the method that dyestuff shifts between fabric in the operating process of yarn dyed fabric, and this method comprises this fabric is contained dye transfer inhibiting composition any among the with good grounds claim 18-20 or a kind of laundry according to claim 21 and 22 detergent composition contacts with washings with a kind of.

26, a kind of epoxidizing method that under the situation that imidazoles exists, carries out, wherein Metallomacrocycle catalyst composition comprises a kind of following title complex:

(i) a kind of transition-metal catalyst, it is selected from:

A. transition metal porphines and composition thereof,

B. transition metal phthalocyanine and composition thereof,

C. the mixture of transition metal porphines and transition metal phthalocyanine and

(ii) a kind of amphiphilic polymer and composition thereof;

This title complex makes the catalyzer transformation period prolong 1.1 times at least.

27, a kind of epoxidizing method according to claim 26 wherein is selected from by epoxidised material: cyclooctene, 1-tetrahydrotoluene and tetramethyl-ethylene.