CA1187655A

CA1187655A - Bleach compositions

Info

Publication number: CA1187655A
Application number: CA000418331A
Authority: CA
Inventors: John Oakes
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1981-12-23
Filing date: 1982-12-22
Publication date: 1985-05-28
Also published as: NO824259L; FI824367L; IN156181B; US4481129A; DE3264333D1; EP0082563B1; AU546367B2; EP0082563A3; DK568782A; PT76019A; NZ202823A; PH19859A; PT76019B; GR77065B; ZA829322B; AU9167682A; NO156757B; GB2112034B; BR8207413A; JPS58111900A

Abstract

Abstract of the Disclosure Bleach compositions comprising a peroxide compound contain manganese (II) in an amount of 0.005 to 5% by weight and a carbonate compound which delivers carbonate ions in aqueous solution in an amount of 1 to 50% by weight of carbonate ions.

The bleach compositions are suitable for bleaching fab-rics at substantially all washing temperatures.

Description

1~8 76~5 C 808 (R) This invention relates to bleach compositions comprising a peroxide compound bleach suitable for bleaching fa-brics. The peroxide compound bleach used herein include hydrogen peroxide and inorganic persalts which liberate hydrogen peroxide in aqueous solutions such as the water-soluble perborate6, percarbonates, perphosphates, persilicates and the like.

Detergent compositions comprising said peroxide com-pounds are known in the art. Since said peroxide com-pounds are relatively ineffective at lower temperatures, e.g. up to 70C, these compositions have to be used at boiling temperatures in order to achieve a satisfactory bleach.
Various proposals have been made to activate peroxide compounds so as to make them usable bleaches at lower temperatures~ One proposed route is the u e of so-called organic activators - usually organic compoun~s having one or moxe reacti~e acyl residues - which in solution react with the peroxide compound, e.g. sodium perborate, to form an organic peroxy-acid e.g. peroxy-acetic acid, which is a more effective bleach at lower temperatures. Such bleach activators are described for example in a serie~ of articles by Allan H.Gilbert in "Detergent Age", June 1967, pages 18-20, July 1967, August 1967, pages 26, 27 and 67.
:
Another approach is the u~e of heavy metal ions of the transition series which cataly~e peroxide decompo~ition, together with a special type of chelating agent for ~aid heavy metal a~ described in US Patent 3,156,654.
' ,~

", C 808 (R) It is disclosed there that only by a proper choice of the heavy metal and of the chelating agent, not only with respect to each other but also in regard of the adsorp--tion power of the material to be bleached i~e. fabrics, relative to the complexing strength of the chelating agent an lmproved bleaching can be obtained. Though the possible use of any heavy metal of the transition series, is disclosed, provided the proper chelating agent is employed therewith, only combinations of cobalt and copper salts with pyridine carboxylic acid chelating agents, preferably as a preformed complex, in bleaching ba~hs comprising sodium perborate are disclosed.

US Patent 3,53~,634 discloses bleaching compositions comprising a persalt, an organic activator and a tran-sition metal, together with specially selected chelating agents. The transition metals applicable according to this US patent have atomic numbers of from 24 to 29.

British Patent 984,459 suggested the use of a copper salt in combination with a sequestering agent which is methylaminodiacetic acid, aminotriacetic acid or hydro-xyethylaminodiacetic acid.

US Patent 4,119,557 suggested the use of a preformed ~erric ion complex with a polycarboxyamine type chela-ting agent.

Still the main problem with heavy metal catalysis is that the re~ultfi are often inconsistent and/or unsatis-factory in the ca~e of use for washing at lower temper-atures.

The present inv0ntion seeks to overcome the above problems.

~ 76~ c 808 (R) It has now been found that one heavy metal in particular, i.e manganese, has surprisingly out~tanding properties with respect to consistently improving the bleach per-formance of peroxide compounds at subs~antially all tem peratures, when used in combination with a carbonate com-pound which delivers carbonate ions (C032 ) in aqueous media, which effect has been observed in the absence of any special type of chelating agents as proposed in US
Patent Specifications 3 156 654 and 3 532 634.
The manganese used in the present invention can be de-rived from any manganese (II) salt, such as manganous sulphate and manganous chloride, or from any manganese compound which delivars manganese (II) ions in aqueous solution.

The effect increases with increased manganese (II) ion concentration in the wash solution up to a certain level, whereupon the effect begins to slow down. On the other hand the carbonate effect increases continuously with the carbonate level, the upper level of which is only limi-ted by other practical limitationæ, such as for-mulation requirements.

The optimum levels of manganese (II) ions - Mn2+ ~ in the wash/bleach solution are dependent upon the formulation in which t'ne manganese as bleach catalyst is appl~ed, especially upon detergency builder type and level. In terms of parts p~r million (ppm) of manganese (II) ions in the wash/bleach solution a suitable range will gener-rally be from 0.1 to 50 ppm, preferably from 0.5 - 25 ppm.

These correspond roughly to a manganese (II) metal con-tent in a bleach or detergent composition of about 0.005 - 5% by weight, preferably from 0~025 - 2.5~ by weight of the composition.

, 6~5 C 808 (R) It was further discovered that alkalimetal triphosphate, particularly sodium triphosphate, has a negative influ-ence on the catalysing effect. ~lence the higher levels within said above range are usable in compositions con-taining alkalirnetal triphosphate as the main builder con-stituent, whereas if the bleach system is free from tri-phosphate builder, the effective level of Mn2~ in the wash/bleach solution will be in the ~ange of about 0.1 -10 ppm, prefsrably 0.5 - 8 ppm which range corresponds to a manganese (II) content in the composition o~ about 0.005 - 1~ by weight, prefer~bly 0.025 - 0.8% by weight.

The carbonate effect on the catalytic activity of manga-nese can be observed already with carbonate ion levels in the wash/bleach solutions of about 150 ppm. This cor-responds roughly with a carbonate ion content in the com positions of about 1~ by weight. The effects increase consistently with increasing levels of carbonate, 50~ by weight of carbonate ion being taken as the practical up-per level in the compositions. In fact the effects areso marked that iarge activation can be achieved with car-bonate-built detergent compositions comprising sodium perborate. A preferred range of carbonate ion level is from about 5-35% by weight.
Accordingly the invention provides a bleach compoqition comprising a peroxide compound which is characterized in that it comprise~ manganese (II) in an amount o~ 0.005 5 by weight, preferably n . 025 - 2.5% by weight, and a cax-bonate compound which delivers carbonate ions in aqueousmedia, in an amount of 1-50 wt.~, preferably 5 -35 wt.%, expressed as carbonate ion level in the composition.

Any manganese (II) salt can in principle be employed, such as for example manganous sulphate (Mn.S04), either in its anhydrous form or as hydrated salt, manganous chloride (MgC12~ anhydrous or hydrated and the like.

11~76~5 c 808 (R) Any carbonate compound w~ich delivers carbonate ions in aqueous media can in principla be employed, including al-kalimetal carbonates and percarbonates, such as for e~am-ple sodium carbonate (Na2C03~, potas~ium carbonate ~K2C03), sodium percaxbonate (~a2C03.1.5H202), p sium percarbonate (K2C03.1 5H2O2). At least 1% by weight preferably from 5% by weight, calculated a~ carbonate ion, of any of these salts or mixtures thereof are con-templated in the practice of thi~ invention.
The bleach composition of the invention may also con-tain a surface active agent, generally in an amount of from about 2~ to 50~ by weight, preferably from 5 - 30%
by weight. The surface active agent can be anionic, non-ionic, zwitterionic or cationic in nature or mixtures thereof.

Preferr0d anionic non-soap surfactants are water-soluble salts of alkyl benzene sulphonate, alkyl ~ulphate, alkyl polyethoxy ether sulphate, paraffin sulphonate, alp~a-olefin sulphonate, alpha-sulfocarbo~ylates and their es-ters, alkyl glyceryl ether sulphonate, fatty acid mono-glyceride sulphates and sulphonates, alkyl phenol poly-ethoxy ether sulphate, 2-acyloxy-alkane-1-sulphonate, and beta-alkyloxy alkane sulphonate. Soaps are also pre-ferred anionic sur~actants.

Especially preferred are alkyl benzene ~u~phonates with about 9 to about 15 carbon atom~ in a linear or branched alkyl chain, more especially about 11 to about 13 c~rbon atoms; alkyl sulphates with about 8 to about 22 carbon atom~ in the alXyl chain, more especially from about 12 to about 18 carbon atom~, alkyl polyethoxy ether sulp~ates with about 10 to about 18 carbon atom~ in the alkyl chain and an average of about 1 to about 12 -CH2CH20-groups per molecule, especially about 10 to about 16 carbon atom~ in 1~76~ C 80~ (R) the alkyl chain and an average of about 1 to about 6 CH2CH20-groups per molecule; linear paraffin sulphonates with about 8 to about 24 carbon atoms, more especially from about 14 to about 18 atoms; and alpha-olefin sul-phonates with about 10 to about 24 carbons atoms, moreespecially about 14 to about 16 carbon atoms; and soaps having from 8 to 24, especially 12 to 18 carbon atoms.

Water-solubility can be achieved by using alkali metal, ammonium, or alkanolamine cations; sodium is preferred.
Magnesium and calcium cations may be preferred under cir-cumstances described by Belgian Patent 843,636. Mixtures of anionic/nonionic surfactants are contemplated by this invention; a satisfactory mixture contains alkyl benzene sulphonate having 11 to 13 carbon atoms in the alkyl group and alkyl polyethoxy alcohol sulphate having 10 to 16 carbon atoms in the alkyl group and an average degree of ethoxylation of 1 to 6.

Preferred nonionic surfactants are water-soluble com-pounds produced by the condensation of ethylene oxide with a hydrophobic compound such as an alcohol, alkyl phenol, polypropoxy glycol, or polypropoxy ethylene di-amine.
25Especially preferred polyethoxy alcohols are ~he conden-sation product of 1 t.o 30 moles of ethylene oxide with 1 mol of branched or straight chain, primary or secondary aliphatic alcohol having from about 8 to about 22 carbon atom: morP especially 1 to 6 moles of ethylene oxide con-densed with 1 mol of straight or branched chain, primary or secondary aliphatic alcohol having from about 10 to about 16 carbon atoms; certain species of poly-ethoxy al-cohol are commercially available under the trade-names of "Neodol" R, "Synperonic" R and "Tergitol" ~.

~ 6~5 C 808 (R) Preferred zwitterionic ~urfactants are water-~oluble de-rivatives of aliphatic quaternary ammonium, phosphonium and sulphonium cationic compounds in which the aliphatic moieties can be straight or branched, and wherein one of the aliphatic substituent~ contains from about 8 to 18 carbon atoms and one contain~ an anionic water-solubil-izing group, especially alkyl-dimethyl-propane-sulphon-ates and alkyl-dimethyl-ammonio-hydroxy- propane-sul-phonates wherein the alkyl group in both types contains Erom about l to 18 carbon atoms.

Preferred cationic surface active agent3 include the quaternary ammonium compounds having one or tw~ hydro-phobic groups with 8-20 carbon atoms, e.g. cetyl tri-methyl ammonium bxomide or chloride, dioctadecyl dimethylammonium chloride; and the fatty alkyl amine~.

A typical listing of the classas and species of surfac-tants u4eful in this invention appear in the books "Sur-face Active Agent~", Vol. I, by Schwartz & Perry (Inter-science 1949) and "Surface Active Agents", Vol. II by Schwarz, Perry and Berch (Interscience 1958), the dis~
closures of which are incorporated herein by reference.
The listing, and the foregoing recitation of speci~lc - 25 surfactant compounds and mixtures which can be used in the specific sur~actant compounds and mixtures which can be used in ~he instant compositions, are representative but are not intended to be limiting.

In addition thereto the compositions of the invention may contain any o~ the conventional components and/or adjuncts usable in fabric wa~hing compositions.

As such can be named~ ~or in~tance, conventional alka-line detergency builder3, inoxganic or organic, which can be used at level3 up to about 80~ by weight of the com-position, preferably from 10% to 50~ by weight.

~j 1187~55 C 808 (R) Examples of suitable i.norganic alkaline detergency buil-ders are water-soluble alkalimetal phosphates, polyphos-phates, borates, silicates and also carbonates. ~pecific examples of such salts are sodium and potassium triphoq-phates, pyrophosphates, orthophosphates, hexametaphos-phates, tetraborates, ~ilicates and carbonates.

Examples of suitable organic alkalinè detergency buil-der salts are: (1) water-soluble amino polycarboxylates, e.g. sodium and potassium ethylenediaminetetraacetate~, ni.trilotriacetates and N-(2-hydroxyethyl)-nitrilodia-cetates; (2) water soluble salts of phytic acid, e.g.
sodim and potassium phytates (see U.S. Patent No~

2,379,942); (3) water-soluble polyphosphonates, inclu-ding specifi.cally, sodium, potassium and lithium saltsof ethane-l-hydroxy~ diphosphonic acid sodium, po-tassium and lithium salts of methylene diphosphonic acid; sodium, potassium and lithium salts of ethylene diphosphonic acid; and sodium, potassium and lithium salts of ethane-1,1,2-tripho~phonic acid. Other e~amples include the alkali metal salts of ethane-2-carboxy-1,1-diphosphonic acid, hydroxymethanediphosphoni.c acid, carboxyldiphosphonic acid, ethane-l hydroxy-1,1,2-tri-phosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propate-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphoni.c acid, and propane-1,2,2,3-tetraphosphonic acid; (4) water-soluble salts of poly-carboxylate polymers and copolymers as described in U.S.
Patent No. 3,308,067.
In addition, polycarboxylate builders can be uqed satis-factorily, including water-æoluble salts of mellitic acid, citric acid, and carboxymethyloxysuccinic acid and alts of polymer~ of itaconic acid and maleic acid.

~ C 808 (R) Certain zeolites or aluminosilicates can also be used.
One such aluminosllicate which is useful in the composi-tions of the invention is an amorphous water-insoluble hydrated compound of the formula Nax(yAl02.Si0~, S wherein x is a number from 1.0 to 1.2 and y is 1, said amorphous material being further characterized by a Mg++
exchange capacity of from about 50 mg eq. CaCO3/g. to about 150 mg eq. CaCO3/g. and a particle diameter of from about 0.01 micron to about 5 microns. This ion ex-change builder is more fully described in British PatentNo. 1,470,250.

A second wa~er-insoluble synthetic aluminosilicate ion exchange material useful herein is crystalline in nature and has the formula Naz ~(A102)y. (SiO~)~xH2o~ wherein z and y are integers of at least 6; the molar ratio of z to y is in the range from 1~0 to about 0.5, and x is an integer from about 15 to about 264, said aluminosilicate ion exchange material having a particle size diameter from about 0.1 micron to about 100 microns; a calcium ion exchange capacity on an anhydrous basis of at least about 200 milligrams equivalent of CaCO3 hardness per gram;
and a calcium ion exchange rate on an anhydrous basis of at least about 2 grains/gallon/minute/ gram. These syn-thetic aluminosilicates are more fully described inBritish Patent No. 1,429,143.
If a carbonate builder is used said carbonate will com-bine builder capacity wi-th the presently found carbonate effect on bleaching.

If other builder substances are used, the required car-bonate ion level should be supplied by e.g. using surplus carbonate builder or replacing part of the builder by sodium carbonate or by using wholly or partly sodium per-carbonate as the peroxide compound bleach.
i C 808 (R) For nominally unbuilt composition3, it is contemplated that compositions can contain minor amounts, i.e. up to about 10%, of compounds that, while commonly classified as detergent builders, are used primarily for purposes S other than reducing free hardne~s ions; for example ele-trolytes used to buffer pH, add ionic strength, control viscosity, prevent gelling, etc.

Other components/adju~cts commonly u~ed in detergent com-positions are for example soil suspending agents such as water-soluble salts of carboxymethylcellulose, carboxy-hydroxymethylcellulose, copolymers of maleic anhydride and vinyl ethers, and polyethylene glycol~ having a mole-cular weight of about 400 to 10.000. These can be used at levels of about 0.5% to about 10~ by w~ight. Dyes, pig~
ments, optical brighteners, p~rfumes, enzymes, anti-caking agents, suds control agentR and fillers can also be added in varying amounts as desired.

One major advantage of the present invention is that ef-fective bleach improvement at substantially all tempera-tures is independent of specially selected chelating agents.

A futher advantage is that the present metal catalysed bleaching becomes more efficient at low temperatures when sodium triphosphate base~ are replaced by alternative low phosphate to non-phosphate builder systems for both per-borate and percarbonate product~.
Furthermore the manganese (II)/carbonate ~ystem is an effective all-temperature catalyst for peroxide compounds, showing minimal wasteful solution decompo~ition.

The invention will now be illu~trated by the following Examples.

C 808 ~R) ~XAMPLE I
-The following compositions were prepared Composition (~ by weight) Sodium C12 alkyl benzene sulphonate12.1 12.1 Nonionic ethoxylate 1.8 1.8 Sodium carbonate 28.5 Sodi~ tri.phosphate - 28.5 Sodium silicate 5.2 5.2 10 Bthylene diamine tetraacetate0.08 0.08 Sodium sulphate 15.0 15.0 Sodium perborate tetrahydrate23.0 23.0 Manganous sulphate +
Water up to 100%

ThesP compositions were tasted at a dosage o 5g/1 in a 30 minute isothermal wa~h at 40C i.n 24~ water using varying amounts o* Mn2~.

The bleaching effects obtained on tea-~tained te~t clothe measured as ~R keflectance) wer~ as follow6s Table I

CMn~+~ .~ R ~ R *
~ .
ppm in ~ in Product solution 0.5 0.01 15.0 3.0 1.0 0.02 17.5 3.0 30 2.0 0.04 1~.5 3~0 5.0 0.10 18.5 3.0 8.0 0.16 15.0 3.0 * Reflectance of product A without carbonate or comparison.

S C 808 (R) EX~MPLE II
The following compo~l~ion ~as prepared:

Composition II
5 (% by weight) Sodi.um C12 alkyl benzene sulphonate 12.1 Nonionic ethoxylate compound1.8 Sodium carbonate 2805 Sodium si.licate 5.2 10 Sodium sulphate 15.0 Ethylen~ diamine tetraac~tate0.08 Sodium percarbonate 23~0 Manganous sulphate Water up to 100~.
This composition was tested at a dosage of Sg/l in a 30 minute isothermal wash at 40C in 24H water, using vary-ing amounts of Mn2+.

The bleaching results obtained on tea-stained test cloths measured as ~R were as follows:

Table 2 - 25 [Mn2t] a R ~ R*
ppm in ~ in Product solution 0.25 O.OOS 15.0 3.0 1.0 0.02 21.0 3.0 2.0 0.04 21.0 3.0 5.0 O.lO 20.0 3.0 8.0 0.16 14.0 3.0 * Reflectance o~ Composition A without carbonate for comparison.

~ 655 C 808 (~) E~AMPLE III
Typical bleaching data obtained when odium triphosphate (STP) in a base composition was successively replaced by carbonate as a builder in a sodium perborate/Mn2~ bleach Rystem, keeping the bui.lder and other components level~ con-stant are shown in the table 3 below:

The base compoRitlon used was: ~ by weight 10 Sodium C12alkyl benzene sulphonate 14.0 Sodium triphosphate/carbonate 30.0 Sodium silicate 8.0 Sodium sulphate 13nO
Sodium carboxymethylcellulose 1.0 15 Ethylene diamine tetraacetate 0.13 Fluorescer 0-5 Sodlum perborate tetrahydrate 23.0 Water up to 100%.

Manganous sulphate added to a [Mn2t~ in solution of 2 ppm.

Table 3 Bleaching results on tea-stained test cloths in 40C iso-thermal wash.

STP/carbonate ratio ~R (Reflectance) .
100 / 0 2.0 87.5/ 12.5 3.0 ~ 25 4.0 / 40 5.5 / 50 6.5 / 60 8.5 / 75 11.0 0 /100 16.0 1~3762:~ c 808 (R) EXAMPLE IVA bleach composition consisting of 99.9~ sodium percar-bonate and 0.1% MnS04.4H20 was prepared.

Bleaching results on tea-stained test cloths in 40~C iso-thermal wash for 20 minutes (dosage adjusted to 0.5 ppm Mn2+) In the absence of Mn2~ R = 8.7 In the presence of Mn2+ R - 19.2 The effectiveness of a carbonate/Mn2~ bleach system according to the invention is again clearly shown.

EXAMP~E V

The following compositions were prepared:

Composition (% by weight) _ _ Sodium Cl2alkyl benzene sulphonate12.1 12.1 Nonionic ethyoxylate compound 1.8 1.8 Sodium triphosphate 28.5 28.5 Sodium silicate 5.2 5.2 25 Sodium sulphate 15.0 15.0 Ethylene diamine tetraacetate0.08 0.08 Sodium percarbonate 23.0 23.0 Manganous sulphate +
Water up to 100~.
Composition V was tested on tea-stained test cloths against composition B in a 60 minutes heat-up-to-boil wash using 24H water. The composition V contained 0.2% by weight of Mn2+ and was used at a 5g/1 dosage giving [Mn2+] in solution of lO ppm. Composition B did not contain Mn2 and was used at the same dosage of 5 g/l.

` 1187GS5 c 80a (~) The following bleach results were obtained.

Table 4 5 Time (min.) Temp. (C)~R (V) ~ R (B) 10.0 3.0 31 60 15.5 8.5 20~0 14.5 46 80 25.5 20.0 31.0 27.0 ~ 95 34~0 31.0 - EXAMPLES VI - X

Some typicaI fabric washi~g compositions within the inven-ti.on are fuxther illustrated below.
Composition VI VII VIII IX X
(% by weight) Sodium C12 alkyl benzene sulphonate 6.0 6.0 6.Q 6.0 6.0 - 25 Nonionic ethoxy-late compound 2.0 2.0 2.0 2.0 2.0 Sodi.um soap 3.0 3.0 3.0 3.0 3.0 Sodium triphosphate15.030.0 - 5.0 Sodium silicate8.0 8.0 8.0 8.0 8.0 30 Sodium carboxymethyl cellulo~e 0.3 0.3 0.3 0.3 0.3 Ethylenediamine tetraacetate 0.1 0.1 0.1 0.1 0.1 Fluore~cer 0.3 0.3 0~3 0.3 0.3 35 Sodium sulphate 17.0 17.017.0 17.0 17.0 Sodium carbonate 15~0 - 30.0 25.0 30.0 ~, , ~ 5 C ~08 (~) Composition (continued) VI VII VIII IX

Manganous sulphate/
chloride 1.52.0 0.5 1.0 0.2 Sodium perbora~e tetra hydrate -- 23.0 23.0 Sodium percarbonate23.0 23.0 - - 23.0 Proteolytic enzyme - - + +
10 Water -~ up to 100~---------Example XI

The following composition was prepared:
Composition (~ by weight) Sodium C12 alkylben~ene sulphonate14.0 Sodium carbonate 30.0 Sodium silicate 8.0 20 Sodium sulphate 13.0 Sodium perborate 25.0 Fluorescer 0.3 Sodium carboxymethylcellulose 1~0 Manganous sulphate 25 Water up to 100%.

This composition was tested at a dosage of 5 g/l in a one hour isothermal wash at 25C in 24~ water, using varying amounts of Mn2~ (manganous sulphate in the product).

The bleaching results obtained on tea-stained cloths, measured as a R, were as ~ollow~:

6~5 _ _ [Mn2+]
___ ppM in solution _ % in product ~R
o 0 8.0 0.5 0.01 14.0 1.0 0.02 17.0 2.0 0.04 17.7 5.0 0.10 16.0 7.0 0.14 1400 lO.0 0.20 ll.0 Example XII

The following compositions were prepared:
Composition (% by weight)XII C
Sodium C12 alkylbenzene 5ul phonate 14.0 6.0 Nonioni~ etho~ylate compound - 4.0 20 Sodium triphosphate - 36.0 Sodium carbonate 30.0 - :
Alkaline sodium silicate 8.0 8.0 Ethylene diamine tet~aacetate 0.1 0.1 Sodium carboxymethylcellulose l.0 l.0 25 Sodium sulphate 13.0 ll.0 Sodium perborate 25.0 25.0 Fluorescer 0.5 0.5 Manganous chloride ~ +
Water up to lO0~.
Composition XII was tested on tea-stained test cloths again~t Composition C in a 60 minute heat-up-to-boil wash, using 24H water. The compo~itions XII and C con-tained 0.04~ by weight of Mn2+ as manganous chloride and were used at a dosage of 5 g/l to giva ~Mn2~] in solution of 2 ppm.
` .-~1876~5 c 808 (R) The following results were obtained.

S Time (min) Temp. (C) ~ R (XII) ~ R (C) _ 11.6 30 1 O.S
17.6 40 5 1.0 24.9 50 12 2~0 31.1 60 16 4.2 40.1 70 20 10.8 46.0 80 22 1~.0 55.0 90 23 22.0 . ~

.

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A bleach composition comprising a peroxide compound and a heavy metal compound, characterized in that it is free from cyanogen compounds and comprises manganese (II) in an amount of 0.005-5% by weight, and a carbonate compound which delivers carbonate ions naqueous solution in an amount of 1-50% by weight of carbonate ions.

2. A composition according to claim 1, characterized in that it comprises 0 .025-2.5% by weight of manganese (II).

3. A composition according to claim 1, characterized in that it comprises 5-35% by weight of carbonate ions.

4. A composition according to claims 1, 2 or 3, characterized in that it comprises a manganese (II) salt selected from manganous sulphate, manganous chloride and mixtures thereof.

5. A composition according to claims 1, 2 or 3 characterized in that it comprises a carbonate compound selected from alkalimetal carbonates and alkalimetal percarbonates and mixtures thereof.

6. A composition according to claims 1, 2 or 3 characterized in that it further comprises from 2-50% by weight of a surface-active agent.

7. A composition according to claim 1, characterized in that it further comprises an alkaline detergency builder in an amount of up to 80% by weight.

8. A bleach composition according to claim 7, wherein the alkaline detergency builder is sodium triphosphate.

9. A bleach composition according to claim 7, which is free from sodium triphosphate.

10. A bleach composition according to claim 9, comprising 0.005-1% by weight of manganese (II).