CA1234456A - Detergent composition - Google Patents

Abstract

ABSTRACT

Improved fabric washing detergent composition especially but not exclusively designed for washing mixed coloured fabrics comprising from 0.5 to 25% by weight of a peracid compound selected from the group consisting of organic peracids, peracid salts and peracid precursors which generate peracids by hydrolysis or perhydrolysis, and from 0.002 to 2.5% by weight of copper, in the absence or substantial absence of a powerful sequestrant which complexes strongly with copper. The composition is effective in minimizing dye transfer but is non-effective or substantially non-effectivs with respect to direct fabric dye or stain bleaching.

Description

~34~5~ C 7016 (R) DETERGENT COMPOSITION

This invention relates to fabric washing detergent come positions which are especially, but not e~clu3ively, designed for the washing of Colorado or mixed colored and white fabric loadings Hitherto fabric-washing detergent compositions of two types were available, i.e. (1) washing products of a non-bleaching type for colored fabrics, which, although safe for the fabric dyes themselves, are not effective to prevent the tendency of some colored fabrics to release into the wash liquor dyes which are then transferred during the washing process onto other fabrics being washed therewith, and I a bleach containing fabric-washing product type which can in-habit dye transfer to a certain extent but at thy sometime will cause bleaching and jading of the colors of the fabrics. Hence, heretofore there has been no good way to wombat the problem of dye transfer other than by mechanically sorting the fabrics to partition fabrics with dark and light shades for separate laundering.

With the fashion of moving towards more colored cloth-in and textile materials, especially multi-coloureds, the problem of dye transfer has become more acute.
Many attempts have been made to resolve this problem, but 80 far without much success.

For example, in GAB 1 368 400 dye-transfer-inhibiting compositions were proposed which comprise a per oxygen compound, e.g. an organic peroxyacid, combined with rather complex alluded or kitten compounds as bleach activator. These compositions have several drawbacks in that not only do they use rather expensive complex or-genie chemical compounds, ire. alluded and stones, but alto in that they are not very effective.

1`2344r~ c 7016 (R) Other compositions having dye-transfer inhibitory of-feats are disclosed in European Patent 0024367 (based on the activation of organic persuades with bromide ions) and European Patent Application 0024368 (based on a system comprising an organic pursued precursor and a bromide activator). Still, the main drawback of these compositions is that they too exert a rather strong direct fabric bleaching, tending to cause fading of the colored fabrics.
European Patent Application 0058444 describes washing compositions useful for the reduction of dye transfer in fabric washing at lower temperatures, comprising a bleach system consisting essentially of an organic per-acid or an organic pursued precursor in conjunction with a water-soluble iodide salt. There are some snags in the use of iodide catalyst, i.e. 1) the risk of staining due to iodine formation and 2) the effect of direct fabric dye bleaching.
It is an object of the present invention to provide an improved fabric-washing detergent composition which is suitable for the washing of mixed floured fabrics, in-cludi~g mixed loads of killed and white fabrics, without the above drawbacks.

It is another object of the invention to provide a soys-them that is effective for dye bleaching in solution, i.e. minimizing dye transfer, but it non-effective or substantially non-effective with respect to direct fabric dye bleaching.

It has now been found that these and other objects which may be apparent hereinafter can be achieved by using a system comprising a peroxyacid and a copper catalyst in the absence or substantial absence of a C 7016 (R) powerful sequestrant which complexes strongly with cop-per.

Internal work has shown that transition metal ions can catalyze dye bleaching in solution by oxygen bleaches.
So hydrogen peroxide or hydrogen peroxide adduces, in-organic persalt/bleach activator systems and proxy-acids per ye can all be activated by copper ions. How-ever, it has been found that copper-catalysed pursued bleach systems were much more effective than copper-catalyzed hydrogen peroxide systems (e.g. sodium per-borate).

The effect of added transition me at ions on the bleach-in of a Direct dye in solution by parasitic acid was investigated under the following test conditions:

Conditions: Parasitic acid (4.6 x 10 4 moles/l) was added to a solution of Direct Red 81 ~0.002% wow) and the dye concentration measured at the wavelength of maximum absorption*. The experiments were repeated with added transition metal compounds (QUIZ, MnS04, Cook, Fake, Nazi, ZnS04, Tess as apt propriety). The experiments were made at pal 9 and at 40C.
The results are tabulated in Table I below o eye Max (490-510 no) and maximum absorption (= 100 dye) were measured at the beginning of each export-mint after the addition of transition metal compound but not before addition of bleach.

I C 7016 (R) Table I

Added transition metal % dye remaining ion (1 ppm) after 30 miss S - _ _ 97 To 97 Or 95 on 83 Fe 80 Co 60 Zen 95 Mechanistically it is very important to recognize that transition-metal-catalysed dye bleaching has only been achieved with transition metal ions which are easily capable of one-electron redo processes leading to the formation of reactive radicals. However, as is shown in Table I, only copper and possibly cobalt gave catalysis of parasitic acid for dye bleaching, whereas all the other metals including chromium and zinc are inactive.

Without wishing to be bound to any theory, to motion-is of dye bleaching with oxidizing bleaches can be en-visage in general terms Jo progress via interactions of two distinct types:

Route A

Metal+ + dye Metal Dodd Metal+ bleach (+ Bleach) oxidized dye ~234~ C 7016 (R) Route B

Metal+ bleach-~[Metaln+ bleach radicals*
\~/
¦ Dye Oxidized dye * The term "radical" is used herein in a very loose manner to describe species which can undergo one-electron reactions. The exact nature of the reactive radicals which undergo reactions with dye has not been determined.

I It has also been found that although transition metal ions are well known to interact with peroxide compounds as in Route B above, thus inducing decomposition to radicals or radical species which are known to have high oxidation potential and are capable of oxidizing I most unsaturated molecules, no other transition metals are as effective for dye transfer inhibition as copper.

A possible explanation therefore may be the less well known mechanism of transition metal ion to complex strongly with zany dyes as in Route A above. This route to the interaction of transition metal with bleach, which is only after its interaction with dye, seems to be followed by copper. There seems also to be little doubt that, when it occurs, complexation of transition metal ion and dye will aid dye bleaching, because metal-catalysed bleach decomposition can thus take place in the vicinity of the dye via a dye-metal bleach complex. Thus the ease with which copper forms such complexes compared with other transition metal ions may be one Ryan why copper has proved to be generally the most useful transition metal ion for dye bleaching in solution. Cupric ion, being the smallest diva lent C 7016 (R) transition metal ion, with the highest charge density, most readily forms stable complexes. Cobalt III and chromium III complexes of dyes are also very stable, but apparently they are canticle inert and, in con-5 tryst Jo copper, severe conditions are generally nieces-spry to introduce cobalt III and chromium III into dye structures .

In fact, copper is not the most powerful decompose of 10 bleach molecules. It is known that cobalt is much more effective in this respect, so the amount of tree radicals or radical like intermediates formed from oxygen bleaches is likely to be higher in the case of cobalt. The experimental observation that cobalt is less useful for bleaching dyes than copper may be attributed to the fact that for cobalt many of these radicals lead to useless bleach decomposition, whereas for copper they are more likely to be produced in the vicinity of the dye molecules.
Also manganese, which is known to be very useful for catalyzing stain bleaching, especially with hydrogen peroxide bleaches in the presence of a carbonate, has proved to be ineffective for dye transfer inhibition.
Experiments have even shown that under practical con-dictions manganese can inhibit the catalytic effect of copper, and Jo the presence of manganese ions in the system of the invention should preferably be avoided .

Some experiments have also been carried out by Apply-cant to determine whether strong metal-dye complex-anion is absolutely essential fox good copper catalysis of dye bleaching in solution. From observations of the UV/visible spectra it is clear that I Direct Red 81 and I Acid Orange 7 dyes complex with copper. On adding copper sulfite to I Acid Orange 52, an ago dye without orthohydroxy groups, there is, however, little C 7016 (R) I

change in the UV/visible spectrum, suggesting that the binding of this dye with copper is very weak. where is, however, a definite increase in the rate of dye bleaching when copper is added to a solution containing this dye and sodium monopersulphate (a peroxyacid salt bleach, just as is obtained with the dye which complex more strongly with copper.

Also when the complexation site of a bus ortho-ortho' dihydroxy ago dye was blocked with chromium, a metal which does not activate dye bleaching, as in I Acid Blue 161, then, although there is no detectable change in the visible absorption spectrum on addition of copper to the dye alone, this addition in the presence of a monopersulphate bleach produces a considerable increase in the rate of dye bleaching. Thus these experiments indicated that copper complexation with dyes is not a necessary criterion for copper-catalysed dye bleaching and it must be concluded that, although the ability of copper to strongly complex with dyes under wash conditions plays a role in its generally found higher catalytic activity compared with other transition metal ions, copper catalysis still occurs even when the metal-dye complexation is weak or non-existent.

There is much evidence that copper-catalysed dye bleaching is intimately connected with the decompose-lion of bleach in solution. Increase in concentration of copper generally increases the rate of dye bleaching as well as the decomposition of bleach. Characteristic-ally, it has been observed that the transition-metal-catalyzed decomposition of a peroxide often exhibits an induction period which is reduced by higher levels of copper ions. Many experiments made with copper-catalysed dye bleaching similarly exhibit induction periods which are reduced by increasing the concentration of copper ~23~56 C 7016 (R) ions.

Thus, although this reduction in induction period is accompanied by an increased decomposition rate of bleach, acceleration of dye bleaching to avoid dye transfer can be effected by:
(a) increase in concentration of the bleach and copper (II) ions;
and furthermore by other means which increase the rate of radical production, viz :
(b) increase in the pi of the bleach liquor; and (c) addition of a suitable reducing agent, e.g. hydrogen peroxide added as solid hydrogen peroxide adduce such as sodium perorate or per carbonate, which liberates hydrogen peroxide in solution.

The influence of cupric ion concentration on an export-mint of dye transfer inhibition is shown in the lot-lowing Table If for the pursued bleaches mono~ersul-plate (Oxen , diperisophthalic acid (Swooper and magnesium monoperphthalate, with and without sodium perbora~e.

The detergent base used in the experiments had the lot-lowing composition :

Composition Parts by weight Sodium dodecylbenzene sulphonate 16.0 30 Coconut ethanolamide owe Sodium Tulane sulphonate 2.0 Sodium triphosphate owe Andre alkaline silicate Sodium sulphatP 10.6 35 Water 9.1 9 Lo n id t) H
I P o o o 000~00~ (Do_ n pa r;
n Us l O
O ED oh I- O cry 9 w I O fed O
(D O 0 3 O P
:1 O C I
ow I pa 3 I_ O I (D J --I to _ O
l _ I} O O
o o I Jo 1 0 ,1- (D o Pi ' aye + O
3 Us J up I I
x a n o I w on I
'I o 3 I w 1- Pi Jo ....... , . ED I I 1'-ED UP Us Us 1- O I * if O
I- a.
I Jo I Jo Jo a on us O Jo Us W to 1-- 0 Clue ) I 0 ID G to I
we I O H
I_ Pi I to O Jo UP N CUD I n ED I ED
9 o w ox 3: n on o I-0 I _ E. ID
rut P
Ox w Jo O I
Ul~90~ I U~o-4 I
a I
3 n n Al Us Us Al Us I I O O
O l I
on ...... ED pa O to O a Dtl rut 3 I- lo or o a n Pi o Jo `10~ Us O ^ O rut I_ ED O ED
a o I O
aye pa I; I n W on O I Y

Us O O I US
Us O

3 I C 7016 (R) The influence of pi on dye transfer inhibition with copper-catalysed monopersulphate bleach systems is shown in Table III.

The influence of increasing pi on the rate of copper-catalyzed bleaching of Direct Red 81 with various per-acids, i.e. I (diperisophthalic acid), II (monomer-sulfite) and III (parasitic acid) is shown in Fig. 1.

The dye concentration in g/l (vertical axis) was set out against pi (horizontal axis) under the following experimental conditions :

Direct Red 81 (0.002 g/l), pursued (4.6xlO 4 g.
atoms of active oxygen), pi stat. at 40C.
The diperisophthalic acid used was a commercial prod-vat "Suprox"; monopersulphate used was a commercial product "Ozone"; and the parasitic acid used was pretreated with kettles to remove ~2 It can be seen from this figure that overall there is a considerable increase in dye bleaching with increasing phi 3 I;
O D O
Us oh We C
I on Al I_ ED
(D I 0 to 9 o us 3 ...... n n ,_ -:~: , a v, Jo 6\ Ox ED 1--~9 O
Jo we o I: ..... . in I o P G up o ED \-O Owe t !- 1-- rut O it a JO I g I- 3 us P) 3 I: O Pi oh x 8 ED ., to O I H Us I I. I
`
O on no It n Us ...... It I SO ED
P oh US
rut I ED ED ` I,.
I I, it w I-Pi o o . ED to ID 1'0 I I;
u, us n O O
(D . . . . , , Jo w on ED It I
I_ 3 pa ID Pi (D (D SKI to (D (US I
I it 5 l I_ a rut n to on or I I I
n I e P
o w o us O us on oh ...... to I ED
ox u, ox I- no 3 o ED
romp a I
g co CO O I o ED
on pa o I C Us O C
,,. O I So I I to Pi It 3 to to O it up O O Us ., ....... Us Hi Us w on to it 3 ED
n O
9 0 ED I Pi I

C 7016 (R) The above Tables II and III also show the influence of adding perorate (sodium perorate) to monopersulphate, diperisophthalic acid or magnesium monoperphthalate on the dye-transfer problem.

It can be teen that, in general, the addition of per-borate gave a considerable enhancement of the dye transfer reduction. A mylar ratio of pursued : perorate of about Al was found to be the optimum. Higher levels of perorate will tend to a reduced enhancement and sometimes even a reduced effect.

The dye bleaching in solution and tergotometer dye transfer experiments were carried out by the following methods:

Bleaching dyes on solution Apparatus The apparatus consists of a Beckman DUB spectrophoto-meter fitted with a 1 cm silica flow cell, a water bath to maintain the temperature of the bulk liquor and a pi stat to control the phi The cell is connected to the solution with small-bore silicon rubber tubing and the liquor is circulated by a Watson Marrow flow inducer.
This is fitted on the return tube from the cell to the bulk solution to prevent accidental flooding of the cell compartment. The silicon rubber tubes enter the cell compartment of the spectrophotometer through small holes in the lid. The small amount of light which must enter here does not affect readings in the visible range.

The Flow Cell .

The silica flow cell has a path length of 1 cm. Its 1~34~G 7016 OR) stopper has a glass Pantry tube almost reaching the both Tom of the cell and set to one side out of the light path. A short exit tube awakes the solution from the top of the cell through the pump and back to the bull solution.

Method A 0.04% w/v stock solution of dye was diluted with de-mineralized water to give 250 ml of 0.004~ solution.
This was poured into a 600 ml beaker set in the water bath preheated to 40C and the pi was adjusted. The solution was then pumped through the cell at a rate of 40 ml per minute. This gives a good flow through the cell without turbulence causing bubbles. The per cent transmission at Max for the dye was monitored on the recorder.

A further 250 ml of demineralized water containing 1.137 x 10 4 m of pursued was warmed to 40C and the pi adjusted. This was added to the dye solution and the change in % transmission was recorded for one hour.
During this time, the solution was stirred constantly and, at various time intervals, 50 ml allocates were taken for titration with M/200 sodium thiosulphate.

When reagents such as electrolytes, surfactants or bleaching aids were to be used, they were added as the first dye solution was prepared.
Bleaches were compared at equal active oxygen concern-tractions.

Calculation of Dye Concentration -The dye solution was scanned from 700 no to 400 no to find the maximum absorption wavelength. Then an Abe C 7016 (R) I

sorption (at Max us concentration (% w/v) graph was plotted and the slope calculated.

The dye solutions were recorded as the change in %
transmission. Therefore, the concentration of dye present at any time was calculated as:

Concentration of dye (% w/v) = 2 - log % T
slope Slope = the slope of the absorption us concentration graph.

Dye Transfer Experiments - Test Method The Dyed Test Fabrics Test fabrics with different dye types are used. One 17.5 cm x 17.5 cm square of dyed test cloth was used in each wash.

The Dye Transfer Monitors The fabrics for dye pick-up were white mercerized, do-sized cotton skirting and white bulked nylon 66, both non-fluorescent. One 17 cm x 12 cm square of each of these was put into the wash, regardless of the dye type, to keep the liquor to cloth ratio the same.

Wash Conditions The sets of test cloths were washed in the Terg-O-Tempter for 30 minutes at a constant 40~C and lQ0 rum.
The product concentration was 0.4~ w/v in 18~ hard water with a liquor to cloth ratio of 50:1. Each set of cloths was rinsed separately with three 600 ml portions of cold 18 hard water.

3 Lo C 7016 OR) Wash Method 450 ml portions of 18~ hard water were poured into thy Tergo pots and allowed to warm up to 40C. The pro-weighed constituents were then added. One dyed test fabric and one each of the clean cotton end nylon test cloths were added and washed for 30 min. at 100 rum.

At the end of the wash, the set of cloths from each pot were put into separate 600 ml portions of cold 18 hard water. The rinses were then continued, each set of cloths being rinsed three times in 600 ml portions of cold 18 hard water.

After rinsing, the cloths were separated, padded on paper toweling to remove excess moisture and dried in a cabinet at 60~C.

Measurement of Dye pickup The reflectance of the cloths way measured at the maxim mum absorbency wavelength of the dye using a Beckman DB-GD grating spectrophotometer pitted with a diffuse reflectance attachment Barium sulfite was used to standardize the instrument and a a reference when measuring the cloths.
From the above experimental result it can be said that the composition of the invention should preferably con-lain at least 0.002~ by weight of copper, i.e. equip-alert to about 0.1 ppm in solution, should preferably have a 5 g/l solution pi of from about 7 to about 11, and should preferably contain a hydrogen peroxide ad-duct at molar ratios to perked which can be as low as about 1:100 up to about 2:1, most preferably from 1:25 to 1:1.

I C 7016 (~) I

For practical reasons, the upper limit of the copper concentration can be set at about 2.5~ by weight based on the total composition.

As the source of copper, any copper salt can be used in the practice of the invention, for example copper 8ul-plate, copper carbonate, copper chloride, copper pros-plate etc.

As already elucidated before, sequestration of copper by strong sequestrants should be minimized so as to Ever dye/copper interaction and the production of radicals from the bleach, but on the other hand ox-cessive bleach decomposition must be avoided during storage of the powder. Hence the presence of very minor amounts of a relatively weak sequeatrant such as ethyl one Damon tetra-acetates (ETA) can be tolerated in the present invention at levels usually below 0.2~ by weight, preferably up to about 0.1~ by weight, based on the oval composition. The level of sequestrant toter-axed will depend on the level of copper added.

In practice, where the invention is used in a normal phosphate-~uilt detergent composition, a higher level of copper in the formulation is required. Hence a pro-furred level of copper in such formulations will in general be at least about 0.02~ by weight.

From theoretical considerations, stain chrcmophores on fabrics, which are generally quinonoid in character, are unlikely to behave very differently to dyes in bleaching reactions. Dyes of different types, e.g. ago, quinonoid and indigo id, have all been found to respond to transition metal ion catalysis in solution. However, whereas dyes can be bleached in solution (i.e. a home-generous reaction), in order to bleach dye on the cloth, ~23~5~ C 7016 (R) the bleach must transfer from the solution phase into (or onto) the substrate phase. A surprising feature of the present invention is that generally no positive catalysis of dye or stain bleaching on the fabric is observed from copper added to the wash solution. The effect of copper in solution is lively to deplete the concentration of transferable bleach species (bleach anion ROW and especially undissociated ROOT) in solution and thus to reduce the amount of bleach avail-able to undergo phase transition into the dye or stain on the fabric, thus reducing direct fabric bleaching.

It should be appreciated that the invention as desk cried herein before for persuades is also applicable to pursued precursor systems which form organic persuades in aqueous media by hydrolysis or per hydrolysis.

The organic persuades which can be used in the present invention are known in the art. They can be either elf-phatic or aromatic and have the general formula-Y-R-C~O-OH
wherein R is an alkaline group containing from 1-16 carbon atoms or an Arlene group containing from 6-8 carbon atoms and Y is hydrogen, halogen, alkyd, aureole or any group which provides an anionic moiety in aqueous solution, for example:
O O O
OX -COMMA or -SIAM
I
wherein M is hydrogen or a water-soluble salt-forming cation.

Examples of aliphatic persuades are parasitic acid, monoperazelaic acid, dipera~alaic acid, diperadipic acid, diperoxy dodecanoic acid and decal butane doper-oxoic acid.

C 7016 (R) ~23~
I

examples of aromatic prosodies are monoperoxy phthalic acid, perbenzoic acid, m-chloro-perbenzoic acid, dip perisophthalic acid or mixtures thereof.

Examples of pursued salts as meant here include mug-noisome monoperphthalate, potassium monopersulphate, and peroxymonophosp~ate~ Mixture of persuades (with or without a hydrogen peroxide adduce) may be useful in practice.
In systems where the pursued is formed in situ from its precursor or precursors, the pursued can be formed from the combination of an organic pursued precursor, so-called "per salt activator" and a per salt of the proxy-hydrate type, e.g. sodium perorate, by perhydrolysis,or from a precursor which generates pursued by hydra-louses. Hence various pursued precursors will fall within the scope of use in the compositions ox the invention. These include bouncily peroxide and dish-thaloyl peroxide, both of which are capable of goner-cling persuades, i.e. perbenzoic acid and monoperoxy-phthalic acid, respectively.

Precursors which generate pursued on per hydrolysis are known in the art and include esters, such as those described in British Patents 836,988 and 970,950, in-eluding glycerol penta-acetate and tetra-acetyl Zulus;
azalea asides, such as N,N,N',M'-tetra-ac~tyl ethylene Damon (TOED), tetra-acetyl glycoluril, NJ~'-diacetyl Aztecs methyl malonamide and others described in British Patents 907,356; 855,735; 1,246,339 and US
Patent 4,128,494; azalea Azores, such as those described in Canadian Patent 844,481; azalea immediacy, such as those described in South African Patent 68/6344; and triacyl senoritas, such as described in US Patent 3,332,882.

~23~L~5 3 The amount of pursued compound in the composition of the invention will be in the range generally of from 0.5 to 25% by weight, preferably from 1 to 15% by weight..
these levels as defined for pursued compound are apt pliable to organic persuades, pursued salts as well as precursors which generate persuades by hydrolysis or per hydrolysis.
In systems comprising an organic pursued precursor and a per salt, the organic pursued precursor will ad van-tageously be used in stoichiometric ratio to the per-salt, though higher ratios of per salt to organic pro-cursors can also be used, particularly if a persaltbleach scavenger, such a kettles, is present. Prefer-red per salts are sodium perorate and sodium perkier-borate.

Precursors which generate persuades on per hydrolysis are therefore usable at levels of about Ooze% by weight, preferably 1-15% by weight, in conjunction with a per-salt at levels of about 0.5~50% by weight, preferably 0.5-30% by weight of the composition.
The invention therefore provides an improved fabric-washing composition especially but not exclusively designed for the washing of mixed colored fabrics, comprising from 0.5 to 25~ by weight of a pursued or a pursued precursor as herein before defined and at least 0.002% by weight of a copper cation in the absence or substantial absence ox a powerful seque~trant which complexes strongly with copper.

Preferably the washing composition of the instant in-mention contains a surfactant. The surfactant can be C 7016 (~) anionic, non ionic, cat ionic, semi-polar, ampholytic or ~witterionic in nature, or can be mixtures thereof.
Anionics/nonionics and cationics/nonionics are typical basic surfactant mixtures. These surfactants can be used at levels from about 5% to about 50~ of the composition by weight, preferably at levels of about 10~ to 35% by weight.

Typical anionic non-soap surfactants are the alkali Bunsen sulphonates having from 8-16 carbon atoms in the alkyd group, e.g. sodium dodecyl Bunsen cellophane-ate; the aliphatic sulphonates, eke. C8-C18 Al Kane ~ulphonates; the olefin sulphonates having from 10-~0 carbon atoms, obtained by reacting an alpha-olefin with gaseous diluted Selfware trioxides and hydrolyzing the resulting product, the alkyd ~ulphates, such as tallow alcohol sulfite; and further the sulphation products of ethoxylated and/or propoxylated fatty alcohols, alkyd phenols with 8-15 carbon atoms in the alkyd group, and fatty acid amid having l-B moles of ethyl-one oxide or propylene oxide groups. Other anionicsurfactants usable in the present invention are the at-kale metal soaps (e.g. of C8-C22 fatty acids).

Typical non ionic surfactants are the condensation pro-ducts of alkyd phenols having 5-15 carbon atoms in the alkyd group with ethylene oxide, e.g. the reaction pro-duct of nonyl phenol with 6-30 ethylene oxide units, the condensation products of higher fatty alcohols, such as tridecyl alcohol and secondary C10-Cl5 at-cools, with ethylene oxide, known under the trade-name of "Tergitols" , supplied by Union Carbide; the condensation products of fatty acid amine with 8-15 ethylene oxide units and the condensation products of polypropylene glycol with ethylene oxide.

I

Typical cat ionic surfactants include the conventional qua ternary ammonium compound and the I C25 alkyd imidazolinium alto Preferred qua ternary ammonia compounds are the di(C16-C20 alkyl)dl(Cl-C4 5 alkyd) anunonium salts such a disallow dim ethyl anonym chloride; disallow dim~thyl Amman r~thyl~ulphate;
dihydrogenated tallow d~nethyl anonym chloride or methyl nulphate; dic>ctadecyl dim ethyl anonym chloride;
dicoconut alkyd dim ethyl anunoni~n chloride. Alto Sue-10 bye are the jingle long chained ~auaternary anunoniwncompourld~ wherein the long chain it a C10-C22 alkyd or alkenyl group.

A preferred. matter of the class owe C10-C25 alkyd 15 imidazolinlum alto, believed to be thy 1-mstllyl-2-telltale aside ethyl) im~d~zolini~n chloride, it sold under the l:rade-name of Varl~of~ 455 or 457 (Ashland Chemical Company or S~emoquat M 5~40/H
( (~hemische Were Roy) .
A typical listing of the clauses and ~pecie-q of turf-act ants u~ul in this invention appear in the book "Surface Active Agent", Vol. I, by Schwartz Perry (Inlterscience Publ~hers 1949) and "Surface Active 25 Agents and Detergent", Vow II, by Schwartz, Perry &
Bench ( Intrusions 1958), G2nera11y, a washing composition of the invention will 30 also include one or morn detergency builder and alga-line materials. Usually the total amount of detergency builder in a detergent composition of the invent sun will be from about to about 70% by weight of the detergent composition. Many detergency builder are 35 known, and those skilled in 'eke art of formulating fabric-w2~hing detergent commotion will be familiar with these materials. Example of known detergency * denotes trade marks C 7016 (~) I

builders are sodium triphosphate; sodium orthophos-plate; sodium pyrophosphate; sodium trimetap~osp~ate;
sodium carbonate, sodium silicate, sodium oxide acetate; sodium salt of long-chain dicarboxylic acids, for instance striation (C10 to C~0) succinic acids and Masonic acids; sodium salts of alpha-sulphon-axed long-chain monocarboxylic acids; sodium salts of polycarboxylic acids, i.e. acids derived from the ~co)polymerisation of unsaturated carboxylic acids and unsaturated car boxy acid androids, such as malefic acid, acrylic acid, itaconic acid, methacrylic acid, crotonic acid and aconitic acid, and the androids of these acids, and also from the copolymerisa~ion of the above acids and androids with minor amounts of other monomers, such as vinyl chloride, vinyl acetate, methyl methacrylate, methyl acrylate and Sterno; and modified starches such as starches oxidized, for example using sodium hypochlorite, in which some anhydroglucose units have been opened to give dicarboxyl unwept Another class of suitably builders is the insoluble alumina-silicates as described in British Patents 1 429 143, 1 470 250 and 1 529 454, e.g. elite A.

Further, a detergent composition of the invention may contain any of the conventional detergent composition ingredients in any of the amounts in which such con-ventional ingredients are usually employed therein.
Examples of these additional ingredients are lather boosters, such as coconut mono-ethanolamide and palm-kernel mono-ethanolamide; lather controllers, inorganic salts, such as sodium sulfite and magnesium sulfite, anti-redeposition agents, such as sodium carboxymethyl-cellulose; and, usually present only in minor amounts, perfume, colorants, fluoresces, corrosion inhibitors and germicides 23 ~34~

The washing composition of the present invention can suitably be used in relatively short washes as well as in relatively longer soak-washings under room tempera-lure conditions up to 60C for colored fabric, with a minimal risk of dye transfer and without the risk of serious direct fabric bleaching.

It should be appreciated that the invention can also be formulated as a washing or bleach adjunct to improve the performance of exiting detergent compositions, e.g. fine wash products. In that case the system will essentially consist of a dry mixture of 9.5 to 25 part by weight of a pursued compound and 0.002 to 2.5 parts by weight of a copper catalyst, e.g. cupric sulfite or cupric chloride, and optionally an inert filler such as sodium sulfite.

The washing compositions of the invention are prefer-ably particulate, either as plowable powders or ago gregates.

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 ~lurry-making followed by spray-drying or spray-cooling and subsequent dry-dosing of sensitive ingredients, erg. the idea organic proxy-acid compound, the peroxyacid procurer and the in-organic peroxyhydrate salt.
Other conventional techniques for taxing precautions to improve storage stability or to minimize undue and us-desirable interactions during storage between the bleaching agents and copper or other component of the detergent compositions, such as noodling, granulation/
poulticing and coating of any of the compounds may be utilized as and when necessary.

Claims (7)

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

1. Fabric washing detergent composition especially but not exclusively designed for washing mixed coloured fabrics, comprising from 5 to 50% by weight of a surfactant, from 5 to 70% by weight of a detergency builder, from 0.5 to 25% by weight of a peracid compound selected from the group consisting of organic peracids and peracid salts and mixtures thereof, from 0.002 to 2.5% by weight of copper and from 0 to 0.2% by weight of ethylene diamine tetraacetate, said composition having a solution pH of from 7-11.

2. Detergent composition according to claim 1, which further comprises a hydrogen peroxide adduct in a molar ratio of peracid compound to hydrogen peroxide adduct of from 100:1 to 1:2.

3. Detergent composition according to claim 2, wherein said molar ratio is from 25:1 to 1:1.

4. Detergent composition according to claim 3, wherein said molar ratio is 2:1.

5. Detergent composition according to claim 1, which further comprises a surfactant selected from the group of an-ionic, cationic, nonionic, semi-polar, ampholytic and zwit-terionic surfactants and mixtures thereof in an amount of from 5 to 50% by weight of the total composition.

6. Detergent composition according to claim 1, wherein said detergency builder is a phosphate builder.

7. Detergent composition according to claim 1, comprising from 0.02 to 2.5% by weight of copper.