CA1174550A - Liquid detergent compositions - Google Patents

Abstract

GC108+

ABSTRACT

Liquid Detergent Compositions The present invention relates to aqueous alkaline built detergent compositions containing hydrogen peroxide.
Alkaline conditions present particular difficulties for preventing the hydrogen peroxide from decomposing excessively rapidly during storage. Aqueous compositions containing a builder, especially polyphosphate or citrate, anionic sulphate or sulphonate surfactant, nonionic ethoxylate surfactant and hydrogen peroxide of acceptable peroxide stability can be obtained by employing an alcohol, preferably ethanol, or a polyhydroxy carboxylate, preferably gluconate, or especially both, in conjunction with a phosphonate, especially an ethylene amine methylene phosphonate. Many of such alkaline compositions are formulated to permit the anionic surfactant to work at or near to its optimum pH in conjunction with the builder. The invention also provides similar, but unbuilt compositions containing instead of the builder, additional surfactant, generally nonionic surfactant, and having a somewhat lower pH.

Description

5 S ~ ` .
~ Cl08+

LIQUID DETERGENT_COMPOSITIONS
The present invention relates to liquid detergent compositions and more particularly to built liquid detergents compositions containing an active oxygen-aon~aining compound.
For many years, many ~olid heavy d~ty washing compositions have contained one or more active oxygen-containing compounds (s~me~imes called per-eompounds :
or peroxygen compoùnds) in order to oxidise and de-colouriæe ~arious stains commonly encoun~ered in household l~undry, and to thereby complement the other components of the washing composition. However, it h~s been reGogni~ed that .
even in such solid co~posltions where the ac~ive oxygen-containing compounds and the alkaline component~ of the ~ashing composition are both in solid form, there iLs a t~ndency for the activity of the active oxyg~n-containing aompound to di~inish during ~torage of the ~ashlng composition, on account o~ :Lnteractio~ of the percompollnd with the alkaline componen~s and water vapour in the air ~urrounding the composition. ~he rate of 108~ of act~vity o~ the ~olid active oxygen-contaIni~g compound aan be ~ . ~
~igniicantly r~duced to acceptable level3 by aontaating the ~:
compoun~ with various peroxygen compound 3tabilisers, o~
which a particularly appropriate qort aompri~es ~lkali or alkalin~ earth matal silicates, as described for example in GBPS 1,553,505 to Interox Che~icals Ltd, and alte~na~ively ~ 17'15~ 0

- 2 - GC108~
or additionally coatin~ the solid particles of the compound with a suitable organic or inorganic barrier to prevent the compound coming into contact with the other ~omponents of the washing co~position. Examples of compositions stabilised by coating are described in VSP 3847830 assigned to Laporte Industries Limited and USP 3992317 and USP
4105827, both assigned to Interox S.A
Examination of the prior art demonstrates a marked reluctance on the part of producers o cletergent compositions to employ built aqueou~ alkaline liquid detergent compositions containing a peroxygen compound. For example, USP 3850831 assigned to Mo Och Domsjo Aktiebolag deliberately employs non-aqueous compositions instea~ of aqueous compositions because they were unable to prevent rapid decomposition of the peroxyge~ compound during ~torage of the aqueous composition. In USP 3852210, a~signecl to Flow Pharmaceuticals Inc., the liquid detergent aompc~sition described was builder-free, and its pH was adjusted by addition of acid to pH 4 in the example in which the stability of ~hat compo ition was tested. More reaently~ in USP 4166794, assigned to Colgate~Palmolive liquid bleach-softener compositions containing hydrogen peroxide were de~cribed, but ~uch compositions contained cationic compounds instead of anionic surfactants, did not include a builder and their pH was adju~ted to pH 4 to 5.
It is not ~urprising that the prior art ~ought ways to side-step the problems of providlng a ~torage-stab~le heavy duty alkaline liquid detergent composition containing an active oxygen-containing compound cuch as hydrog~n peroxide, because the problems are much greater than for solid compo~itions. By virtue o~ the faat that all the components are in the li~uid phase, they are inevitably alway~ in intimate contact with each other and cannot be separated ~rom the others simply by a coating technique.
3r~ Thi~ would not matter i~ the other aomponent~ in aombination were comp~tlble with hydrogen peroxide, ~ut in praatice thia ia not the aa~e. Two of the main contributora to hydrogen _ 3 _ GC108+
peroxide instability are anionic surfactants and builders such as polyphosphate which are both time-honoured, readily available and cost effective components of washing compositions, but which generate mildly alkaline conditions in an aqueous concentrate, often from pH 8~5 to 9.5 when present in the ranges of concentrations suitable for a detergent concentrate. The instability of hydrogen peroxide under such conditions can be seen from the~following results. A solution of 10 per cent tetra-potassium pyrophosphate and 5 per cent hydrogen peroxide in demineralized water lost 62 per cent of the available oxygen (activity of the active oxygen-containing compound) within a fortnight and a similar composition containing the corresponding sodium salt lost: 44 per cent within a week.
The significance of this becomes more plain when it is recalled that pyrophosphate in low concentrations, and especially ~nder acidic conditions, is employed as a stabilizer for hydrogen peroxide. It will, thus, be recognised that the problem of providing a storage stable aqueous alkaline detergent composition and especially a built detergent composition presents difficulties that are peculiar to such compositions.
It has also been suggested that detergent compositions can include organic complexing agents as builders. When small amounts of organic complexing agents, such as about 1 per cent by weight were tested at 32C for long-term storage compatibility with hydrogen peroxide under mildly alkaline conditions, the result was, in general, an unacceptable loss of peroxidic activity. For example, an aqueous hydrogen peroxide solution containing 1 per cent o~ ethylenediamine tetraacetic acid,tetra sodium salt lost a remarkable 96 per cent within two weeks and that containing 1 per cent o~
nitrilotriacetic acid, trisodium salt lost an incredible 79 per cent in one week. A solution of hydrogen peroxide ~S containing 1~3 per cent o~ ethylene diamine tetra(methylene phosphonic acid), potassium salt lost 50 per cent within a week. Clearly, the a~orementioned results demonstrate that :~ 1745~0 - 4 - GC108~
in such compositions the hydrogen peroxide is not storage stable under such alk~line conditions. ~oreover, when alkali metal silicates which act as stabilisers fo~ solid percompounds are introduced even at 1 % into s~abilised alkaline detergent compositions described hereinafter a more rapid loss of available oxygen occurs.Therefore, the need for a storage-stabilised aqueous alkaline detergent composition is still to be satisfied.
There is a further complicating fac~or to ~e borne in mind when considering the feasibility of producing a useful liquid detergent composition that is stabilised against loss o peroxide activity. When such liquid compositions are used for laundering, their primary use, they are merely diluted so that there is no change in the physical state of the composition such as occurs when a solid compo ition is dissolved. Hence, those compounds which are includ~d in the concentrated detergent composition to prevent interaction of the peroxide with other components during storage inevitably are still present in the wash solution in the same weight 2~ ratio to the peroxide and with continuing capability to prevent interaction. It would therefore be expectçd that if a high ratio of stabiliser to peroxide is ~employed in~order to obtain a mix of improved storage stability, the rate and extent of utilisation of the peroxide would be impaired, which would manifest itself in impaired washing performance.
It is an object of the present invention to provide an li~uid detergent composition in a concentrated form which can be diluted to form a washing and laundering solution.
It is a further object of some embodiments of the present lnvention to provide aqueous alkaline detergent compositions containing a builder and hydrogen peroxide stabiliaed suf~icently to avoid the use of ~pecial vent~d containers.
It is a ~till urther object o~ certain embodiments o~
the present invention to provide aqueous alkaline detergent compositions containing a builder and hydrogen peroxide stabilised against excessive decomposition during ~torage, ~ 7~55~
- 5 - _ v~
which provide a washing performance substantially the s~me as for the corresponding un~tabilised composition.
According to the present inv~ntion there is provided a stabilised aqueous built liquid detergent composition comprising at least 4 % of an ani~nic sulphate or sulphonate surfactant and/or of a non-ionic ethoxylate surfactantr at least 5 % of a builder selected from alkali metal polyphosphates, and carboxylic acid complexing builders, at least 2 % hydrogen peroxide, sufficient alkali metal aryl sulphonate hydrotrope to maintain the cornposition in a single phase, either by itself or in conjunction with other component~, and a stabilising amount of a combination comprising a low molecular weight mono-hydroxy aliphatic alcohol, and/or a polyhydroxy alipha~ic carboxylate and an aminomethylene phosphonate ~r hydroxy alkyl diphosphonate.
Percentages for any componer.t herein are by weight, based on the composition, unless specifically stated to the contrary.
The anionic surfactant, especlally suita~ly, is an alkyl aryl sulphonate and in order to a~sist its 1 20 biodegradability is preferably a linear alkyl aryl ! sulphonate. The alkyl group preferably contains from 9 to 1 18 carbon atoms, particularly the decyl, dodecyl or ¦ tetradecyl g~oups. Although o~her aryl groups can be used, I the aryl group is normally benzene. Examples of suitable ! 25 commercially available alkaIi metal alkyl aryl sulphonates ~ are available under ~he trade names WARCODE~ K54 from j Warwick Chemicals, England, NANSA SS60 from Albright and I Wilson, England and especially HETSULF 60S from Heterene j Chemical~ Co, New ~ersey. Other anionlc ~urfactanta that :3~1 demonstrate compatability wlth hydrogen peroxide include alkyl ~ulpho~uccinamate, the alkyl group prePerably cont.aining ~rom 12 to 18 carbon atoms. A commercially available example o~ suah a compound is ALCOPOL FA from Allied Colloid~, England. 9uitable anionic ~ulphate surfac~ants include primary alcohol ~ulph~te~ and primary alcohol ether sulphate~, the alkyl group in the alcohol moiety of ~uch compound~ normally containlng frcm 9 to 18 ~ 17~550 - 6 - ~C108 and frequently from 12 to 15 carbon atoms. Commercially available examples of such compounds include PERLANKROL
D.S.A., E~S.D. and E.A.D. being respec~ively a sodium primary alcohol sulphate, sodium pri~lary alcohol ether sulphater and ammonium primary alcohol ether sulphate, all available from Diamond Shamrock. Other us~able sulphonate surfactants include n alkane and olefin sulphonates, the aliphatic moiety normally containing at least 12 and often from 13 to 18 carbon atoms. Examples of such compounds are available under the trade name HOSTAPUR S.A.S. and O~S. from Hoechst (UK). Mixtures of any two or more of the foregoing anionic surfactants can be employed.Generally the concentrate contains at least 3 ~ of the anionic sulphate and/or sulphonate surfactant and usually not more than 15 %.
In many embodiments of the present invention, the non-ionic surfactant component of the composition is selected from primary alcohol ethoxylates and linear secondary alcohol ethoxylates. The alcohol component in each of these compounds preferably has a carbon chain length of R
in the yeneral formula RO(C2H~O)nH of at least 9 and frequently not more than 18 carbon atoms extending away from the ethoxylate moiety. In many commercially available compounds, the linear carbon chain of R is in the range of from 11 to 16 carbon atoms and in many cases the surfactant is derived from a mixture of alcohols.
In the ethoxylate moiety of such compounds, the degree of ethoxylation n is generally in the range of from 5 to 20 and in many very desirable ethoxylates, n is from 7 to 12.
~owever,it is desirable also to take into account the relative proportions o the two moieties in the non-ionic surfactant involved, and this is oten expressed in terms o~
the weight proportion of the ethoxylate moiety in the molecule. The proportion is desirably at least 50 %, normally not more than 85 % and preerably at least 60 % up to 80 ~. ~ most desirable range o suractants contains from 60 to 80 %, preferably 65 to 75 ~ by wèight of the ethoxylate moiety and ~he alcohol moiety is a linear Cl~, i i 7~ 55 (:~
- ? GC10 C13, C1~, Cls or Cl~ or a mixture of linear alcohols havin~
an average carbon chain length within the range of 1~ to 16.
It will be recognised that in many p~eferred alcohol et~oxylates, the ratio oc.the num.ber of carbon atoms in R to the degree of ethoxylation n in the ethoxylate ~oiPty is generall~l in the range o Erom 3:2 to 2:1~ Examples OL
suitable commerc1ally available alcohol ethoxylates are available under the trademark ~Y~PERONIC grades A.7, A.9, and A.ll, all from I.C.I., EnglandJ in which R is a mi~ture ~0 'f ~13 and Cls and the degree of etho,~ylation are respectively 7, 9 and 11, TER~ITOL (Trademark) q~ades 15-.S-9 and 15-S-12, from Union Carbide, U.~.A., being Cll_l~ linear secondary alcohol ethoxylates, having degrees of ethoxylation of respec~ively 9 and 12, LUBROL (Trademar~) grades 12 A.9 and 17 A.10 from I.C.I., England~ the aqerage chain lengths of ~ being respectively 1~. and 17 and the degrees of ethoxylaticn 9.5 and 10 ET~YLAN (Trademark) arades CD9112 and D259, both from Dia~ond Shamrock, and ~IJ
(Trademark) grades 3~ 7~ and 98, being respectively the lauryl, stearyl and oleyl ethers of polyoxyethylenes and RENEX ~Trademark) grade 20 being a polyoxyethylene mixed fa~ty acid ester available from Honeywell Atlas. ~ ~urther polyethylene oxide condensate that can be employed is available under the trade mark MY~ON grade 100 from Warwick Chemicals. Mixtures of two or more ethoxyl~ted surfac~an~s can be used. The amount of nor. ionic surfac~ant used is normally at least 3 % and frequently not mo~e than 15 ~.
A third essential component o~ the built liquid detergent comp~sition o~ the presen~ invention is a hu1lder selected ~rom polyphosphate and car~o~ylic acld complexin~
builder~. Among~t ~he polyphosphates, it is e~peciall~
suitab}e to empl~y pyrophosphates, an~ ore partlc~lar~y ~.h~
tetra potassium or tetra sodium ~alts or mix~ure~ thereof.
In many embodiments, the tetra-potas~ium pyropho~phate sa~.t i~ ~elec~ed, by vir~ue of its solubiliLy being 3uperior to that o the corresponding sodium ~a~t in concentrated li~uid detergent composition~. ~lthough it is possibl~ to employ a di-alkali metal dl-hydrogen pyrophosphate as a propor~ion of the polyphosphate builder, its incorporation, eg ~0-~0 ~ of ~ ~ 7~5!~g3 - 8 - GC108+
the polyphosphate builder mix tends to produce a lower pH in the washing solution obtained simply by dissolution of the liquid detergent composition, providing a wash ahd stain removal detectably inferior to that obtained when the tetra c alkali metal salt is employed instead, in otherwise identical compositions. The polyphosphate can be introduced into the detergent composition either as a solid which is dissolved, or in the form of an aqueous solution, but the percentages given herein are of a dry weight basis.
n The organic complexing builders conte~plated herein tend to fall into three classes, hydroxycarboxylic acid, aminocarboxylic acid and oxacarboxylic acid. Amongst hydroxycarboxylic acid builders, a particularly suitable one is citric acid, usually introduced as the tri~alkali lS metal salt, and on cost grounds, as the trisodium salt.
Mixtures of the hydroxycarboxylic acid builders and polyphosphates, for example citric acid and tetrapyrophosphate both in salt form, can also be usedt often in a weight ratio of 2:1 to 1:2. Where a rather higher pH of the mix is desired, an alkaIine adjuster, sodium metaborate is very suitable.It is desirable to use not more than about 20 % of pyrophosphates amd where tripolyphosphate is used not more than about 10 to 15 %.
Within the class of aminocarboxylic acid builders, nitrilo triacetic acid, normally alkali metal sal~ thereof, I (NTA) is most prominent. Generally use of the salt tends to j produce a somewhat higher pH than of a corresponding weight ! of hydroxycarboxylic acid complexing builder and probably as ¦ a result thereof the resultant built detergent composition 1 30 tend8 to show ~lightly in~erior hydrogen peroxide ~tability.
¦ At higher conaentrations within ~he a~orementioned range or j b~lilder* it is pre~erable to downwardly adjust the pH of the mix hy introducing it in part acid ~orm. In practice, o~ten not more than 10% N~A is employed. It can be employed to complement hydroxycarboxylic acid builders, the resulting mixture therewith generating an intermediate pH, ~or example a mixture o~ 12 to 6~ sodium citrate and 3 to 9% N~A.

~ 5t~
- g - GCl08+
Similar mixtures of NTA with polyphosphates such as ~etrapyrophosphates can also be utilised.
Within the class of oxacarboxylic acids, carboxymethyloxysuccinate deserves mentioned. For practical reasons it is preferable to employ from 5 to 8% of this builder. Where higher than 8% builder is desiredr the balance above 8% is more advantageously provided by one of the other aforementioned builders.
The sulphonate hydrotropes are suitably the alkali metal salts of benzene or methyl-sub~tituted benzene sulphonates, most commonly xylene sulphonate and toluene sulphonate. Preferably the sodium or potassium salt is employed. A proportion of the hydrotrope can be provided by incorporation of one or more ethoxylated phosphate esters.
Such esters chemically can be regarded as phosphate ester derivatives of the aforementioned non-ionic ethoxylate surfactants described hereinbefore. In many embodiments, the product used is a mixture of the two. The degree of ethoxylation in the ethoxylated moiety is generally the range from 2 to 12 and often in the range of 2 to 6, and the carbon chain length of the hydrophobic alkyl group R is normally from 9 to 18. Whilst it is possible to employ the closely related ethoxylated alkyl phenol phosphate esters, in which the alkyl group is often from C8 to C12, their use ~S for such purposes is being in~reasingly viewed with hostility by water authorities because suitable methods have not yet been found to degrade them biologically. The phosphate esters often are available in the acid form and they can be employed as such in the liquid detergent compositions oE the pre~ent invention, but their use in that way does tend to lower the pH of the composltion and o~ the subseque~nt washlng solution and i~ desired, the phosphate e~ter can be partially or completely neutralised with alkali metal hyclroxide, espe~lally sodium or potassium hydroxide,

3~, ox ammonium hydroxide~
~ n general, the total proportion of sulphonate hydrotrope plus ethoxylated phosphate ester is normally . ' - 10 - GC108+
selected within the range of from 3 % to 12 %, of which the sulphonate hydrotrope is ~requently from 3 to 9 % and the ethoxylated phosphate ester the balance. A small proportion of ethoxylated phosphate ester, for example from 1 to 3 %
r,can be advantageous in improving the washing abillty of the composition for certain commonly encountered stains like cocoa, for example where the ratio of the anionic to non-ionic sur f actant is relatively high, such as at approximately 1:1 or higher.
10The stabiliser system for hydrogen peroxide in the composition comprises an amino methylene phosphonate or hydroxy alkyl diphosphonate and either or both of a low molecular weight aliphatic alcohol, and a polyhydroxy aliphatic carboxylate. The low molecular weight aliphatic alcohol is most preferably ethanol, particularly in the view of its combination of properties in that, not only does it effectively and surprisingly improve the storage stability of hydrogen peroxide in the composition, in combination with the other components despite the fact that its presence tends to increase the alkalinity of the solution, as measured by a standard pH electrode, but it also cooperates with the aforementioned hydrotropes in retaining a one phase system and consequently provides higher flexibility in formulating compositions. The low molecular weight aliphatic alcohol is employed, preferably, in an amount of at least 5 % of the composition and are generally not more than 15 %. In many embodiments it is employed within the range of from 7 to 12 %. The higher weight aliphatic alcohols such as propanol and butanol are considerably less 3n desirable by virtue, it is believed, of their poorer water solubility 90 that the compounds can be employed to only a much smaller proportion of the composition than can ethanol.
By way o~ example, many o~ the compositions described herein containin~ comparatively high amounts of sur~actant and ~S builder can remain in a single-storage stable phase when they contain ln ~ of ethanol, but when the same amount of butanol or propanol is employed instead, phase separation S ~ ~
~ GC108+
oc~urs.
The polyhydroxy aliphatic carboxylate generally contains at least 5 carbon atoms and normally up to 10 carbon atoms. Although the carbon chain in the molecule can be branched, in many effective examples the compound is linear, terminating at one end in a carboxylate group, and preferably having a chain length of 5, 6 or 7 carbon atoms.
Desirably all, or at least the majority of the remaining carbon atoms are substituted by an hydroxyl group. The compound can be in acid form, but preferably is neutralised with an alkali metal, preferably sodium or potasium.
Preferred compounds of this class include the acid or neutralised forms of gluconic acid and glycero-ido heptonate. Preferably, the polyhydroxy compound is employed 1~ in an amount of at least 0.08 % of the composition and in many cases not more than 1 ~.
The phosphonate component of the stabilised system can be introduced in the acid form, but it will be recognised that, if the acid form is employed initially, to a certain 2~ extent the resultant solution will have a lower pH and impairment of overall washing performance can thereby ensue.
The phosphonate component is therefore introduced preferably in an at least partial alkali metal salt ~orm. By the term "amino methylene phosphonates" is meant any compound containing an amino group substituted by a methylene phosphonic acid group or salt thereo~. Many suitable phosphonates can be represented by the general formula, in acid form:-[H2o3PcH2~ ~N(cH2po3H2)(c~2)p ~ q ~N(MePO3H2)~
in which p is normally ~rom ~ to 6 and q is normally ~rom 0 I to ~. ~lighly desirable examples are ethylene diamino tetra I (methylene pho5phonic acid) hexa potassium salt, and diethylene triamino penta (methylene phosphonic acid) or h~x potassium salt. Further suitable examples include hexamethylene diamino tetra (methylene phosphonic acid), penta sodium salt and amino tri(methylene phosphonic acid) penta sodium salt. Where desired, one or more of the 5 ~j ~
- 12 - GC108+
methylene groups linking the amino group~ can be substituted at the carbon atom by a lower alkyl group or at one carbon only by an hydroxyl group or the substituents of two such suitably spaced, preferably adjacent carbon atoms can combine to form cyeloaliph~tic ring preferably containing 5 or 6 carbon atoms.
The aliphatic dipho~phonates can conveniently be represented in acid form by the formula YZC(PO3H2)2 in which Y represents an hydroxyl or amino group, the amino group itself optionally being substituted by a lower alkyl, a lower alkylamino or a lower hydroxyalkyl ~roup, lower indicating from 1 to 4 carbon atoms, and Z represents a lower alkyl, preferably methyl group. Examples of such diphosphonates include 1 - amino ethane ~ diphosphonic acid and 1 - hydroxyethane ~ diphosph~nic acid, and preferably the alkali metal salts thereof. Mixtures of any two or more of the aforementioned amino-methylene phosphonates and/or diphosphonates can be employed, as desired. Such a compound or compounds are preferably employed in an amount of at least 0.075 ~ by weight of the composition and generally an amount of not more than 1 % and often the amount is selected from the range of 0.1 ~ to 0.4 %. Use of larger amounts than 1 % do not in yeneral repay the additional cost of their incorporation, and for each phosphonate an amount is reached beyond which increasing the amount leads to impaired stabilisation.
When it is desired to include both the polyhydroxy carboxylate and the phosphonate in the compostion, an extremely convenient and desirable way of so doing is to firs~ obtain or produce a premix o~ these two components in the desired weight ratio e.g. 4:3 of the former to the latter and then u~e the premix.
In many of the detergent compositions of the present 'invention~ the weight ratio o~ the polyhydroxy compound to the phosphonate i~ within the range of 3 to 1 to 1 to 3 and often within the range of 2 to 1 to 1 to 1, and their combined % is preferably f~om 0.2 to 1.0 %. In other highly .

5 ~ ~
~ 13 - GC108+
desirable embodiments of the present inventiorl, the lower molecular weight aliphatic alcohol is selected within a weight ratio to the phosphonate of from 50:1 to 2.5:1, and pre~erably from 50 to 1 to 20 to 1, when the stabiliser system consists of the phosphonate and the al¢ohol, preferably employing a comparatively high amount of the phosphonate, namely at least 0~15 % generally up to 0O4 %.
Most desirably the weight ratio is varied inversely to variation in the phosphonate concentrate. The product of the weight ratio of alcohol to phosphonate and the concentration of the phosphonate expressed as a percentage in the two component stabiliser system is preferably at least 8 and often from 9 to 12. It is specially desirable to employ all three stabiliser components together in the detergent composition especially in a combined amount of at least 0.2 ~ for the polyhydroxy compound and the phosphonate, and at least 5 % of the aliphatic alcohol. In many embodiments, it is convenient and advantageous to select the components within the ranges of 0.1 to 0.4 ~ for each of the polyhydroxy and phosphonate components and from 5 to 12 and particularly from 8 to 12 % for the aliphatic alcohol, especially ethanol.
The hydrogen peroxide can conveniently be incorporated in the form of the appropriate amount of concentrated hydrogen peroxide, eg 35 to 85 % W/W hydrogen peroxide commercially available, which often contains from 10 ppm pyrophosphate. It is often incorporated in the solution in the range of from 3 to 10 %, frequently from 5 to 8 % and for industrial uses often from 10 to 20 % (expressed as 100%~) Lower concentration of hydrogen peroxide could be employed, but in general these would not enable a desirable amount of active oxygen to be provided in the washing ~olution unless the concentration of the other components in the detergent composition were correspondingly reduced also.
It will be recognised that the concentration of hydrogen peroxide in the range 5 to 8 % in the detergent composition when diluted to form a washing solution by a ~actor selected ~7~5~
- 14 - GC108+
within the range of 100:1 to 1000:1 and often preferably from 200:1 to 500:1 can readily provide active oxygen concentrations commensurate with those provided by normal concentrations of many heavy duty solid detergent compcsitions or by the addition of an active oxygen bleach at recommended levels to commercially obtainable active oxygen-free liquid detergents.
In practice, the total proportion of components other than water and hydrogen peroxide normally is selected to be not greater than 52 %. Use of a higher proportion, particularly where the composition contains relatively high proportions of builder and anionic surfactants tends to become more sensitive to phase separation. Although a total proportion, eg below 20 % of such components could be lS employed in compositions, whether built or not, it is more desirable to provide such components to a total proportion of at least 20 ~ and more preferably at least 30 % of the liquid composition, not only from the point of view of reducing the volume of unnecessary water to be transported but also because the user often associates dilute products with inferior products. In many embodiments, the totaled proportions of components other than water and hydrogen peroxide in the built compositions is at least 35 % and frequently not more that 45 %.
The prefered concentration of polyphosphate or citrate in the detergent compositions is from 9 to 16 %. The proportion of anionic sulphate or sulphonate surfactant plus ethoxylated non-ionic surfactant in the concentrate is preEerably within the range of from 6 to 15 %, the weight ratio o~ anionic to non-ionic surEactants normally being selected within the range o~ 5:2 to 2:S, in order to produce a balanced surfactant mix Eor the treatment of the general mix of household stains. Where the composition is intended for a more speci~ic stain, one that is known to be sensitive 3~ to a particular type of surfactant, then anionic to non-ionic surfactant weight ratios outside the aforementioned range can be readily contemplated. Hence~

1 17'15'~
- 15 - GC108+
e.g. where the product is intended primarily for greasy stains, a lower anionic to non-ionic ratio can be mor~
desirable, for example in the range of 1 t~ 2.5 ~to 1 to 5.
Additionally, in determining the actual amounts of various components to be incorporated in the mixture, it is desirable to maintain the builder e.g. polyphosphate or citrate to anionic surfactant ratio within the range of 1:1 to 5:1 and particulary from 2:1 t~ ~1 so as ~o take advantage of the synergistic interaction between those two components. The anionic surf~ctants are present preferably in an amount from 3 to 8 %, and often at least 4 %, and the builder is preferably polyphosphate or citrate, frequently at from 9 to 16 %, and the non-ionio surfactant content is ,normally at least 3 % and again often at least 4 %, with the lS result that the anionic sulphonate or sulphate surfactant and nonionic ethoxylated surfactant are pr~sent in such compositions in to~al amount advantageously o at lea~t 8 ~
Addi~ionally; it is desirable for the clstomary reasons to incorporate in the detergent composition a qmall proportion of detergent adjuvant~, the ~total amount of adjuvants, generally up to 8% and in many ca~es, being fro~
1 to 5 ~. Examples of adjuvan~ include soil anti-redeposition agents, for example polyvinylpyrrolidon~, and sodium carboxymethylcellulose, often in an ~mount o~
from 0.1 to 0.3 % and an optical brightener or a range of brighteners to allow for the various sorts of fibre~ rom which household laundry articles are made, to a total amount often in the range of 0. 5 to 2 % of the` composition. It is generally desirable to select as brightener those o~ the stilbene type which have demonstratable ~torage comp~tibility with hydrogen peroxide in ~olution. In general, the aomposition will also contaln a very sm~11 proportion of alkali metal sulphate formed during the neutrali~ation of the anionic surfactant during i~
3S preparation. The compositlon~ can al90 include a ~mall amount of mono-or di or tri ethanolamine, or alkali metal borates as pH ad~uster~, but alkali metal silicates and ~ 1 7~ 5 5~

carbonates axe excluded, or of amphoteric surfactants such as imidazoline based fatty acid carboxysulphates. e9. from 0.5 to 2 %. The adjuvants can also include a small amount of fo~m regu~ators, for example ethylene o~ide/propylene oxide copolymers such as are available from Ugine Kuhlmann, France under the Trademark PLURONIC, grades L42 and F.108, and soaps i e. al~ali metal salts of aliphatic carboxylic acids, having a chain length of at least 8 carbon atoms and normally from 10 to 20 carbon atoms, examples of which include stearate, and soaps derived from natural sources, particularly tallow and coconut oils, again often up to 2~
by weiqht. Other adjuvants can comprise compatible tarnish -~
inhibitors, cationic softeners, dyes, perfumes and thickeners, such as xanthan gum for citrate-built for~ulation~.The amounts of the adjuvants can be varied by the skilled worker within or outside the exemplified ran~es.
Some especially preferred built compositions according to the prese~t invention compri~e from B to 12 ~ in total of anionic sulphate or sulphonate surfactant and nonionic ethoxylated surfactants of which preferably from 3 to 8 anionic sulphate or sulphon~te surfactan~ and preferabiy from 3 to 8 3 is non-ionic ethoxylated surfactant, from 9 to lS ~ alkali metal preferably, potassium tetra pyrophosphate;
from 3 to 6 % alkali metal aryl sulphonate hydrotrope; from 5 to 1~ %, pr~ferably 8 to 12 ~ ethanol; from 5 to 10 %, preferably 5 to a % hydrogen peroxide; from 0.2 to 1 ~ in total of a polyhydroxy linear C~ or C7 aliphatic carboxylate, preferably an alkali metal gluconate an~ an alkali metal methylene phosphonate complexing agent, pre~erably ~thylene diaminetetra methylene phosphonate or hexamethylene diamine tetra methylene phosphonate or diethylene triamine penta methylene phosphonate, pre~erably in a weight ratio o~ ~rom 2:1 to 1:1; up to 3 ~ of detergent adjuvants such a~ described herein, including a 40il antiredeposition agent and an optical brightener; and the balance, water, pre~erably from 55 to ~5 %. Other composltions include corresponding compositions containing at lea~t 5% builder and in which all or part of ~he 9-16~

~ ~ 7 - 17 - GCl~8 po~yphosphates or citrate builder is replaced by 4 to 7%
carhoxymethyloxy succinate or 3 to 9% NTA.
In a modification of the invention, no builder is employed, and instead the compositions contain additional CJ surfactant, mainly nonionic surfactant~ Consequently, unbuilt detergent compositions according to the present invention contain at least 5% nonionic surfactant and in total at least 10% surfactants. The presence of the extra;
surfactants means th~t the balance of anionic to nonionic generally favour~ the nonionic to a much greater extent than in built composi~ions according to the present invention.
Thus, in unbuilt compositions, the anionic surfactant is normally selected in the range of 3 to 15%, but the nonionic is normally selected in the range of 5 to 35%. The weight ratio of anionic surf~ctant to nonionic surfactant is preferably selected in the range of 1:1 to 1:6, and in practice is often likely to be in the range of 1:3 to 1:6.
The anionic surfactant often represents ~rom 3 to 10% of the unbuilt composition and the nonionic sur~actant at least 15%
and frequently from 20 to 35%. In a specially preferred unbuilt compositions/ the surfactants concentration i3 not more than 40% and particularly i~ from 25 to 40~, of which the anionic comprise~ from 3 to 8~ and the nonionia ~rom 22 to 3S~. The unbuilt aompo~itions can, in practice, be slightly more concentrated than the built compositions.
Thus, the total proportion of components other than water and hydrogen peroxide is generally up to 65% and frequently from 40 to 60~.
In the other respect~, for example ~election o~ and aoncentrations o~ hydrotrope, ~tablll8er, hydro~en peroxide and ad~uvants~the aorementloned description or th~ built compo~ition~ applies likewise to the unbuilt aompo5ition~
according to the present invention.
It i~ especially desir~ble that the aompo~ition3, either built or unbuilt, be ~ree from alkali metal carbonate~ or silicates.
The compo~itions desaribed herein can be made ~ 1 7~
- 18 - GC108+
conveniently by mixing the components in the desi~ed proportions in a mixing tank, and to avoid and minimi~e lo~s of hydrogen peroxide by decomposition it is preferable to add it as the last step, or at least after the two stabiliser components have been introdu~ed. The surfartants are preferably mixed at a moderately elevated temperature, often from 35 to 60 C, and then combined with the other components which brings the mixture to near ambient for the introduction of the hydrogen peroxide. Preferably the 1~ polypho~phate is introduced in aqueous solution, either supplied as such by the manufacturer or prepared on site by dissolution. The minor components, detergent adjuvants and sulphonate hydrotrope can be mixed in with the surfactant mix. The variou~ solutions ~nd water can be introduced consecutively or concurrently in~o the mixing tank except as mentioned hereinbefore that the hydrogen peroxide solution is preferably introduced last or star~ing last. Although the proces~ has been described in a batch manner it wi:Ll be readily apparent to a skilled engineer how to carry out the process on a continuo~s basis. The ~omposition~ when throroughly mixedj can then be poured in~o containers or dispensers. By virtue of the superior ~torage stabllity of at least some of the embodiments, of the inventionj such as those losing leas then 1 % Avox a week the cont~iner~ or ~5 dispensers for such embodlment~ need not be o~ the speciaily vented and thus expensive types, but instead container~
having a slightly loose fitting closure means, such as cap or stopper can be used.
According to a further aspect o~ the pre~ent invention, 3n wa~hing proces~es, or laundering, aacording to th~ pre~ent invention aan be carrled out by diluting the liqu1d concentrate o~ the pre~ent lnvention with water to a des~red extent, and contactlng the a~ueou~ washing solution with the articles to be washed at any temperature ~rom ambient to the boiling point o~ the ~olution. In many proce~ses, the process i~ carried out at hand hot temperature or hotter, often a temperature of at least 45 C and, dependi~g on 455~
- l9 - GC108+
local washing customs, fr~quently at a temperature of at least 60 C.
It is a feature o the present invention that there is provided a one shot liquid detergent composition containing not only hydrogen peroxide, but also a high concentration of anionic and non-ionic surfactants of the order needed to form a washing solution without the addition of any further components. However, if it is desired, the detergent composition described herein before can be employed in conjunction with one or more bleach activators, i.e.
compounds which react in aqueous solution with hydrogen peroxide to generate peroxy acids, preferably added separately to the washing solution to prevent premature interaction. Such compounds are normally N-acyl or 0-acyl compounds. Typical examples of the classes of each ~ctivator which each represents, includes N,N,N',N',-tetraacetylethylene-diamine of N-acylated alkyleneamines, benzoic or phthalic anhydride, tetra acetyl glycoluril,N-alkyl-N-sulphonyl-carbonamides, N-acyl hydantoins, carbonic acid esters, triacetyl cyanurate, 0,N,N'-tri substituted hydroxylamines and diacyl peroxides such as benzoyl glutaryl peroxide and diphthaloyl peroxide.
In comparison with the use of such activators in conjunction with solid detergent compositions, inter-reaction between -~5 the active oxygen containing compound and the activator can occur more quickly by virtue of the fact that the hydrogen peroxide is already in solution whereas for solid peroxygen compounds, and especially the commonly used sodium perborate tetrahy~rate at hand-hot temperatures or cooler, its rate of dissolution can be a restraining factor. I~ an activator i5 employed in conjunction with the detergent aomposition, then the preferred washing temperatures tend to be ~omewhat lower, pre~erably ~alling in the the range from ambient to fiO C. Naturally, a convenient mole ratio of activator to 3S hydrogen peroxide is from 2 to l to l to 2l and esp~cially l to 1 in the washing solution.
Generally, the concentrates of the present invention 1 ~7~5~
- 20 - GC108+
are diluted to produce washing solutions containing from 0.1 to 1.5 gpl surfactant. In many cases, the concentration of surfactants is within the range of 0.2 to 0.6 gpl and such concentrations can be obtained from many of the preferred detergent compositions of the present invention such as those containing at least 8 ~ surfactants at a dilution of greater than 100 to 1, and often at a dilution of from 200 to 1 to 300 to 1.
The washing period can range from as low as a minute or 1~ a few minutes e.g. 5 minutes at washing temperature at or near the boiling point of the washing solution, e~g. from 90 to 100 C up to a period of several hours at cooler wash temperatures, such as overnight steeping at ambient temperature. The washing period can be varied at the iS discretion of the user. Typical washing times at a temperature of 40 to 70 C are of the order from 5 to 40 minutes.
In addition to laundry use, the compositions can be used neat or after dilution to cleanse hard surfaces, such 2~ as those of enamel, paint, metal, plastic, wood, glass or ceramics.
Having described the invention in general terms, specific embodiments will be described hereinafter more fully by way of example only. It will be recognised that by , employing his general knowledge and the information contained herein before, the expert in the field of liquid detergents will be able to vary the proportions of components in the composition.

7~5~
- 21 - GC108+ Can Examples 1-4~ and 43-6~
Liquid detergent compositions according to the present invention were prepared by the following ~eneral ro~te, employing the weight proportions summarised in Tables 1, 2 and 3 below.
First, a mixture of the anionic and ncnionic sur~actants in the correct proportions was heated to approximately 4~ to 45 C
with constant s~irring until a clear sol~tion occured. The sulphonate hydrotrope and ethoxylated phosphate ester when employed were then introduced in the desired proportions with stirring followed by the builder, often together with a proportion of the total deionised water content of the mixture which cooled the mixture~ Next the ethanol the residual amount of water the polyhydroxy carboxylate and the phosphonate component~ were added as well as the detergent adjuvants, where employed. Finally, the hydrogen peroxide solution was introduced. The mixture was vigorously stirred.
In the Examples (tm) indicates the preceding word to be a trademark which is often followed by a product/grade description. The components used in the compositions were as follows:
anionic surfactan~s Al so~iu~ dodecyl benzene sulphonate - HETSULF 60S (tm) A2 sodium linear alkyl benzene sulphonate - ~ANSA
SS60 ~tm) A3 sodium primary alcohol sulphate - PERLANKROL DSA ttm) amphoteric suractant A~ imidazollne based - coconut carboxys~lphate hydrophile M~R~NOL 3MCT (tm) nonionia ~ur~actants Nl Cls sec alcohol ethoxylate (n-~) T~RGITOh 15S9 (tm) N2 middle cut primary C12 ~ ClS alcohol ethoxylate ~na9) ETHYLAN D259 (tm) N3 syn~hetic primary alcohol ethoxylate (n~7) SYNPERONIC
A7 ~tm) N~ lower cut primary alcohol ethoxylate (n=9 ~THY~N CD919 (tm) ' ~

5 ~
~ 22 - GC108+ Cn~
Hydrotropes HXl sodium xylene sulphonate (SX96) HX2 sodium xylene sulphonate - ELTESOL SX30 ttm~
Phosphate esters HEl ethoxylate~ phosphate ester - TRITON QS3~ ~tm) HE2 ethoxylated phosphate ester (n=2) - BRIPHOS ~2D
ttm) polyhydroxycarboxylate SG sodium gluconate phosphonate stabiliser SPl hexapotassium ethylene diamine tetra (methylene phosphonate) SP2 aminotris(methylene phosphonic acidl SP3 diethylene~riaminepenta~me~hylene phosphonic acid SP4 hexamethylenediaminetetra(methylene phosphonate) hexapotassium salt SE Ethanol-industrial grade methylated spirits HP Hydrogen peroxide - 35 % W~W aqueous solution containing 50 pp~ pyrophosphate ~uilder Bl Potassium tetra pyrophosphate (solid) B2 Potassium tetra pyrophosphate (aqueous solution) - KALIPOL 4KP (tm) B3 Potassium polyphospate (chain length 4~ KALIPOL
18 (tm) B4 Sodium Citrate B5 Nitrilotriacetic acid, sodium salt B6 Trisodium carboxymethyloxysuccinate.
Water Deionised except where marked * in which Widnes, Cheshire municipal water was used untreated~
~imilar compositions to one or more of the exempl1fied compositions were obtained by substi~.utinq alternative nonionic suractants such as poly oxyethylen~ alkyl ethers or poly oxyethylene alkyl ethers for the speci f ied ethoxylates, and/or substituting ammonium primary alcohol ;i ,1 ;

, ~17~55~3 - 23 - GC108+
ether ~ulphate for the specified sulphate surfactant, and/or by substituting ethoxylated phosphate mono ester of higher degree of ethoxylation for the specified di-ester, and or by substituting other polyphosphate builders for those specified.
The storage stability trial for Tables 1 and 2 was effected by transferring a small sample of the given composition into a clean plastic bottle housed in a constant temperature enclosure at 32 C. The available oxygen concentration (Avox) in the composition was determined by the standard acidified potassium permanganate titration method on a small portion extracted from the sample and the result obtained after storage for a given period compared with the original content. The result given in Tables 1 and 2, is the percentage of Avox lost from the hydrogen peroxide after 3 weeks storage, except in Examples 43 to 52 in which it is after 4 weeks storage. The storage stability trials for Table 3 were carried out in the same manner as that for Tables 1 and 2 except that the temperature of the enclosure was 50C in order to accelerate proceedings. The result is given after 24 hours, approximately. The gluconate and phosphonate were introduced separately, except in Examples 1 to 30 and 43 to 58 were they were provided in th e form of a premix of SG and SPl available under the tradename POLYRON
1020.

~0 1 ~745~3 - 24 - GC108+
~able 1 Ex Weight % of component in composition Surfactant ~ydrotrope Builder No Nonionic Anionic Nl N4 i~l A2 HXl HX2 HEl Bl B2 B4

4 5 5 5 15 4 6 6 lS

.~ ~7~ 5.~

Tab1e 1 cont inued .
Ex Weight 96 of component pH ~vox No Stabiliser HP Water loss SE SG SPl SP2 0.20 0.15 7 B 9.3 4 2 10 " " 7 a 9. 5 3 " " 7 1 9.3 7 4 10 " " 7 a gO4 " " 7 n 9. 2 2 6 10 " " 7 c 9.2 2 7 " " 7 e 9. 2 8 10 ~ I- 7 9. 3 3 9 " " 7 8.2 4 10 10 " " 7 8. 3 2 11 n ~ 7 7~8 2 12 10 " " 7 8 . 0 13 10 0. 05 0. 04 7 9. 412 14 lû 0 . 10 0 . 0~ 7 9. 2 10 15 10 0~20 0.15 7 9.0 3 16 10 0 ~ 30 0 ~ 23 7 9. 0 3 17 10 0 . 40 0 . 31) 7 9 ~ ~ 5 43 10 0.20 0.15 7 9.4 2 44 10 0. 20 0. 15 7 9 . 1 3 0 . 20 0 15 7 7 ~ 4 3 46 10 0.20 0.15 7 7.4 2 47 0 . 20 0 . 15 7 7 . 6 3 48 10 0 . 20 0 . 15 7 7 . 7 2 49 0. 20 0 . 15 7 * 9~ 4 4 50 10 0 . 20 0. 15 7 * 9. 2 3 1 5 ~ ~

Table 2 Ex Weight % oE component in composition Surfactants Hydrotrope Builder No Nonionic Anionic Amph N2 N3 A2 A3 A4 HX2 HE2 Bl B2 B3 lg 3 7 5 1 15 '22 3 7 5 15 31 10 3.3 2 ~.5 32 10 3.3 2 6.5 33 10 3.3 3 6.5 34 10 3.3 3 13.5 3.3 3 13.5 3~ 5 5 5 10

5 5 Q

- 27 - . GC108+
Table 2 con~
Ex Weight ~ of component pH Avox No Stabiliser HP Water loss 18 0.20 0.15 7 b 8.9 18 19 " " 7 a 8.2 14 ll .. 7 1 8.1 8 21 " " 7 a 8. 7 10 22 10 " " 7 n 9.1 4 23 10 " " 7 c 9. 2 3 24 10 " " 7 e 9 . 2 2 ll Il 7 9 . 2 4 26 10 ll I- 7 ~ 1 2 27 Il - 7 7.8 4 28 " ~ 7 8.0 6 29 ". . " 7 8.1 4 " " 7 8 . 5 31 6~5 to pH 3.3 7 2 32 6.5 to pH 3.3 7 33 6.5 to pH 3~ 3 7 6 34 6.5 to pH: 3.3 7 3 to pH 3.3 7 3 36 0.27 7 7.g 37 ll 7 8.5 2 38 ll 7 7.7 2 3~ ll 5 8.7 7 0.54 5 8.6 8 51 0~2 0.15 7 9.4 2 52 10 0.2 0.15 7 9.5 3 5 ~ ~
- 28 - GC108+
Table 3 Ex Weight ~ of component in composition Surfactant Hydrotrope Builder HP
No ~onionic Anionic N4 A2 HX2 Bl B4 B5 B6 53. 4 6 6 15 7 58 4 ~ 6 15 7 ~4 4 6 6 15 7 Table 3 Continued Ex Weight of components in composition pH Avox No Stabiliser Water loss SE SG SPl SP3 SP4 %
53 10 0.2 0.15 B 9.3 7 54 10 0.2 0.15 a 9 7 0.2 0.15 1 8 13 56 10 0.2 0.15 a 8.3 10 57 10 0.2 0.15 n 4 58 10 0.2 0.15 c 3 59 0.2 0~15 e 6 0.2 0.15 5

6~ 0.2 0.15 S
6~ 10 0.2 0.15 4 63 0.2 0.15 6 6~ 10 0.2 0.15 5 Under the storage conditions, lt was observed that almost all the compositions exemplified remained thro~ghout storage in a single phase despite the presence of both i 1745~

~ 29 - GC108 hydrogen ~eroxide and polyphosphate builder in high concentrations, and that phase stable compositions similar to those (18,37) which separated after several months~ were obtainable by a modest redution in the polyphosphate concentration or addition of ethanol in amounts suE~icent to enhance the stability of the hydrogen peroxide in the composition or slightly more hydrotrope.
From Tables 1, 2 and 3 it can be seen that incorporation of ethanol within the limits specified herein in conjunction with phosphonate or phosphonatefgluconate improves the storage stability of the alkaline composition, and that as the level of glyconate/phosphonate stabiliser mix is increased, the storage stability of the co~position increases up to certain level and thereafter declines.
The washing capability of various of the above mentioned compositions have been tested and the results are summarised in Tables 4, 5 and 6.
The washing trials were carried out in the following manner:-Prestained swatches of cotton were washed in alaboratory scale washing machine, sold under the trademark TERGO~OMET~R (US Testing Corporation) which simulates the action of a vertical agitator type of domestic washing machine. The machine trials were carried out under standard conditions of two stained swatches, each of 59, being washed at a temperature maintained at 60 C with one litre of an aqueous washing solution containing 4 grams of the selected detergent composition. Por the compositions according to the present invention this resulted generally in an initi~l ~urfactant concentration in the range of ahout 0.3 to 0.5 gpl, and an initial builder concentration in the range of rom 0.2 gpl to 0.8 gpl. The ~irst washed swatches were removed from the wash water after 10 minutes washin~, rinsed with cold water and dried, and the second removed after 20 or 30 minute~ washing and si~ilarly rinsed and dried. The extent of stain removal from each swatch was determined by mea~uring the reflectance of the swatches before and after ~ 1 7 - 30 - GC108+
washing, using a Zeiss E~EPHO (tm) Reflectance Photometer having a Xenon lamp light source equipped with a y-tristimulus filter. Each swatch was measured four times with a backing of three thicknesses of material. The S reflectance readings were averaged and the % stain removal (abbreviate~ to %SR~ was obtained using the following formula:
% stain removal = 100 x (R~ - Ri)/(RU - Ri~ where Ru represents reflectance of the unstained cloth, Ri reflectance of the cloth after staining, and Rf reflectance of the the stained cloth after bleachingO Swatches of cotton stained with red wine were obtained from E.M.PDA., St. ~allen, Swi~zerland. Swatches of other stained fabrics were obtained by padding the appropriate fabric through an appropriate stain solution, partially drying the fabric with an infra red drier, and repeating the padding and drying cycle twice more.
In the washing ~rials summarised in Table 4 and 5, the washing solution water had a hardness of 150 ppm as calcium carbonate in a Ca:Mg ratio of 2:1 and in those summarised in Table 6, a hardness of 250 ppm as calcium carbonate in a Ca:Mg ratio of 3:1 In Tables 5, and 6 the detergent composition of the present invention additionally contained 0.5 % by wei~ht of a bleach stable stilbene optical brightener obtainable under the name UVITEX BHT Itm). Washing trials using compositions C41, and C42 are present by way of comparison only. The composition C41 was a commercially available built liquid detergent composition WISK (tm), and C42 was an approximately SO/SO W~W mixture of WISK (tm) with an active~o~ygen containing bleach additive CLOROX ~ ttm).
Analysis o~ the products C41 and C42 showed that at the levels o~ detergent compositicn employed, the wa~hing solution contained total sur~actants in the range of 0.3 to 0.4 gpl and an initia1 builder plus p~ adjuster concentration of about 0.4 gpl. These concentrations are very comparable with the concentrations of surfactants and builders present under standard conditions of use of the invention compositions (4 gpl) and ~ 17~5t~
- 31. - GC108+
in broad terms double those when ~he invention compositions are used at only 2 gpl.
Table 4 Example/ Washing Stain% Stain removal comparison conditions a~ter composition 10 min 20 min used 48 Standard Red Wine 61 67 48 " Cocoa 28 30 48 " Tea 52 58 48 ll EMPA 101 42 47 C42 4 g/l Red Wine 56 63 C42 " Cocoa 14 19 C42 " Tea 51 60 C42 " EMPA 101 27 32 48 2 g/l Red Wine 56 63 48 " Cocoa 25 27 48 " Tea 47 54 48 " EMPA 101 33 39 C41 2 g/l Red Wine 52 60 C41 " Cocoa 16 20 C41 " Tea 40 43 C41 " EMPA 101 34 41 `1 17~5$~?

Table 5 Example/ Washing Stain % Stain rem~val compar~son conditions after - composition . 10 min 20 min used 4 Standard Red Wine63.4 65.4 4 " Cocoa 28.7 33.3 4 " Tea 53.5 55.8 4 " EMPA Standard 51.7 57.4 2 . " Red Wine59.6 64.5 2 " Cocoa 38.5 43.8 2 " Tea 42.9 56.5 2 " EMPA Standard 52.4 59.6 6 " Red Wine .59.7 66.2 6 " Cocoa 33.0 37.3 : 6 " Tea 49.7 59.8 6 I- EMPA Standard 52~5 59.1 12 " Red Wine57~6 61.8 12 " Cocoa 25.6 36.6 12 " Tea 49.1 55.5 12 " EMPA Standard 50.0 54.8 22 9/l Red Wine ; 50.8 54.6 2 n Cocoa 6.6 8.6 2 1I Tea 28.5 33.8 4 " Red Wine 53.1 56.5 4 " Cocoa 6.0 9.5 4 " ~ Tea 26.5 29.9 6 " Red Wine 50~1 52.6 6 " Cocoa 6.5 9.1 6 " Tea 26.3 29.4 C41 " Red Wine 38.5 40.6 C41 " Cocoa 2.2 3.6 C41 " Tea 4.4 10.9 C42 4 g/l mix Red Wine 44.9 53.4 C42 " Cocoa -l.S 7.8 C42 " Tea 6.2 31.6 - ~ ~ 7'1~
_ 33 _ GC108+
Table 6 Example/ Washing Stain% Stain removal comparison conditions after composition 10 min 20 min used 18 Standard Red Wine 71.8 79.7 18 " Cocoa 23.7 39.1 18 " Tea 46.9 62.0 19 " Red Wine 72.7 79.8 19 " Cocoa 16.4 33.0 19 " Tea 46.6 61.2 21 " Red ~ine 71.9 80.4 21 : " Cocoa 29.0 37c8:
~ 21 " Tea 47.3 :63.2 : 26 " Red Wine 74.9 81.9 26 " Cocoa ~ 22.2 37.4 26 " Tea 50.4 66.4 2g " Cocoa 14.0 24.0 " Cocoa 15.0 14.0 : C41 2g~1 Red Wine 60.4 66.2 C41 n Cocoa 17.6 ~9.1 C41 " Tea 23.9 27.6 C41 4g/1 Red Wine 65. 67.0 C41 " Cocoa 18.2 33.9 C41 " Tea 18.2 33.9 ; C42 4g/1 mix Red Wine 66.3 76.6 C42 " Cocoa 12.2 26.9 C42 " ~ea 25.2 62.3 From Tables 4, 5 and ~ it can be readily seen that the invention compositions were very effective and, in several, better stain removers on the range o~ stains tested than were comparison compositions C41, C42 and C43. It will be recogni~ed therefore, that the composi~ions oP the instant invention combine the advantages o~ good storage stability with good washing performance. Moreover, when washing trials were repeated employing washing compositions that 5 5 ~
_ 34 - GC108+
omitted the phosphonate and gluconate stabilisers, but were otherwise identical, the washing results were also identical, being within 1 ~ stain removal, i.e. within the limits of reproducibility of the washing tests, indicating that the presence of the phosphonate and gluconate stabiliser had not impaired the washing performance even though they had considerably improved the storage stability of the composition Examples 65 to 69 Compositions were prepared by the method for Examples 1 to 64 except that the step relating to incorporating builder was omitted. Tne Avox of the compositions was required after 4 weeks storage at 32C and the washing trials were carried out in exactly the same manner as those whose results are summarised in Tables 4 to 6, in hard water having a hardness of 150ppm as calcium carbonate in a Ca:Mg ratio of 2:1.
The compositions and results are summarised in Table 7 below.

1 ~t~55~

- 35 - GC108+ Can Table 7 Example No 65 66 67 68 69 Composition weight %
Surfactant Nl 30 30 35 2~ 20 ~ydrotrope HX2 5 5 5 5 5 Ethanol SE 10 10 10 10 10 Hydrogen Peroxide 7 7 7 7 7 Gluconate SG 0.20 0.20 0.20 0.20 0.20 Phosphonate SPl 0.15 0.15 0.15 0.15 0.15 Water balance Stability Avox Lost 3.9 1.8 1.8 3.4 2.2 ~ Soil Removal Red Wine 10 Mins 63 63 66 66 68 Red Wine 30 Mins 68 67 72 71 73 Cocoa 10 Mins 10 9 8 9 8 Cocoa 30 Mins 13 11 10 11 11 The effectiveness of the soil removal can be judged by comparison with commercially available detergent compositions in the USA, viz WISR (tmj and DYNAMO (tm) each at 2 gpl, on urther examples of the stains under the same conditions of wash temperature, water hardness and wash duration, either alone or in 50:50 weight mix with a bleach additive CLOROX 2 .(tm) The comparative results are summarised below in Table 8.
Table 8 Red Wine Cocoa 10 Mins 30 10 ~ins 30 WISR ~tm) 37 40 1 6 WISR (tm) ~ CLOROX (tm) 44 61 3 DYN~MO ~tm) 50 5~ 5 10 ~YNAMO (tm) ~ CLOROX (tm) 45 62 8 From the above it can be seen that the invention compositions obtained significantly better results in the i ~17~ )3~
- 36 - GC108+
respected red wine stain than did the commercial compositions and in respect of the cocoa stain obtained much better result than did the sample of WISK, alone or with added ble.ch and comparahle with or better than the results obtained using DYNAMO, alone or with added bleach.

Claims (41)

CLAIMS:-

1. A stabilised aqueous built liquid detergent composition comprising at least 4 % of an anionic sulphate or sulphonate surfactant and/or of a non-ionic ethoxylate surfactant, at least 5 % of a builder selected from alkali metal polyphosphates and carboxylic complexing builders at least 2 % hydrogen peroxide, sufficient alkali metal7 aryl sulphonate hydrotrope to maintain the composition in a single phase, either by itself or in conjunction with other components, and a stabilising amount of a combination comprising an aminomethylene phosphonate or hydroxyalkyl diphosphonate and at least one member of the group consisting of low molecular weight mono-hydroxy aliphatic alcohols and polyhydroxy aliphatic carboxylates, %'s being by weight.

2. A composition according to claim 1 wherein the proportion of anionic sulphate or sulphonate surfactant is selected within the range of 3 to 15 % weight.
.

3. A composition according to claim 1 wherein the proportion of nonionic alcohol ethoxylate is selected within the range of 3 to 15 % by weight.

4. A composition according to claim 1 wherein the weight proportion of ethoxylate in the nonionic alcohol ethoxylate is from 60 to 80 % of the molecule.

5. A composition according to claim 1 wherein the total proportion of anionic sulphate or sulphonate and nonionic alcohol ethoxylate surfactants is from 6 to 15 %.

6. A composition according to claim 1 wherein the weight ratio of anionic sulphate or sulphonate surfactant to _ 38 _ CAN CLS

nonionic alcohol ethoxylate surfactant is from 5:2 to 2:5.

7. A composition according to claim 1, 5 or 6 wherein the builder is a polyphosphate or an hydroxy carboxylic acid complexing builder.

8. A composition according to claim 1, 5 or 6 wherein the builder is potassium tetra pyrophosphate.

9. A composition according to claim 1, 5 or 6 wherein the builder is an alkali metal citrate.

10. A composition according to claim 1, 5 or 6 wherein the proportion of builder is selected within the range g to 16% by weight of a polyphosphate or hydroxy carboxylic acid complexing builder.

11. A composition according to any of claims 1, 5 or 6 wherein the builder comprises up to 10%
nitrilotriacetic acid, alkali metal salt or up to 8%
carboxymethylsuccinate, alkali metal salt.

12. A composition according to claim 1, wherein the total proportion of all components except for water and hydrogen peroxide is from 30 to 45 % by weight.

13. A modification of the stabilised aqueous liquid detergent composition according to claim 1, being an unbuilt detergent composition comprising at least 10 %
of an anionic surfactant and/or of a non-ionic ethoxylate surfactant, of which at least 5 % is nonionic surfactant, at least 2 % hydrogen peroxide, sufficient alkali metal aryl sulphonate hydrotrope to maintain the composition in a single phase, either by itself or in conjunction with other components, and a stabilising amount of a combination comprising an aminomethylene phosphonate or hydroxyalkyl diphosphonate and at least one member of the group consisting of low molecular weight mono-hydroxy aliphatic alcohols and polyhydroxy aliphatic carboxylates, %'s being by weight.

14. A composition according to claim 13 wherein the proportion of anionic sulphate or sulphonate surfactant is selected within the range of 3 to 15 % weight.

15. A composition according to claim 13 wherein the proportion of nonionic alcohol ethoxylate is selected within the range of 5 to 35 % by weight.

16. A composition according to claim 13 wherein the weight proportion of ethoxylate in the nonionic alcohol ethoxylate is from 60 to 80 % of the molecule.

17. A composition according to claim 13 wherein the total proportion of anionic sulphate or sulphonate and nonionic alcohol ethoxylate surfactants is from 6 to 40 %.

18. A composition according to claim 13 or 17 wherein the weight ratio of anionic sulphate or sulphonate surfactant to nonionic alcohol ethoxylate surfactant is from 1:3 to 1:6.

19. A composition according to claim 13 wherein the total proportion of all components except for water and hydrogen peroxide is from 40 to 55 % by weight.

20. A composition according to claim 1 or 13 wherein the proportion of hydrogen peroxide is selected within the range 5 to 15 % by weight.

21. A composition according to claim 1 or 13 wherein the proportion of sulphonate hydrotrope is selected within the range 3 to 9 % by weight.

22. A composition according to claim 1 or 13 which contains from 1 to 3 % by weight of an ethoxylated phosphate ester.

23. A composition according to claim 1 wherein the proportion of low molecular weight aliphatic alcohol is selected within the range 5 to 15 % by weight.

24. A composition according to claim 23 wherein the low molecular weight aliphatic alcohol is ethanol.

25. A composition according to claim 24 wherein the ethanol is introduced in the form of methylated spirits

26. A composition acording to claim 1 or 13 wherein the proportion of polyhydroxy carboxylate as from 0.1 to 0.4 % by weight.

27. A composition according to claim 1 or 13 wherein the polyhydroxy carboxylate is an alkali metal gluconate.

28. A composition according to claim 1 or 13 wherein the proportion of phosphonate is selected within the range of 0.075 to 1 % by weight.

29. A composition according to claim 1 or 13 wherein the phosphonate is an ethylene diamine tetra (methylene phosphonic acid) or hexamethylene diamine tetra (methylene phosphonic acid) or diethylene triamine penta (methylene phosphonic acid) or an alkali metal salt thereof.

30. A composition according to claim 1 or 13 which contains from 5 to 12 % by weight ethanol, a polyhydroxy carboxylate and a phosphonate.

31. A composition according to claim 1 or 13 wherein the weight ratio of the polyhydroxy carboxylate to the phosphonate is from 2:1 to 1:1, in a total proportion the two components of from 0.2 to 1 % by weight.

32. A built liquid detergent composition which comprises from 8 to 12 % in total of anionic sulphate or sulphonate surfactant and nonionic ethoxylated surfactants, from 9 to 15 % builder selected from alkali metal, tetra pyrophosphate or alkali metal citrate from 3 to 9 % alkali metal aryl sulphonate hydrotrope; from 5 to 12 %, ethanol; from 5 to 10 %, hydrogen peroxide; from 0.2 to 1 % in total of a polyhydroxy linear C6 or C7 aliphatic carboxylate, and an alkali metal methylene phosphonate complexing agent, up to 5 % of detergent adjuvant or adjuvants and the balance, water, %s being by weight

33. A composition according to claim 32 characterised by one or more of the following features :-(i) from 3 to 8 % of the surfactant is anionic and 2 to 8 % is nonionic;

(ii) the builder is selected from potassium tetrapyrophosphate and sodium citrate;

(iii) from 8 to 12 % ethanol is used;

(iv) the aliphatic carboxylate is an alkali metal gluconate;

(v) the phosphonate complexing agent is an ethylene diamine tetramethylene phosphonate, hexamethylene diamine tetramethylene phosphonate or diethylene triamine pentamethylene phosphonate;

(vi) the aliphatic carboxylate and phosphonate complexing agent are in a weight ratio of 2:1 to 1:1.

(vii) the water content is from 55 to 65 %.

34. An unbuilt liquid detergent which comprises from 25 to 40 % in total of anionic sulphate or sulphonate surfactant and nonionic ethoxylated surfactants, from 3 to 9 % alkali metal aryl sulphonate hydrotrope; from 5 to 12 % ethanol; from 5 to 10 % hydrogen peroxide; from 0.2 to 1 % in total of a polyhydroxy linear C6 or C7 aliphatic carboxylate, and an alkali metal methylene phosphonate complexing agent, up to 5 % of detergent adjuvant or adjuvants and the balance, water, %s being by weight.

35. A composition according to claim 34 characterised by one or more of the following features :-(i) from 3 to 8 % of the surfactant is anionic and 20 to 35 % is nonionic;

(ii) from 8 to 12 % ethanol is used;

(iii) the aliphatic carboxylate is an alkali metal gluconate;

(iv) the phosphonate complexing agent is an ethylene diamine tetramethylene phosphonate, hexamethylene diamine tetramethylene phosphonate or diethylene triamine pentamethylene phosphonate;

(v) the aliphatic carboxylate and phosphonate complexing agent are in a weight ratio of 2:1 to 1:1.

(vi) the water content is from 40 to 50 %.

36. A process for the production of a liquid detergent composition comprising:

(a) (1) at least 4% of an anionic sulphate or sulphonate surfactant and/or of a nonionic ethoxylate surfactant, and at least 5% of a builder selected from alkali metal polyphosphates and carboxylic complexing builders or (2) at least 10% of an anionic surfactant and/or of a nonionic ethoxylate surfactant, of which at least 5% is nonionic surfactant;

(b) at least 2% hydrogen peroxide;

(c) sufficient alkali metal aryl sulphonate hydrotrope to maintain the composition in a single phase, either by itself or in conjunction with other components, and;

(d) a stabilising amount of a combination comprising an aminomethylene phosphonate or hydroxyalkyl diphosphonate and at least one member of the group consisting of low molecular weight mono-hydroxy aliphatic alcohols and polyhydroxy aliphatic carboxylates %'s being by weight in which the components a, b, c and d are mixed to form an homogenous mixture and further in which components a and b are brought into contact only in the presence of component d.

37. A process according to claim 36 in which components a, c and d are mixed and then component b is introduced.

38. A process for washing or laundering comprising the steps of bringing into contact an article to be washed or laundered with a liquid detergent composition comprising:

(a) (1) at least 4% of an anionic sulphate or sulphonate surfactant and/or of a nonionic ethoxylate surfactant, and at least 5% of a builder selected from alkali metal polyphosphates and carboxylic complexing builders or (2) at least 10% of an anionic surfactant and/or of a nonionic ethoxylate surfactant, of which at least 5% is nonionic surfactant;

(b) at least 2% hydrogen peroxide;

(c) sufficient alkali metal aryl sulphonate hydrotrope to maintain the composition in a single phase, either by itself or in conjunction with other.
components, and;

(d) a stabilising amount of a combination comprising an aminomethylene phosphonate or hydroxyalkyl diphosphonate and at least one member of the group consisting of low molecular weight mono-hydroxy aliphatic alcohols and polyhydroxy aliphatic carboxylates %'s being by weight as such or after aqueous dilution, at a temperature of from ambient to the boiling point of the aqueous solution.

39. A composition according to claim 13 wherein the proportion of low molecular weight aliphatic alcohol is selected within the range 5 to 15 % by weight.

40. A composition according to claim 39 wherein the low molecular weight aliphatic alcohol is ethanol.

41. A composition according to claim 40 wherein the ethanol is introduced in the form of methylated spirits.