CA2083661A1 - Detergent bleach compositions - Google Patents

Detergent bleach compositions

Info

Publication number
CA2083661A1
CA2083661A1 CA 2083661 CA2083661A CA2083661A1 CA 2083661 A1 CA2083661 A1 CA 2083661A1 CA 2083661 CA2083661 CA 2083661 CA 2083661 A CA2083661 A CA 2083661A CA 2083661 A1 CA2083661 A1 CA 2083661A1
Authority
CA
Canada
Prior art keywords
weight
characterised
composition according
alkyl
bleach
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA 2083661
Other languages
French (fr)
Inventor
Rudolf J. Martens
Ton Swarthoff
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever PLC
Original Assignee
Rudolf J. Martens
Ton Swarthoff
Unilever Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to EP91203078.0 priority Critical
Priority to EP91203078 priority
Application filed by Rudolf J. Martens, Ton Swarthoff, Unilever Plc filed Critical Rudolf J. Martens
Publication of CA2083661A1 publication Critical patent/CA2083661A1/en
Application status is Abandoned legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3902Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905Bleach activators; Bleach catalysts
    • C11D3/3932Inorganic compounds or complexes

Abstract

C7291 (L) ABSTRACT

Detergent bleach compositions are disclosed comprising a surface active material, a peroxide bleaching agent and a dinuclear manganese complex as the bleach catalyst, characterised in that the composition comprises from 0-25%
by weight of anionic surfactant and from 7.5-55% by weight of nonionic surfactant, the weight ratio of nonionic surfactant to anionic surfactant being at least 0.75 if the composition contains not more than 7.5% by weight of a carbonate, expressed as sodium carbonate, and at least 2.2. if the composition contains more than 7.5% by weight of a carbonate.

Description

3 ~ $ ~

- 1 - C7291 (L) DETERGENT BLEACH_COMPOSITIONS

This invention relates to detergent bleach compositions.
More particularly, it relates to improved detergent bleach compositions, espscially but not exclusively adapted for washing and cleaning of fabrics, containing, a surfactant material, a peroxide bleaching agent and a manganese complex as bleach catalyst.
The manganese complex used in the present invention is a dinuclear manganese complex of the formula:

~ M~

wherein Mn is manganese which can individually be in the III or IV oxidation state; X1, X2 and X3 each independently represent a coordinating or bridging species selected from the group consisting of H2O, o22-, o2-, OH-, HO2-, SH-, S2-, >SO, Cl-, N3-, SCN-, RCOO-, RSO-3, NH2- and NR3, with R being H, alkyl, aryl, both optionally substituted, or R'COO-where R' is alkyl, aryl, both optionally substituted; L is ; 6 ~

- 2 - C7291 (L) a ligand which is an organic molecule containing at least three nitrogen atoms which coordi.nates via all or some of the nitrogen atoms to the manganese centres; z denotes the charge of the complex and is an integer which can be positive or negative; Y is a monovalent or multivalent counter-ion, leading to charge neutrality, which is dependent upon the charge z of the complex; and q --Z/[charge Y].

Preferred manganese-complexes are those wherein ~1' X2 and X3 are either CH3COO- or o2- or mixtures thereof and, most preferably, wherein the manganese is in the IV oxidation state and X1, X2 and X3 are o2-.

Particularly preferred complexes are those in which the ligand is of formula l{NR3 - (C~l(R2)U)t]~

wherein t is an integer from 2 to 3; s is an integer from 3 to 4; u is zero or one; Rl, R2 and R3 are each independently selected from H, alkyl, aryl, both optionally substituted.

Other preferred complexes are those which comprise two ligands of formula _[NR 3 ~ (R Z) ) 1~

wherein t is an integer from 2 to 3;
s is an integer from 3 to 4;

- 3 - C7291 (L) u is zero or one;
Rl and R2 are each independently selected from H, alkyl, aryl, both optionally substituted; and R3 is independently selected from hydrogen, alkyl, aryl, both optionally substituted, with the proviso that a bridging unit ~4 iS ~ormed by one R3 unit from each ligand where R4 is the group CnRsR6-(D)p-CmR9R6 ~here p is zero or one;
D is selected from a heteroatom such as oxygen and NR7 or is part of an aromatic or saturated homonuclear or heteronuclear ring, n is an integer from 1 to 4;
m is an integer from 1 to 4;
with the proviso that n ~ m <= 4 if p is zero or p is one and D is part of an aromatic or saturated homonuclear or heteronuclear ring; and that n + m <=3 if p is one and D
is a heteroatom such as oxygen or NR7;
Rsand R6 are each independently selected from H, MR8 and OR9, alkyl, aryl, optionally substituted and R7, R~, R9 are each independently selected from H, alkyl, aryl, both optionally substituted.

Examples of suitable ligands in their simplest forms are:

25 (i) 1,4,7-triazacyclononane;
1,4,7-triazacylclodecane;
1,4,8-triazacycloundecane;
1,5,9-triazacyclododecane.
1,4,7-trimethyl-1,4,7-triazacyclononane 1,4,7-trimethyl-1,4,7-triazacyclodecane;
1,4,8-trimethyl-1,4,8-triazacycloundecane;
1,5,9-trimethyl-1,5,9-triazacyclododecane.
1,2-bis-(4,7-dimethyl-1,4,7-triaza-1,-cyclononyl)ethane.

- 4 - C7291 (L) (ii) Tris(pyridin-2-yl)methcme;
Tris(pyrazol-l-yl)methane;
Tris(imidazol-2-yl)methane;
Tris(triazol-1-yl)methane.
S
(iii) Tris(pyridin-2-yl)borate;
Tris(triazol-1-yl)borate;
Tris(pyra201-1-yl)borat:e;
Tris(imidazol-2-yl)phosphine;
Tris(imidazol-2-yl)borate.

(iv) 1,3,5-trisamino-cyclohexane;
1,1,1-tris(methylamino)ethane.

15 (v) Bis(pyridin-2-yl-methyl)amine;
Bis(pyrazol-1-yl-methyl)amine;
Bis(triazol-1-yl-methyl)amine;
Bis(imidazol-2-yl-methyl)amine, all optionally substituted on amine N-atom and/or CH2 carbon atom and/or aromatic ring.

Of these the ligands of group (i) and their carbon-substituted derivatives are especially preferred, particularly:

(1) 1,4,7-trimethyl-1,4,7 triazacyclononane (Me3TACN~, and (2) 1,2,4,7-tetramethyl-1,4,7-triazacyclononane ( Me4TACN ) (3) 1,2,2,4,7-pentamethyl-1,4,7-triazacyclononane ( MesTACN ) c~3~

- 5 - C7291 (L) (4) 2-benzyl-1,4,7-trimethyl-1,4,7-triazacyclononane (5) 1,2-bis(4,7-dimethyl-1"4,7-triaza-1-cyclonoyl)ethane(Et-br:idged(Me2TACN) 2 ) The type of counter-ion Y for charge neutrality is not critical for the activity of the complex and can be selected from for example any of the following counter-ions: chloride; sulphate; nitrate; methylsulphate;
surfactant-anions, such as the long-chain alkyl~ulphates, alkylsulphonates, alkylbenzenesulphonates, tosylate;
trifluormethylsulphonate; perchlorate (C104-), BPh4- and PF6-, though some counter-ions are more preferred than others for reasons of product property and safety.
However the most preferred manganese complexes as used in the present invention are:

tI) [ (Me3TACN)MnIV~-0)3MnIv(Me3TACN) ]2~(PF6-)2 (II) [ (Me4TACN)MnIV(~-O) 3MIlIV ( Me4TACN ) ] 2~ ( PF6- ) 2 (III) [ (Me3TACN)Mn~ O)(~-OAc)2MnIII(Me3TACN) ] 2t (PF6 )2 (IV) [ (Me4TACN)MnIII(~-O) (Il-OAc)2MnIII(Me4TACN) ]2 (PF6 )2 (V) [ (Et-bridged(Me2TACN)2)MIlIIIMnIV(~1-0)2(11-OAc) ]2 (C104 )2 which are hereinafter also abbreviated as:

(I) [MnIV2(~-O) 3 (Me3TACN) 2] ( PF6) 2' æo~3~

- 6 - C7291 (L) ( I I ~ [MnIVz ~ O ) 3 (Me4TACN~ 2 ] ( PF6 ) 2 (III) [MnIII2 (~-O) ('~I-OAc) 2 (Me3l~AcN)2] (PF6)2 5 (IV) ~Mn~II2(~-O) (,U-OAc)2(Me4l'AcN)2] (PF6)2 It is believed that for complex I the structural formula is as given below: 2f ~ n~V / o ~ N~> (P~6-)2 ~ / ~ N ~ l These manganese complexes are reported in Applicant's co-pending European Patent Specification No~s 458 397 and 458 398 as unusually effective bleach and oxidation catalysts. In the further description of the invention they will also be referred to as th~ "bleach catalyst~ or simply ~'catalystl~.

The invention now relates to detergent bleaching compositions comprising a surface-active material, a peroxide bl~aching agent and the above-described dinuclear manganese-complex as bleach catalyst.

~LL~ 3 -G~ 7~-9~

The peroxide bleaching agents are normally compounds which are capable of yielding hydrogen peroxide in aqueous solution. Hydrogen peroxide sources are well known in the art. They,include the alkali metal peroxides, organic 2~3~
_ 7 _ C7291 (L) peroxides such as urea peroxide, and inorganic persalts, such as the alkali metal perborates, percarbonates, perphosphates, persilicates and persulphates. Mixtures of two or more such compounds may also be suitable.
Particularly preferred are sodium perborate tetrahydrate and, especially, sodium perborate monohydrate. Sodium perborate monohydrate is preferred because of its high active oxygen content. Sodium percarbonate may also be preferred for environmental reasons. The amount thereof in the composition of the invention usually will be within the range of about 5-35% by weight, preferably from 10-25%
by weight.

Alkylhydroxy peroxides are another class of peroxide bleaching agents. Examples of these materials include cumene hydroperoxide and t-butyl hydroperoxide.

Organic peroxyacids may also be suitable as the peroxide bleaching agent. Such materials normally have the general formula:
o HOO - C - R- Y
wherein R is an alkylene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally having an internal amide linkage; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a COOH or C - OOH group or a quaternary ammonium group.

Typical monoperoxy acids useful herein include, for example:

3~
- 8 - C7291 (L) (i) peroxybenzoic acid and ring-substituted peroxybenzoic acids, e.g. peroxy-a-naphthoic acid;

5 (ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids, e.g. peroxylauric acid, peroxystearic acid and N,N-phthaloylaminoperoxy caproic acid (P~P); and (iii) 6-octylamino-6-oxo-peroxyhexanoic acid.

Typical diperoxyacids useful herein include, for example:

(iv) 1,12-diperoxydodecanedioic acid (DRDA);
(v) l,9-diperoxyazelaic acid;

(vi) diperoxybrassilic acid; diperoxysebasic acid and diperoxyisophthalic acid;
(vii) 2-decyldiperoxybutane-1,4-dioic acid; and .

(viii) 4,4'-sulphonylbispero~ybenzoic acid.

Also inorganic peroxyacid compounds are suitable, such as for example potassium monopersulphate (MPS). If organic or inorganic peroxyacids are used as the peroxygen compound, the amount thereof will normally be within the range of about 2-10% by weight, preferably from 4-8% by weight.

All these peroxide compounds may be utili~ed alone or in conjunction with a peroxyacid bleach precursor and/or an organic bleach catalyst.

~3~

- 9 - C7291 (L) Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836,988;
864,798; 907,356; 1,003,310 and 1,519,3~1; German Patent 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591; and US Patents 1,246,339; 3,332,882i 4,128,494; 4,412,934 and 4,675,393.

Another useful class of peroxyaci.d bleach precursors is that of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US Patents 4,751,015 and 4,397,757, in EP-A-284292 and EP-A-331,229. Examples of peroxyacid bleach precursors of this class are:

2-(N,N,N-trimethyl ammonium) ethyl sodium-4-sulphonphenyl carbonate chloride - (SPCC);
N-octyl,N,N-dimethyl-N10-carbophenoxy decyl a~nonium chloride - IODC~;
3-tN,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate; and N,N,N-trimethyl ammonium toluyloxy benzene sulphonate.

A further special class of cationic peroxyacid bleach precursors is formed by the cationic nitriles as disclosed in EP-A-0303520 and in European Patent Specification No.'s 458396 and 464880.

Any one of these peroxyacid bleach precursors can be used in the present invention, though some may be more preferred than others.

Of the above classes of bleach precursors, the preferred classes are the esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates; the acyl-amides; and ~. . . . . . .

2 ~

-- 10 - C7291 (L) the quaternary ammonium substituted peroxyacid precursors including the cationic nitriles.

Examples of said pre~errad peroxyacid bleach precursors or activators are sodium-4-benzoloxy benzene sulphonate (SBOBS); N,N,N',N'-tetraacetyl ethylene diamine (TAED);
sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoloxy benzoate; SPCC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5-trimethyl hexanoyloxybenzene sulphonate (STHOBS); and the substituted cationic nitriles.

The precursors may be used in an amount of about 1-8%, preferably from 2-5% by weight, of the composition.
Organic bleach catalyst most suitable for being utilized here are the so-called suphonimides as disclosed in EP-A-0,453,003 and EP-A-0,446,982.

The Surface-Active Mate The surface-active material normally used in detergent bleach compositions may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwiterionic, cationic actives and mixtures thereof. Many suitable actives are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Sch~artz, Perry and Berch.
Typical synthetic anionic surface-actives are usually water-soluhle alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the al}cyl portion of higher aryl radicals.

~3~

- 11 - C7291 (L) Examples of suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (Ca-C18) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium alkyl (Cg-ClO) benzene sulphonates, particularly sodium linear secondary alkyl (C10 C1s) benzene sulphonates;
sodium alkyl glyceryl ether sulphates, especially those esters of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum;
sodium coconu~ oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (Cg-C18) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (Ca-C20) with sodium bisulphite and those derived by reaction paraffins with SO2 and Cl2 and then hydrolysing with a base to produce a random sulphonate; sodium and ammonium C7-Cl2 dialkyl sulphosuccinates; and olefin sulphonates, which term is used to describe material made by reacting olefins, particularly C1o-C20 alpha-olefins, with S03 and then neutralising and hydrolysing the reaction product.
The preferred anionic detergent co~pounds are sodium (C10-C1s) alkylbenzene sulphonates, sodium (C16-C18) alkyl ether sulphates.

Examples of suitable nonionic surface-active compounds which may be used, preferably together with the anionic surface-active compounds, include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-C22) phenols, generally 5-25 EO, i.e.
5-25 units of ethylene oxides per molecule; the 2~36~

- 12 - C7291 (L) condensation products of aliphatic (C8-Cla) primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO, and products may be condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine. Other so-caIled nonionic surface-actives include alkyl polyglycosides, sugar esters, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and diallkyl sulphoxides.

Amount of amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.

It has been found however, that if the catalysts hereinbefore described are used in detergent bleach compositions their performance is highly dependent upon the active detergent system and the builder system of the composition. Experiments have shown that anionic surfactants in general and long chain Cl6-C22 fatty acid soaps in particular have a strong negative effect on the catalyst activity, thereby decreasing the performance dramatically, whereas nonionic detergent surfactants do not interact with the catalyst. Short chain Cl2-Cl4 fatty acid soaps at lower levels up to about 10% by weight have a positive effect on the catalyst activity, but at high concentrations, e.g. >20% by weight they also become detrimental.

The mechanism causing these effects is not fully understood, though it can be hypothesized that by some mechanism the catalyst is believed to be (partly) 2~3~

- 13 - C7291 (L) withdrawn from the solution in the presence of anionic surfactants. This may for instance happen by precipitation o the negatively charged actives with the positively charged catalyst molecule or only by ion pair formation which causes catalytic inactivi~y. Another possibility may be that the catalyst is enclosed in the micelles of the anion-active surfactant.

Whatever the reason may be, it is clear that the bleach performance of deter~ent bleach compositions comprising a dinuclear manganese complex catalysed peroxide bleach system, is not optimal if the active detergent system comprises an anionic surface-active material.

It is therefore an object of the present invention to provide a detergent bleach composition comprising a surface-active material, a peroxide bleaching agent and a dinuclear manganese complex as hereinbefore described having optimal bleaching action.
It has now surprisingly been found that by including a nonionic surfactant in sufficient amounts it is possible to enhance the bleaching action back to optimal.

Without wishing to be bound to any theory, it is believed that the nonionic, provided it is present in sufficient amounts, compensates the strong negative effect of anionic surfactants by resolubilization of the catalyst.

Accordingly the invention provides a detergenk bleach composition comprising a surface-active material, a peroxide bleaching agent and a dinuclear manganese complex as the bleach catalyst, which composition is characterized in that it comprises from 0-25% by weight of anionic surfactant and from 7.5-55% by weight of nonionic ~3~
- 14 - C7291 ~L) surfactant, the weight ratio of nonionic surfactant to anionic surfactant being at least 0.75 if the composition contains 0-7.5~ by weight of a carbonate builder, expressed as sodium carbonate, and at least 2.2 if the composition contains more than 7.5~ by weight of carbonate builder.

Preferably the composition will comprise from 0-15% by weight of anionic surfactant and from 10-40% by weight of nonionic surfactant.

In a further preferred embodiment the detergent active system is free from C16-C22 fatty acid soaps. In another preferred embodiment the detergent bleach composition is an all-nonionic based formulation exempt from any anionic surfactant.

The composition of the invention normally and preferably also contains a detergency builder in an amount of from about 5-80% by weight, preferably from about 10-60% by weight.

The DeterqencY Builder Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixture thereof.

Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble saltsi the alkali metal salts of carboxymethyloxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic 2~3~

- 15 - C7291 (L) acids, citric acid; and polyacetal carboxylates as disclosed in US patents 4,14~,~26 and 4,146,~95.

Examples of precipitating builder materials include sodium orthophosphate and sodium carbonate.

Examples of calcium ion-exchange builder materials include the various types of water-insolllble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, ~eolite B (also known as Zeolite P), zeolite C, zeolite ~, zeolite Y and also the zeolite P type as described in EP-A-0,384,070.

In particular, the compositions of the invention may contain any o~e of the organic or inorganic builder materials, though, for environmental reasons, phosphate builders are preferably omitted or only used in very small amounts.

Typical builders usable in the present invention are, for example, sodium carbonate, calcite/carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyloxy malonate, carboxymethyloxy succinate and the water-insoluble crystalline or amorphous aluminosilicate builder material, each of which can be used as the main builder, either alone or in admixture with other builders or polymers as co-builder.

As to the builder system, it has been furthermore o~served that alkalimetal carbonates and phosphates, especially sodium carbonate, sodium bicarbonate and sodium triphosphate, also have a negative influence on the catalytic bleach performance of hydroperoxide bleaches, but surprisingly, only to a much lesser extent on the catalytic bleach performance of peroxyacid bleaches. The ~3~

- 16 - C7291 (L) carbonate effect is however pH dependent in that upon increasing the pH to above 10, particularly to 10.5 and above, the negative effect is largely removed.

Accordingly when using a hydroperoxide, such as sodium perborate or sodium percarbonate, as the bleaching agent, it is preferred that the composition contains not more than 5% by weight of a carbonate builder, expressed as sodium carbonate, more preferable not more than 2.5% by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.

Apart from the components already mentioned, the detergent compositions of the invention can contain any of the conventional additives in amounts of which such materials are normally employed in fabric washing detergent compositions. Examples of these additives include buffers such as carbonates, lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkernel fatty acids and coconut fatty acids;
lather depressants, such as alkyl phosphates and silicones; anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; stabilizers, such as ethylene diamine tetraacetic acid (EDTA) and the phosphonic acid derivatives (i.e. Dequest ~ types); fabric softening agents; inorganic salts and alkaline buffering agents, such as sodium sulphate, sodium silicate etc.; and usually in very small amounts, fluorescent agents; perfumesi en7ymes, such as proteases, cellulases, lipases, amylases and oxidases; ~ermicides and colourants.

When using a hydroperoxide, such as sodium perborate or sodium percarbonate, as the bleaching agent, it is preferred that the composition contains not more than 5%

2~ 6~
- 17 - C7291 (L) by weight of a carbonate buffer, expressed as sodium carbonate, more preferable not more than 2.5% by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.
Of the additives, transition metal sequestrants, such as EDTA and the phosphonic acid der:ivatives, e.g. ethylene diamine tetra- (methylene phosphonate) -EDTMP- are of special importance, as not only do they improve the stability of the catalyst/H2O2 system and sensitive ingredients, such as e~zymes, fluorescent agents, perfumes and the like, but also improve the bleach performance, especially at the higher pH region of above 10, particularly at pH 10.5 and above.
Accordingly detergent bleach compositions comprising a surface-active material, a peroxide bleaching agent, the manganese complex bleach catalyst, a carbonate builder and a transition metal sequestxant, having pH in solution of above 10, especially of 10.5 and above, are within the purview of the present invention.

Also within the purview of the present invention are detergent bleach compositions comprising a surface-active material, a peroxyacid bleach, such as DPDA, PAP and MPS, the bleach catalyst, and a phosphate builder, preferably sodium triphosphate.

Another optional but highly desirable additive ingredient with multi-functional characteristics in detergent compositions is from 0.1~ to about 3% by weight of a polymeric material having a molecular weight of from 1,000 to 2,000,000 and which can be a homo- or co-polymer of acrylic acid, maleic acid, or salt or anhydride thereof, vinyl pyrrolidone, methyl- or ethylvinyl ethers, and other - 18 - C7291 (L) polymerizable vinyl monomers. Preferred examples of such polymeric materials are polyacry]ic acid or polyacrylate;
polymaleic acid/acrylic acid copolymer; 70:30 acrylic acid/hydroxyethyl maleate copolymer; 1:1 styrene/maleic acid copolymer; isobutylene/maleic acid and diisobutylene/maleic acid copolymers; methyl- and ethyl-vinylether/maleic acid copolymers; ethylene/maleic acid copolymer; polyvinyl pyrrolidone; and vinyl pyrrolidone/maleic ac-d copolymer.
Detergent bleach compositions of the invention, when formulated as free-flowing particles, e.g. in powdered or granulated form, can be produced by any of the conventional techniques employed in the manufacture of detergent compositions, for instance by slurry-making, followed by spray-drying to form a detergent base powder to which the heat-sensitive ingredients including the peroxide compound bleach and optionally some other ingredients as desired, and the bleach catalyst, can be added as dry substances.

It will be appreciated, however, that the detergent base powder compositions, to which the bleach catalyst is added, can itself be made in a variety of other ways, such as the so-called part-part processing, non-tower route processing, dry-mixing, agglomeration, granulation, extrusion, compacting and densifying processes etc., such ways being well known to those skilled in the art and not forming the essential part of the present invention.
The invention will now be illustrated by way of the following non-limiting Examples.

20~3~6~

- 19 - C7291 (L) Example 1 The following examples were carried out in glass vessels, equipped with a temperature controlled heating spiral in ~uartz, magnetic stirrer, thermo-couple and pH
electrode.

At 40C isothermal, experiments in demineralised water at pH 10, were carried out to determine the effect of soaps, primary alcohol sulphate (PAS), alkyl benzene sulphonate (ABS), and nonionic surfactant (NI) on the bleach performance of sodium perborate monohydrate (PBM) and [ Mn 2(~-O)3(Me-TACN)2 ](PF6)2, i.e. complex (I), as the bleach catalyst, on standard tea-stained test cloths.
The bleach system in the wash solution was added at a concentration of 2.5 ~mol/l catalyst and 8.6 mmol/l PBM, corresponding to 0.03% by weight of catalyst and 14.3% by weight of PBM if a detergent bleach formulation is dosed at 6 g/l.

Test cloths were immersed for 30 minutes in each of the compositions of the examples. After rinsing with tap water, the cloths were dried in a tumble drier. The reflectance (R460.) was measured on a Zeiss Elrephometer before and after treatment. The difference (~R460.) in the value gives a measure of the effectiveness of the treatment.

The results are shown in the following Table 1.

21~3~

~ 20 - C7291 (~.) ~ T _ ~--= ~ ==~ =;~= _= __ Addition _ Cl8-soap Cl2~ Cl2~ ABS NI2) soap P~S
~ ~ __ ~ ~ _. _ .
wt.% _ 1.6 9 9 9 9 4 _ ~ ~ ~ __ ~ _ ~ ~ __ R460~ 25.0 22.8 8.7 28.6 15.7 16.6 26 8 __ ~ _ __ ~ = _ 1) = Empicol LXV ex Albright & Wilson 2) = Synperonic A7 ex ICI
The results show that when a Cl8-soap is present in a very low quantity eg. 1:6% by weight there is a detectable decrease in the performance of the catalyst. At 9% by weight Cl8-soap decreases the performance dramatically from 25 ~ R units to about 9 units. Surprisingly, Cl2-soap at 9% enhances the catalytic bleach performance up to 29 units. Both synthetic anionic surfactants PAS (at 9%) and ABS (at 9%) also have a strong negative effect on the catalyst activity, decreasing the catalytic bleach performance from 25 units to about 16 units.

On the other hand 4~ of NI hardly influences the catalyst activity.

Example II

This Example shows the effect of nonionic addition on the bleach performance of a formulation containing 9% Cl8-soap.
The experiments were carried out under exactly the same conditions as used in Example 1.

The results are shown in Table 2.

- 21 - C7291 (L) Table 2 ~ = == - ___ _ __ present _ _ _ 9% Cl~-soap I - ~
addition . ~ NI
wt.% _ - ~ 4 16 ~ R4 60 * 25.0 8.7 _ = 21.0 25.7 These results clearly show that addition of 4% NI is not sufficient to adequately improve the bleach performance, whereas an addition o 16% (NI: Anionic ratio of 1:8), enhances the catalytic bleach performance back to optimal approximately 25 ~R units.

Exam~le III

This Example shows the effect of nonionic addition on the bleach performance of a formulation containing 9% ABS.
The experiments were carried out under exactly the same conditions as used in Example II and the results are shown in Table 3.

Table 3 _ . _ _ ~
¦present _ _ 9% ABS
30 ¦addition _ - --- - NI2~ NI~
l _ .
¦~ R460 _ 25.0 16.6 23.9 26.7 _ These results clearly show that addition of 4% NI is not sufficient to adequately improve the bleach performance, 2~83~

- 22 - C7291 (L) whereas an addition of 8% (NI:anionic ratio 0.9) enhances the catalytic bleach performance and gives a better result than the control experiment without active.

Example IV

This Example shows the effect of increasing amounts of C12-soap on the catalytic bleach performance of a catalyst/PBM
bleach system on tea-stained test cloths. The experiments were carried out under the same conditions as used in Example I. The results are given in Table 4.

Table 4 ~ _ - , _ _ C12-soap(% by weight) 0 9 21 33 74 I _ _ ----1 Immol/l _ O _ 2.4 5.8 _9.0 20 20~ R460* 25.028.625.1 23.4 20.2 ~ J _ . = _ ~ _ _ . _ , Example V

This Example shows the effect of Na2CO3 on the bleach performance of a detergent bleach composition of the following nominal formulation:

2~3~

- 23 - C7291 (L) _~ I
¦ % by Weight __ Alkyl benzene sulphonate (ABS) 3.0 l ~ ~ . _, _ ~
Cl8-soap _ 1.7 _ _ Nonionic (Synperonic A3/A7) ~ _ 9 S ¦Zeolite _ _ _ _ 2~ ~
¦Polymer (Sokalan CP5 ex BASF) 4.0_ _ Sodium carboxymethylcellulose O.6 Sodium perborate monohydrate __ 14.3 _ . _ 11 Mn-complex (I) catalyst 0.03 The washing experiments were carried out at 40C
isothermal, using tap water of 16FH at pH lQ and pH 10.5.
Tea-stained test cloths were immersed in the wash solution, contalning the bleach composition dosed at 6g/l, for 30 minutes The results expressed as reflectance difference ~ R~60* are shown in the following Tables.

~able 5 (at pH 10) _ "=-- - _ _ _ Na2CO3 added _ 2.5 5.0 10.0 20.0 ¦
(% by weight) I . . _ ~ . _ _ _ ~ 25.6 21.6 21.7 16.8 15.7 The slightly negative effect of sodium carbonate at levels up to 5.0% and the significance decrease of catalytic bleach performance by the addition of higher levels, i.e.
10% and 20%, of sodium carbonate are clearly shown.

~3~3 - 24 -C7291 (L) Tabl3 6 (at pH 10.5) r ~ T----~~~~ - _ ¦Na2CO3 added (% by weight) I _ 10.0 20.0 ¦A ~460* (-EDTA) ¦ 24.9 22.0 18.1 I __ I _ _ ¦~ R460~ (+ 0.3% EDTA) ¦ 28.0 26.1 The positive effect of increasing pH and adding EDTA are shown by the results in Table 6.

Example VI

Example I was repeated except the bleach catalyst used was MnIII MnIV (~-0)2(~-OAc)(Et~bridged(Me2TACN)2)~ and millipore water (ie. demineralised water which was further purified by treatment through a Milli-Q plus water purification system ex Millipore Corporation).
The level of catalyst corresponds to 0.037% by weight and of PBM to 14.3% by weight if a detergent bleach formulation is dosed at 6g/1.

(~ - prepared according to a method described by Prof Wieghardt at the 1991 ICBIC Conference in Oxford (UK)) The results obtained are set out in Table 7.

'~83~

- 25 - C7291 (L) Table 7 . ~ =~
Addition _ABS NI- ABS+NI
. ~
wt.% _ 9 4 _ 9~8 1 9+ ~ 7+16 4+16 MIlIV2 (,U-O) 3 (Me3TACN) 2 .__ ~ _. ___ ~ _ -~ I
~R460- 25.0 16.6 l26.8 26.7 _ _ I _ . . __ _ __ MllIIIMnIV ( ~- ) 2 ( ~-OAc)(Et-bridged(Me2TACN) 2 ) 0 ~R~60. 127.2~ 14. 127. ~ ~9.1 1_22.3_ ~ 8 ~ 28.0 Synperonic A7 ex ICI.

The results show a bridged material related to Mn2~IV~
0) 3 (Me3TACN) 2 catalyses perborate bleaching. The bleach catalysis i5 significantly reduced by the use of ABS but not if nonionic is used. However, if ABS as well as nonionic are present, a larger amount of nonionic is required to compensate for the poor effect of ABS than in the case when a non-bridged complex is used as bleach catalyst.

Claims (13)

1. A detergent bleach composition comprising a surface active material, a peroxide bleaching agent and a dinuclear manganese complex, as the bleach catalyst, having the formula:

wherein Mn is manganese which can individually be in the III or IV oxidation state; Xl, X2 and X3 each independently represent a coordinating or bridging species selected from the group consisting of H20, o22-, o2-, OH-, HO2-, SH-, S2-, >SO, Cl-, N3-, SCN-, RCOO-, RSO-3, NH2- and NR3, with R being H, alkyl aryl, both optionally substituted, or R'COO- where R' is alkyl, aryl both optionally substituted; L is a ligand which is an organic molecule containing at least three nitrogen atoms which coordinates via all or some of the nitrogen atoms to the manganese centres; z denotes the charge of the complex and is an integer which can be positive or negative; Y is a monovalent or multivalent counter-ion, leading to charge neutrality, which is dependent upon the charge z of the complex; and q = Z/[charge Y], characterised in that the composition comprises from 0-25% by weight of anionic surfactant and from 7.5-55% by weight of nonionic surfactant, the weight ratio of nonionic surfactant to anionic surfactant being at least 0.75 if the composition contains 0-7.5% by weight of a carbonate, expressed as sodium carbonate, and at least 2.2. if the composition contains more than 7.5%
by weight of a carbonate.

C7291 US (L)
2. A composition according to claim 1, characterised in that it comprises from 0-15% by weight of anionic surfactant and from 10-40% by weight of nonionic surfactant.
3. A composition according to claim 1 characterised in that the detergent active system is free from Cl6-C22 fatty acid soaps.
4. A composition according to claim 1 characterised in that the surface active agent is a nonionic surface active agent.
5. A composition according to claim 1 characterised in that the bleaching agent is a hydroperoxide compound.
6. A composition according to claim 1, characterised in that it has a pH of up to 10 and contains not more than 5% by weight of a carbonate, expressed as sodium carbonate.
7. A composition according to claim 1, characterised in that it is substantially free of carbonate.
8. A composition according to claim 1 characterised in that the bleaching agent is a peroxyacid compound.
9. A composition according to claim 1 wherein the bleach catalyst comprises a ligand of formula C7291 US (L) wherein t is an integer from 2 to 3; s is an integer from 3 to 4; u is zero to one; Rl, R2 and R3 are each independently selected from H, alkyl, aryl, both optionally substituted.
10. A composition according to claim 1 wherein the bleach catalyst comprises two ligands of formula wherein t is an integer from 2 to 3;
s is an integer from 3 to 4;
u is zero or one;
Rl and R2 are each independently selected from H, alkyl, aryl, both optionally substituted; and R3 is independently selected from hydrogen, alkyl, aryl, both optionally substituted, with the proviso that a bridging unit R4 is formed by one R3 unit from each ligand where R4 is the group CnR5R6-(D)p-CmR5R6 where p is zero or one;
D is selected from a heteroatom such as oxygen and NR7 or is part of an aromatic or saturated homonuclear or heteronuclear ring, n is an integer from 1 to 4;
m is an integer from 1 to 4;
with the proviso that n + m <= 4 if p is zero or p is one and D is part of an aromatic or saturated homonuclear or heteronuclear ring; and that n + m <=3 if p is one and D is a heteroatom such as oxygen or NR7;
R5 and R6 are each independently selected from H, NR8 and OR9, alkyl, aryl, optionally substituted and R7, C7291 US (L) R8, R9 are each independently selected from H, alkyl, aryl, both optionally substituted.
11. A composition according to claim 1, characterised in that the bleach catalyst is selected from the complexes:

(I) [MnIV2(µ-O) 3 (Me3TACN) 2] (PF6) 2 (II) [MnIv2(µ-O)3(Me4TAcN)2](pF6)2 (III) [MnIII2(µ_O)(µ-0Ac) 2 (Me3TACN) 2] ( PF6) 2 (IV) [Mn III2(µ-O) (µ-OAc)2(Me4TACN>2] (PF6)2 (V) [ (Et-bridged(Me2TACN)2)MnIIIMn IV(µ-O )2(µ-OAc) ]2 (C104) 2
12. A composition according to claim 11, characterised in that said bleach catalyst is complex (I).
13. A composition as claimed in claim 1 and substantially as described herein.
CA 2083661 1991-11-26 1992-11-24 Detergent bleach compositions Abandoned CA2083661A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP91203078.0 1991-11-26
EP91203078 1991-11-26

Publications (1)

Publication Number Publication Date
CA2083661A1 true CA2083661A1 (en) 1993-05-27

Family

ID=8208033

Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2083661 Abandoned CA2083661A1 (en) 1991-11-26 1992-11-24 Detergent bleach compositions

Country Status (11)

Country Link
EP (1) EP0544490A1 (en)
JP (1) JPH0768543B2 (en)
KR (1) KR960000205B1 (en)
CN (1) CN1031647C (en)
AU (1) AU661522B2 (en)
BR (1) BR9204549A (en)
CA (1) CA2083661A1 (en)
MX (1) MX9206779A (en)
TR (1) TR27075A (en)
TW (1) TW234144B (en)
ZA (1) ZA9208188B (en)

Families Citing this family (138)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU6000594A (en) * 1993-02-22 1994-09-14 Unilever Plc Machine dishwashing composition
GB9305599D0 (en) * 1993-03-18 1993-05-05 Unilever Plc Detergent compositions
US5686014A (en) * 1994-04-07 1997-11-11 The Procter & Gamble Company Bleach compositions comprising manganese-containing bleach catalysts
CA2187175A1 (en) * 1994-04-07 1995-10-19 Alastair John Pretty Bleach compositions comprising metal-containing bleach catalysts and antioxidants
US5560748A (en) * 1994-06-10 1996-10-01 The Procter & Gamble Company Detergent compositions comprising large pore size redox catalysts
BR9507984A (en) * 1994-06-13 1997-11-18 Unilever Nv bleaching and oxidation catalyst and bleach composition
AT269392T (en) 1994-07-21 2004-07-15 Ciba Sc Holding Ag Bleaching composition for tissue
WO1996006157A1 (en) * 1994-08-19 1996-02-29 Unilever N.V. Detergent bleach composition
WO1996006154A1 (en) * 1994-08-19 1996-02-29 Unilever N.V. Detergent bleach composition
US5578136A (en) 1994-08-31 1996-11-26 The Procter & Gamble Company Automatic dishwashing compositions comprising quaternary substituted bleach activators
US5968881A (en) * 1995-02-02 1999-10-19 The Procter & Gamble Company Phosphate built automatic dishwashing compositions comprising catalysts
MX9705985A (en) * 1995-02-02 1997-11-29 Procter & Gamble Automatic dishwashing compositions comprising cobalt chelated catalysts.
CA2211717C (en) * 1995-02-02 2001-04-03 The Procter & Gamble Company Automatic dishwashing compositions comprising cobalt (iii) catalysts
GB2297978A (en) 1995-02-15 1996-08-21 Procter & Gamble Detergent compositions containing amylase
WO1997000311A1 (en) * 1995-06-16 1997-01-03 The Procter & Gamble Company Bleach compositions comprising cobalt catalysts
DE69613842D1 (en) * 1995-06-16 2001-08-16 Procter & Gamble containing cobalt catalysts automatic dishwasher detergents,
DE19523891C1 (en) * 1995-06-30 1996-11-21 Hoechst Ag Chiral manganese triazanonankomplexe and processes for their preparation
DE19535082A1 (en) 1995-09-21 1997-03-27 Henkel Ecolab Gmbh & Co Ohg A paste detergents and cleaners
US5703034A (en) * 1995-10-30 1997-12-30 The Procter & Gamble Company Bleach catalyst particles
GB9523654D0 (en) 1995-11-18 1996-01-17 Ciba Geigy Ag Fabric bleaching composition
DE19545729A1 (en) 1995-12-08 1997-06-12 Henkel Kgaa Bleach and detergent with an enzymatic bleaching system
DE19605688A1 (en) * 1996-02-16 1997-08-21 Henkel Kgaa Transition metal complexes as activators for peroxygen compounds
GB2311078A (en) * 1996-03-16 1997-09-17 Procter & Gamble Bleaching composition containing cellulolytic enzyme
EP0891415A1 (en) * 1996-04-01 1999-01-20 Henkel Kommanditgesellschaft auf Aktien Cleaning agent with oligoammine activator complexes for peroxide compounds
DE19620411A1 (en) 1996-04-01 1997-10-02 Henkel Kgaa Übergangsmetallamminkomplexe as activators for peroxygen compounds
JP2974786B2 (en) 1996-05-03 1999-11-10 ザ、プロクター、エンド、ギャンブル、カンパニー Detergent composition comprising a polyamine polymer having improved stain dispersibility
DE19620241A1 (en) * 1996-05-20 1997-11-27 Patt R Prof Dr A method for delignification of pulps using a catalyst and
CA2257891A1 (en) * 1996-06-19 1997-12-24 Roelant Mathijs Hermant Bleach activation by an iron catalyst comprising a polydentate ligand containing at least six heteroatoms
US5850086A (en) * 1996-06-21 1998-12-15 Regents Of The University Of Minnesota Iron complexes for bleach activation and stereospecific oxidation
DE19636035A1 (en) 1996-09-05 1998-03-12 Henkel Ecolab Gmbh & Co Ohg A paste detergents and cleaners
DE19649375A1 (en) 1996-11-29 1998-06-04 Henkel Kgaa Acetonitrile derivatives as bleach activators in detergents
DE19703364A1 (en) 1997-01-30 1998-08-06 Henkel Ecolab Gmbh & Co Ohg A paste detergents and cleaners
DE19714122A1 (en) 1997-04-05 1998-10-08 Clariant Gmbh Bleach actives metal complexes
DE19719397A1 (en) * 1997-05-07 1998-11-12 Clariant Gmbh Bleach actives metal complexes
DE19728021A1 (en) * 1997-07-01 1999-01-07 Clariant Gmbh Metal complexes as bleach activators
DE19732749A1 (en) 1997-07-30 1999-02-04 Henkel Kgaa Glucanasehaltiges detergent
DE19732751A1 (en) 1997-07-30 1999-02-04 Henkel Kgaa New beta-glucanase from Bacillus
DE19732750A1 (en) 1997-07-30 1999-02-04 Henkel Kgaa Glucanasehaltiges cleaners for hard surfaces
AR015977A1 (en) 1997-10-23 2001-05-30 Genencor Int Multiply-substituted protease variants with altered net charge for use in detergents
US6992056B1 (en) 1997-12-30 2006-01-31 Henkel Kgaa Process for preparing detergent tablets having two or more regions
US6410500B1 (en) 1997-12-30 2002-06-25 Henkel Kommanditgesellschaft Auf Aktien Moulded body dishwasher detergents with soil release polymers
DE19758262A1 (en) 1997-12-31 1999-07-08 Henkel Kgaa Alkylaminotriazolhaltige, granular component for use in dishwashing detergents (MGSM) and methods for its preparation
DE19819187A1 (en) 1998-04-30 1999-11-11 Henkel Kgaa Solid machine dishwasher detergent with phosphate and crystalline layered silicates
DE19850100A1 (en) 1998-10-29 2000-05-04 Henkel Kgaa Polymer granules by fluidized bed granulation
DE19908051A1 (en) 1999-02-25 2000-08-31 Henkel Kgaa A process for preparing compounded acetonitrile derivatives
DE19914811A1 (en) 1999-03-31 2000-10-05 Henkel Kgaa Detergent compositions containing a bleaching agent include a combination of a cyanomethyl ammonium salt bleach activator and an enzyme
DE19943254A1 (en) * 1999-09-10 2001-03-15 Clariant Gmbh Bleach active metal complexes
DE19944218A1 (en) 1999-09-15 2001-03-29 Cognis Deutschland Gmbh detergent tablets
US6610752B1 (en) 1999-10-09 2003-08-26 Cognis Deutschland Gmbh Defoamer granules and processes for producing the same
US6686327B1 (en) 1999-10-09 2004-02-03 Cognis Deutschland Gmbh & Co. Kg Shaped bodies with improved solubility in water
US6696401B1 (en) 1999-11-09 2004-02-24 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines
DE19953792A1 (en) 1999-11-09 2001-05-17 Cognis Deutschland Gmbh detergent tablets
US6812198B2 (en) 1999-11-09 2004-11-02 The Procter & Gamble Company Laundry detergent compositions comprising hydrophobically modified polyamines
US6846791B1 (en) 1999-11-09 2005-01-25 The Procter & Gamble Company Laundry detergent compositions comprising hydrophobically modified polyamines
DE19956802A1 (en) 1999-11-25 2001-06-13 Cognis Deutschland Gmbh detergent tablets
DE19962883A1 (en) 1999-12-24 2001-07-12 Cognis Deutschland Gmbh detergent tablets
DE19962886A1 (en) 1999-12-24 2001-07-05 Cognis Deutschland Gmbh Surfactant granules with an improved dissolving rate
DE10003124A1 (en) 2000-01-26 2001-08-09 Cognis Deutschland Gmbh A process for the production of surfactant granules
DE10019344A1 (en) 2000-04-18 2001-11-08 Cognis Deutschland Gmbh Washing and cleaning agents
DE10019405A1 (en) 2000-04-19 2001-10-25 Cognis Deutschland Gmbh Dry detergent granulate production comprises reducing fatty alcohol content in technical mixture of alkyl and/or alkenyl-oligoglycosides and mixing resultant melt with detergent additives in mixer or extruder
DE10031620A1 (en) 2000-06-29 2002-01-10 Cognis Deutschland Gmbh liquid detergent
DE10044472A1 (en) 2000-09-08 2002-03-21 Cognis Deutschland Gmbh laundry detergent
DE10044471A1 (en) 2000-09-08 2002-03-21 Cognis Deutschland Gmbh Fabric-conditioning detergent composition comprising an anionic surfactant, a nonionic and amphoteric surfactant, a cationic polymer and a phosphate
DE10046251A1 (en) 2000-09-19 2002-03-28 Cognis Deutschland Gmbh Detergents and cleaning agents based on alkyl and / or alkenyl oligoglycosides and fatty alcohols
AU3947502A (en) 2000-10-27 2002-05-27 Procter & Gamble Stabilized liquid compositions
DE10058645A1 (en) 2000-11-25 2002-05-29 Clariant Gmbh The use of cyclic sugar ketones as catalysts for peroxygen compounds
DE10102248A1 (en) 2001-01-19 2002-07-25 Clariant Gmbh Use of transition metal complexes with oxime ligands as bleach catalysts
DE10163331A1 (en) 2001-12-21 2003-07-10 Henkel Kgaa Although supported bleach catalyst complexes useful as catalysts for peroxygen compounds
DE10163856A1 (en) 2001-12-22 2003-07-10 Cognis Deutschland Gmbh Hydroxy mixed ethers and polymers in the form of solid compositions as a starting compound for washing, rinsing and cleaning agents
DE10304131A1 (en) 2003-02-03 2004-08-05 Clariant Gmbh Transition metal complexes with nitrogen-containing ligands are used as catalysts for peroxy compounds, especially in detergent, bleaching and cleansing agents
BRPI0407114B1 (en) 2003-02-03 2018-09-11 Unilever Nv Composition for washing
US20090205143A1 (en) 2005-05-27 2009-08-20 Ronald Hage Process of bleaching
DE602006006325D1 (en) 2005-10-12 2009-05-28 Unilever Nv A method for bleaching substrates
AT466923T (en) 2006-07-27 2010-05-15 Evonik Degussa Gmbh coated sodium
EP1903098B1 (en) 2006-07-27 2008-10-15 Evonik Degussa GmbH Coated sodium percarbonate particle
EP1889901B1 (en) 2006-07-27 2008-09-24 Evonik Degussa GmbH Coated sodium percarbonate particle
ES2394847T3 (en) 2007-01-16 2013-02-06 Catexel Limited Bleaching of substrates
DE102007003885A1 (en) 2007-01-19 2008-07-24 Bk Giulini Gmbh Use of a builder system comprising alkali metal tripolyphosphate and iminodisuccinic acid to produce automatic dishwasher formulations
AT522595T (en) 2007-10-12 2011-09-15 Basf Se Dishwashing formulations containing a mixture of hydrophobically modified polycarboxylates and hydrophilically modified polycarboxylates
JP5401034B2 (en) 2007-12-19 2014-01-29 ライオン株式会社 Bleaching aids, and bleaching aid particles containing bleaching aids
DE502007005869D1 (en) 2007-12-19 2011-01-13 Evonik Degussa Gmbh A process for producing coated sodium
DE102008000029A1 (en) 2008-01-10 2009-07-16 Bk Giulini Gmbh Use of phosphate reduced building system comprising alkali tripolyphosphate and imino disuccinic acid, for manufacturing formulations e.g. for the automatic or mechanical dish cleaning and crockery cleaning machines on ships
US20090325841A1 (en) 2008-02-11 2009-12-31 Ecolab Inc. Use of activator complexes to enhance lower temperature cleaning in alkaline peroxide cleaning systems
DE102008024800A1 (en) 2008-05-23 2009-11-26 Henkel Ag & Co. Kgaa Method for washing textiles in the presence of a peroxygenated bleaching agent and a bleach boosting transition metal complex
GB0813460D0 (en) 2008-07-23 2008-08-27 Reckitt Benckiser Nv Container
DE102008045297A1 (en) 2008-09-02 2010-03-04 Friedrich-Alexander-Universität Erlangen-Nürnberg Method for washing textiles in the presence of a peroxygenated bleaching agent and a bleach boosting transition metal complex
BR112012000520A2 (en) 2009-07-09 2016-02-16 Procter & Gamble catalytic detergent composition for clothes washing comprising relatively low concentrations of water soluble electrolyte
CA2767170A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company A catalytic laundry detergent composition comprising relatively low levels of water-soluble electrolyte
WO2011005910A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Method of laundering fabric using a compacted laundry detergent composition
WO2011005623A1 (en) 2009-07-09 2011-01-13 The Procter & Gamble Company Laundry detergent composition comprising low level of bleach
EP2451919A1 (en) 2009-07-09 2012-05-16 The Procter and Gamble Company Method of laundering fabric using a liquid laundry detergent composition
ES2581916T3 (en) 2009-08-13 2016-09-08 The Procter & Gamble Company Method of washing fabrics at low temperature
US8933131B2 (en) 2010-01-12 2015-01-13 The Procter & Gamble Company Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same
EP2550283B1 (en) 2010-03-03 2016-05-11 Catexel Limited Preparation of bleaching catalysts
WO2011146602A2 (en) 2010-05-18 2011-11-24 Milliken & Company Optical brighteners and compositions comprising the same
JP5698348B2 (en) 2010-05-18 2015-04-08 ミリケン・アンド・カンパニーMilliken & Company Fluorescent whitening agents and compositions containing the same
US8476216B2 (en) 2010-05-28 2013-07-02 Milliken & Company Colored speckles having delayed release properties
CN103025929B (en) 2010-07-02 2015-11-25 宝洁公司 Containing the active agent filaments, nonwoven webs and methods for their preparation
EP2588652B1 (en) 2010-07-02 2019-06-12 The Procter and Gamble Company Method for treating a fabric
CN103025930B (en) 2010-07-02 2014-11-12 宝洁公司 Method for delivering an active agent
MX345026B (en) 2010-07-02 2017-01-12 Procter & Gamble Web material and method for making same.
WO2012003316A1 (en) 2010-07-02 2012-01-05 The Procter & Gamble Company Process for making films from nonwoven webs
WO2012009660A2 (en) 2010-07-15 2012-01-19 The Procter & Gamble Company Detergent compositions comprising microbially produced fatty alcohols and derivatives thereof
EP2593075A2 (en) 2010-07-15 2013-05-22 The Procter and Gamble Company A personal care composition comprising a near-terminal branched compound
US8715368B2 (en) 2010-11-12 2014-05-06 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
CA2827627C (en) 2011-02-17 2016-10-11 The Procter & Gamble Company Compositions comprising mixtures of c10-c13 alkylphenyl sulfonates
MX2013009546A (en) 2011-02-17 2013-11-22 Procter & Gamble Bio-based linear alkylphenyl sulfonates.
JP2014512257A (en) 2011-02-25 2014-05-22 ミリケン・アンド・カンパニーMilliken & Company Capsules and compositions comprising the same
US20140141126A1 (en) 2011-06-29 2014-05-22 Solae Llc Baked food compositions comprising soy whey proteins that have been isolated from processing streams
CN107428787A (en) 2011-09-08 2017-12-01 卡特克塞尔科技有限公司 Catalysts
US20130072413A1 (en) 2011-09-20 2013-03-21 The Procter & Gamble Company DETERGENT COMPOSITIONS COMPRISING PRIMARY SURFACTANT SYSTEMS COMPRISING HIGHLY BRANCHED ISOPRENOID-BASED and OTHER SURFACTANTS
WO2013043852A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company Easy-rinse detergent compositions comprising isoprenoid-based surfactants
WO2013043855A2 (en) 2011-09-20 2013-03-28 The Procter & Gamble Company High suds detergent compositions comprising isoprenoid-based surfactants
BR112014006583A2 (en) 2011-09-20 2017-03-28 Procter & Gamble detergent compositions comprising organic surfactant systems comprising surfactants derived from isoprenoid
EP2758503A2 (en) 2011-09-20 2014-07-30 The Procter and Gamble Company Detergent compositions comprising specific blend ratios of isoprenoid-based surfactants
US20130171421A1 (en) 2012-01-04 2013-07-04 The Procter & Gamble Company Active containing fibrous structures with multiple regions having differing characteristics
CN104508103A (en) 2012-07-26 2015-04-08 宝洁公司 Low PH liquid cleaning compositions with enzymes
BR112015021923A2 (en) 2013-03-28 2017-07-18 Procter & Gamble Cleaning compositions containing a polyetheramine a dirt remover polymer and carboxymethyl cellulose
CN105980618A (en) 2013-12-09 2016-09-28 宝洁公司 Fibrous Structures Including An Active Agent And Having A Graphic Printed Thereon
US20150275143A1 (en) 2014-03-27 2015-10-01 The Procter & Gamble Company Cleaning compositions containing a polyetheramine
JP6275864B2 (en) 2014-03-27 2018-02-07 ザ プロクター アンド ギャンブル カンパニー Cleaning compositions containing polyetheramine
EP3152288A1 (en) 2014-06-06 2017-04-12 The Procter and Gamble Company Detergent composition comprising polyalkyleneimine polymers
US9624119B2 (en) 2014-06-13 2017-04-18 Ecolab Usa Inc. Enhanced catalyst stability in activated peroxygen and/or alkaline detergent formulations
US10196592B2 (en) 2014-06-13 2019-02-05 Ecolab Usa Inc. Enhanced catalyst stability for alkaline detergent formulations
DK2966161T3 (en) 2014-07-08 2019-02-25 Dalli Werke Gmbh & Co Kg Enzymblegemiddelkatalysatorcogranulat suitable for detergent compositions
EP3075832A1 (en) 2015-03-30 2016-10-05 Dalli-Werke GmbH & Co. KG Manganese-amino acid compounds in cleaning compositions
US10155868B2 (en) 2015-10-13 2018-12-18 Milliken & Company Whitening agents for cellulosic substrates
US9902923B2 (en) 2015-10-13 2018-02-27 The Procter & Gamble Company Polyglycerol dye whitening agents for cellulosic substrates
US9745544B2 (en) 2015-10-13 2017-08-29 The Procter & Gamble Company Whitening agents for cellulosic substrates
US20170101602A1 (en) 2015-10-13 2017-04-13 The Procter & Gamble Company Novel whitening agents for cellulosic substrates
US9777250B2 (en) 2015-10-13 2017-10-03 Milliken & Company Whitening agents for cellulosic substrates
US9976035B2 (en) 2015-10-13 2018-05-22 Milliken & Company Whitening agents for cellulosic substrates
US10308900B2 (en) 2015-12-22 2019-06-04 Milliken & Company Occult particles for use in granular laundry care compositions
DK3190168T3 (en) 2016-01-06 2019-07-15 Dalli Werke Gmbh & Co Kg Coating cleaner catalyst
US20180216285A1 (en) 2017-01-27 2018-08-02 The Procter & Gamble Company Active Agent-Containing Articles that Exhibit Consumer Acceptable Article In-Use Properties
US20180216287A1 (en) 2017-01-27 2018-08-02 The Procter & Gamble Company Active Agent-Containing Articles and Product-Shipping Assemblies for Containing the Same
US20180216286A1 (en) 2017-01-27 2018-08-02 The Procter & Gamble Company Active Agent-Containing Articles that Exhibit Consumer Acceptable Article In-Use Properties
WO2018140472A1 (en) 2017-01-27 2018-08-02 The Procter & Gamble Company Active agent-containing articles that exhibit consumer acceptable article in-use properties

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9003741D0 (en) * 1990-02-19 1990-04-18 Unilever Plc Bleach activation
EP0458398B1 (en) * 1990-05-21 1997-03-26 Unilever N.V. Bleach activation

Also Published As

Publication number Publication date
CN1031647C (en) 1996-04-24
AU2962092A (en) 1993-06-17
CN1073714A (en) 1993-06-30
KR930010171A (en) 1993-06-22
AU661522B2 (en) 1995-07-27
ZA9208188B (en) 1994-05-26
JPH0768543B2 (en) 1995-07-26
TR27075A (en) 1994-10-18
BR9204549A (en) 1993-06-01
JPH0641586A (en) 1994-02-15
MX9206779A (en) 1993-05-01
EP0544490A1 (en) 1993-06-02
TW234144B (en) 1994-11-11
KR960000205B1 (en) 1996-01-03

Similar Documents

Publication Publication Date Title
CN1040020C (en) Bleaching or sterilizing composition and method
US5047163A (en) Activation of bleach precursors with sulfonimines
AU732147B2 (en) Bleach compositions
US5045223A (en) N-sulfonyloxaziridines as bleaching compounds
CA2282406C (en) Catalysts and methods for catalytic oxidation
ES2226429T3 (en) Composition and method for bleaching a substrate.
DE69827738T2 (en) bleach activation
CA1324379C (en) Quaternary ammonium or phosphonium peroxycarbonic acid precursors and their use in detergent bleach compositions
US5965506A (en) Fabric bleaching composition
ES2314492T3 (en) Bispidon ligand derivatives and complexes thereof for the catalytic bleaching of a substrate.
US20020198128A1 (en) Bleach compositions containing metal bleach catalyst, and bleach activators and/or organic percarboxylic acids
AU2002233187B2 (en) Ligand and complex for catalytically bleaching a substrate
CA2176228C (en) Activation of bleach precursors with imine quaternary salts
JP3960620B2 (en) Imine salts as bleach catalysts
AU749512B2 (en) Bleach catalysts and formulations containing them
CA2342616C (en) Method of treating a textile
CN1185242C (en) Ligand and complex for catalytically bleaching substate
EP0399584B1 (en) Bleach activation and bleaching compositions
KR101912962B1 (en) Bleach catalysts
US4988451A (en) Stabilization of particles containing quaternary ammonium bleach precursors
KR950001046B1 (en) Bleach activation
US6153576A (en) Transition-metal complexes used as activators for peroxy compounds
AU649803B2 (en) Concentrated detergent powder composition
CA2037800C (en) Bleach catalysts and compositions containing the same
US3775332A (en) Method of activating per-compounds and solid activated per-compound compositions

Legal Events

Date Code Title Description
EEER Examination request
FZDE Dead