Detergent bleach compositions

A solid detergent bleach composition adapted for use at substantially any washing temperature, comprising essentially a detergent active compound and a synergistic mixture of a solid organic peroxy acid compound e.g. diperoxyazelaic acid, an inorganic peroxy compound e.g. sodium perborate and a stabilizing sequestering agent. The composition which is preferably presented in the form of a particulate product, shows improved bleaching effect at substantially all washing temperatures. It has also advantages over compositions comprising bleaching activators in that it does not suffer from problems of in situ peroxy acid generation.

TECHNICAL FIELD 
The invention relates to detergent bleach compositions and in particular to 
solid detergent bleach compositions adapted for use at substantially any 
washing temperature. 
It is well known in washing and/or bleaching of textiles to make use of 
compositions containing inter alia inorganic peroxy compounds, such as the 
alkali metal perborates, percarbonates, perphosphates, persilicates, 
hydrogen peroxide and sodium peroxide, having a bleaching effect on the 
textiles treated therewith. However, washing and/or bleaching compositions 
containing such inorganic peroxy compounds generally have the disadvantage 
that their bleaching effect is relatively low at temperatures below 
80.degree. C. and substantially nil at temperatures below 60.degree. C., 
which gives rise to difficulties when these compositions are used in 
domestic washing machines wherein the temperature of the wash water is not 
higher than 70.degree. C. 
The addition of organic bleaching activators for the peroxy compound to 
such compositions is known, owing to which the active oxygen of the peroxy 
compound becomes effective also at temperatures below 80.degree. C. Such 
compositions are believed to function by the generation of organic 
peroxyacids during use, for example peroxyacetic acid. A fundamental 
problem in this type of systems is that the peroxyacid is generated in 
situ which under practical conditions gives rise to yield difficulties. 
BACKGROUND ART 
U.S. Pat. No. 4,128,495 discloses bleaching compositions comprising 
phthaloyl peroxide and sodium perborate. Phthaloyl peroxide is a 
peroxyacid precursor and is hydrolysed or perhydrolysed in aqueous medium 
to produce monoperoxyphthalic acid or diperoxyphthalic acid. Detergent 
and/or bleaching compositions comprising organic peroxyacids, such as 
diperoxyisophthalic acid, are also known from e.g. British Pat. Nos. 
1,387,167; 1,456,591 and U.S. Pat. No. 4,100,095. 
British Pat. No. 1,269,677 discloses bleaching compositions comprising a 
percarboxylic acid, e.g. perbenzoic acid, and an inorganic persulphate, 
particularly the mixed salt KHSO.sub.4, K.sub.2 SO.sub.4, 2KHSO.sub.5. 
DISCLOSURE OF THE INVENTION 
It is an object of the present invention to provide a detergent bleach 
composition having an improved bleaching effect at substantially all 
washing temperatures. 
It has now been found that this object can be achieved by using a 
synergistic mixture of a solid organic peroxyacid compound, an inorganic 
peroxy compound generating H.sub.2 O.sub.2 in solution and a stabilizing 
sequestering agent. 
Accordingly the invention provides a solid detergent bleach composition, 
characterised in that it comprises essentially a detergent active 
compound, a solid organic peroxyacid compound, an inorganic peroxy 
compound which generates hydrogen peroxide in solution and a stabilising 
sequestering agent as hereinafter defined. 
The organic peroxyacid compounds used in the present invention are solid at 
room temperature and should preferably have a melting point of at least 
50.degree. C. 
Such peroxyacid compounds are the organic peroxyacids and water-soluble 
salts thereof having the general formula: 
##STR1## 
wherein R is an alkylene group containing 1 to 16 carbon atoms or an 
arylene group containing from 6 to 8 carbon atoms and Y is hydrogen, 
halogen, alkyl, aryl or any group which provides an anionic moiety in 
aqueous solution. Such Y groups can include, for example: 
##STR2## 
wherein M is H or a water-soluble, salt-forming cation. 
The organic peroxyacids and salts thereof usable in the present invention 
can contain either one or two peroxy groups and can be either aliphatic or 
aromatic. When the organic peroxyacid is aliphatic, the unsubstituted acid 
may have the general formula: 
##STR3## 
wherein Y can be 
##STR4## 
and n can be an integer from 1 to 12. Peroxyazelaic acids (n=7) are the 
most preferred compounds of this type, particularly diperoxyazelaic acid. 
Examples of other preferred compounds of this type are diperoxyadipic acid 
and diperoxysebacic acid. 
When the organic peroxyacid is aromatic, the unsubstituted acid may have 
the general formula: 
##STR5## 
wherein Y is, for example, hydrogen, halogen, alkyl, 
##STR6## 
The percarboxy and Y groupings can be in any relative position around the 
aromatic ring. The ring and/or Y group (if alkyl) can contain any 
non-interfering substituents such as halogen or sulphonate groups. 
Examples of suitable aromatic peroxyacids and salts thereof include 
monoperoxyphthalic acid, diperoxyterephthalic acid, 
4-chlorodiperoxyphthalic acid, m-chloroperoxybenzoic acid, 
p-nitroperoxybenzoic acid and diperoxyisophthalic acid. Preferred aromatic 
peroxyacids are monoperoxyphthalic acid and diperoxyisophthalic acid. 
The amount of organic peroxy acid compound in the composition of the 
invention will generally be in the range of from 1 to 25% by weight, 
preferably from 2 to 10% by weight. 
The inorganic peroxy compounds usable in the present invention are 
compounds which liberate hydrogen peroxide in aqueous solutions. Examples 
of such inorganic peroxy compounds are the perborates, the perortho-, 
perpyro- and perpolyphosphates, and the percarbonates; the perborates, 
particularly the alkali metal perborates, being preferred because of their 
commercial availability. They can be present in the tetrahydrate form as 
well as in partially dehydrated forms up to the lowest hydrate form. 
The amount of inorganic peroxy compound in the composition of the invention 
will generally be in the range of from 2 to 40% by weight, preferably from 
5 to 30% by weight. 
The sequestering agents usable in the present invention should have the 
ability of stabilising the bleach system by inhibiting the mutual 
decomposition reaction between the peroxyacid and the inorganic 
peroxycompound. Examples of such sequestering agents are compounds having 
the following general formulae I, II and III: 
##STR7## 
wherein n is an integer from 0 to 4 and X is H or an alkali metal, 
alkaline earth metal or ammonium cation; 
##STR8## 
wherein n is an integer from 0 to 2; X is H or an alkali metal, alkaline 
earth metal or ammonium cation; 
Y=CH.sub.2 COOX or CH.sub.2 PO.sub.3 X.sub.2 ; 
Z=CH.sub.2 COOX or CH.sub.2 PO.sub.3 X.sub.2 ; 
(X=H or alkali, alkaline earth metal or ammonium cation); 
##STR9## 
wherein n is 1-3 and X is H, or an alkali metal, alkaline earth metal or 
ammonium cation. 
These sequestering agents are disclosed in U.S. Pat. No. 4,225,452 and 
British Pat. No. 1,392,284. 
The amount of sequestering agent used in the composition of the invention 
will generally be in the range of from 0.05 to 5% by weight, preferably 
from 0.1 to 2% by weight. The detergent bleach compositions of the 
invention will also contain at least one detergent active compound, which 
may be anionic, cationic, nonionic or amphoteric in character, the amount 
of which generally will be from about 3 to about 40%, preferably from 10 
to 35% by weight. 
Generally mixtures of the above detergent active compounds are used; 
mixtures of anionic and nonionic detergent active compounds are commonly 
used. 
Typical anionic detergent-active compounds are water-soluble or 
water-dispersible salts of various organic acids. The cations of such 
salts are generally alkali-metals, such as sodium and, less preferably, 
potassium, but other cations, such as ammonium and substituted ammonium, 
can be used if desired. Examples of suitable organic acids are: alkyl 
benzene sulphonic acids, the alkyl chains of which contain from about 8 to 
about 20 carbon atoms, such as p-dodecyl benzene sulphonic acid and linear 
alkyl (C.sub.10-15)) benzene sulphonic acid; the mixtures of sulphonic 
acids obtained by reacting linear and branched olefins, particularly 
linear "cracked-wax" or "Ziegler" alpha-olefins, containing from about 8 
to about 22 carbon atoms, with sulphur trioxide; alkyl sulphonic acids 
obtained by reacting alkanes containing from about 8 to about 22 carbon 
atoms with sulphur dioxide/oxygen or sulphur dioxide/chlorine (followed by 
hydrolysis in the latter case), or by the addition of bisulphite to 
olefins, particularly linear "cracked-wax" or "Ziegler" alpha-olefins, 
containing from about 8 to about 22 carbon atoms; alkyl sulphuric acids 
obtained by reacting aliphatic alcohols containing from about 8 to about 
22 carbon atoms with sulphur trioxide; alkyl ether sulphuric acids, 
obtained by reacting molar quantities of aliphatic alcohols containing 
from about 6 to about 18 carbon atoms with from about 1 to about 15 moles 
of ethylene oxide, or a suitable mixture of ethylene oxide and propylene 
oxide, and subsequently reacting the alkoxylated alcohol with sulphur 
trioxide to yield the required acid; and natural or synthetic aliphatic 
carboxylic acids, particularly those derived from natural sources such as 
tallows, coconut oil, palm oil, palm kernel oil and groundnut oil. 
Examples of suitable nonionic detergent-active compounds are condensates of 
alkyl-phenols having an alkyl group (derived, for example, from 
polymerized propylene, diisobutylene, octene, dodecene or nonene) 
containing from about 6 to 12 carbon atoms in either a straight chain or 
branched chain configuration, with about 5 to 25 moles of ethylene oxide 
per mole of alkylphenol; condensates containing from about 40 percent to 
about 80 percent polyoxyethylene by weight and having a molecular weight 
of from about 5,000 to about 11,000 resulting from the reaction of 
ethylene oxide with the reaction product of ethylenediamine and excess 
propylene oxide; condensates of linear or branched-chain aliphatic 
alcohols containing from 8 to 18 carbon atoms with ethylene oxide, e.g. a 
coconut alcohol-ethylene oxide condensate containing about 6 to 30 moles 
of ethylene oxide per mole of coconut alcohol; long-chain tertiary amine 
oxides corresponding to the general formula R.sub.1 R.sub.2 R.sub.3 
N.fwdarw.O, wherein R.sub.1 is an alkyl radical containing from about 8 to 
18 carbon atoms and R.sub.2 and R.sub.3 are each methyl, ethyl or hydroxy 
ethyl radicals, such as dimethyldodecylamine oxide, dimethyloctylamine 
oxide, dimethylhexadecylamine oxide and N-bis (hydroxyethyl) dodecylamine 
oxide; long-chain tertiary phosphine oxides corresponding to the general 
formula RR'R"P.fwdarw.O, wherein R is an alkyl, alkenyl or 
monohydroxyalkyl radical containing from 10 to 18 carbon atoms and R' and 
R" are each alkyl or monohydroxyalkyl groups containing from one to three 
carbon atoms, such as dimethyldodecylphosphine oxide, 
dimethyltetradecylphosphine oxide, ethylmethyltetradecylphosphine oxide, 
dimethylstearylphosphine oxide, ethylpropylcetylphosphine oxide, 
diethyldodecylphosphine oxide, bis (hydroxymethyl) dodecylphosphine oxide, 
bis (2-hydroxyethyl) dodecylphosphine oxide, 
2-hydroxypropylmethyltetradecylphosphine oxide, dimethyloleylphosphine 
oxide and dimethyl-2-hydroxydodecylphosphine oxide; and dialkyl 
sulphoxides corresponding to the general formula RR'S.fwdarw.O, wherein R 
is an alkyl, alkenyl, beta- or gamma-monohydroxyalkyl radical or an alkyl 
or beta- or gamma-monohydroxyalkyl radical containing one or two other 
oxygen atoms in the chain, the R groups containing from 10 to 18 carbon 
atoms and wherein R' is methyl, ethyl or alkylol radical, such as dodecyl 
methyl sulphoxide, tetradecyl methyl sulphoxide, 3-hydroxytridecyl methyl 
sulphoxide, 2-hydroxydodecyl methyl sulphoxide, 
3-hydroxy-4-dodecyloxybutyl methyl sulphoxide, 2-hydroxy-3-decyloxypropyl 
methyl sulphoxide, dodecyl ethyl sulphoxide, 2-hydroxydodecyl ethyl 
sulphoxide and dodecyl-2-hydroxyethyl sulphoxide. 
Examples of suitable amphoteric detergent-active compounds are: derivatives 
of aliphatic secondary and tertiary amines, in which the aliphatic radical 
may be straight chain or branched and wherein one of the aliphatic 
substituents contains from about 8 to 18 carbon atoms and one contains an 
anionic water solubilizing group, such as sodium-3-dodecylaminopropionate, 
sodium-3-dodecylaminopropanesulphonate and sodium 
N-2-hydroxydodecyl-N-methyl-taurate; and derivatives of aliphatic 
quaternary ammonium compounds, sulphonium compounds and phosphonium 
compounds in which the aliphatic radical may be straight chain or branched 
and wherein one of the aliphatic substituents contains from about 8 to 18 
carbon atoms and one contains an anionic water solubilizing group, such as 
3-(N,N-dimethyl-N-hexadecylammonium) propane-1-sulphonate betaine, 
3-(N,N-dimethyl-N-hexadecyl-ammonium)-2-hydroxy-propane-1-sulphonate 
betaine, 3-(dodecylmethylsulphonium) propane-1-sulphonate betaine, and 
3-(cetylmethylphosphonium) ethane sulphonate betaine. 
Further examples of suitable detergent-active compounds commonly used in 
the art are given in "Surface Active Agents, Volume I" by Schwartz and 
Perry (Interscience 1949) and "Surface Active Agents, Volume II" by 
Schwartz, Perry and Berch (Interscience 1958), the disclosures of which 
are included by reference herein. 
Hence in a more specific embodiment of the invention, a detergent bleach 
composition will comprise: 
(a) from 3 to 40%, preferably 10-35%, by weight of a detergent active 
compound; 
(b) from 1 to 25%, preferably 2-10%, by weight of a solid organic 
peroxyacid compound; 
(c) from 2 to 40%, preferably 5-30%, by weight of an inorganic peroxy 
compound, and 
(d) from 0.05 to 5%, preferably 0.1-2%, by weight of a stabilising 
sequestering agent. 
Generally, a detergent composition of the invention will also include one 
or more detergency builders. Usually the total amount of detergency 
builders in a detergent composition of the invention will be from about 5 
to about 70 percent by weight of the detergent composition. Many 
detergency builders are known, and those skilled in the art of formulating 
fabric-washing detergent compositions will be familiar with these 
materials. Examples of known detergency builders are sodium 
tripolyphosphate; sodium orthophosphate; sodium pyrophosphate; sodium 
trimetaphosphate; sodium ethane-1-hydroxy-1,1-diphosphonate; sodium 
carbonate; sodium silicate; sodium citrate; sodium oxydiacetate; sodium 
nitrilotriacetate; sodium ethylenediaminetetraacetate; sodium salts of 
long-chain dicarboxylic acids, for instance straight chain (C.sub.10 to 
C.sub.20) succinic acids and malonic acids; sodium salts of 
alpha-sulphonated long-chain monocarboxylic acids; sodium salts of 
polycarboxylic acids; i.e. acids derived from the polymerization or 
copolymerization of unsaturated carboxylic acids and unsaturated carboxy 
acid anhydrides such as maleic acid, acrylic acid, itaconic acid, 
methacrylic acid, crotonic acid and aconitic acid, and the anhydrides of 
these acids, and also from the copolymerization of the above acids and 
anhydrides with minor amounts of other monomers, such as vinyl chloride, 
vinyl acetate, methyl methacrylate, methyl acrylate and styrene; and 
modified starches such as starches oxidized, for example using sodium 
hypochlorite, in which some anhydroglucose units have been opened to give 
dicarboxyl units. 
Further, a detergent composition of the invention may contain any of the 
conventional detergent composition ingredients in any of the amounts in 
which such conventional ingredients are usually employed therein. Examples 
of these additional ingredients are lather boosters, such as coconut 
mono-ethanolamide and palm kernel monoethanolamine; lather controllers; 
inorganic salts such as sodium sulphate and magnesium sulphate; 
antiredeposition agents, such as sodium carboxymethylcellulose; and, 
usually present only in minor amounts, perfumes, colorants, fluorescers, 
corrosion inhibitors, germicides and enzymes. 
The detergent bleach compositions of the invention are preferably 
particulate, either flowable powders or aggregates. 
They can be prepared using any of the conventional manufacturing techniques 
commonly used or proposed for the preparation of particulate detergent 
compositions, such as dry mixing, or slurry making followed by 
spray-drying or spray-cooling and subsequent dry-dosing of sensitive 
ingredients, e.g. the synergistic mixture of the solid organic peroxyacid 
compound, the inorganic peroxyhydrate salt and the sequestering agent. 
Other conventional techniques for taking precautions to minimise undue and 
undesirable interactions between the bleaching agents and other components 
of the detergent compositions, such as noodling, granulation, pelletising 
etc. may be utilised as and when necessary.