IE840417L - Detergent ingredients - Google Patents

Description

'.» tf » U b 2 This invention relates to the field of axidi sable stain removal, especially but not solely to the removal of oxidisable stains from fabrics and is particularly concerned with the removal of these stains using peroxygen bleaches at 5 tenperatures £60*C such as are encountered in dcnestic weishing and laundering operations.

The removal of oxidisable stains from either hard surfaces or fabrics by means of peroxygen bleaches at tenperatures less than 60*C is a well known technique and customarily involves the 10 use of organic percoty acids, the most commonly used peroxy acid is peracetic acid, normally generated in situ in the bleaching or laundry liquor by the reaction, of alkaline hydrogen peroxide with a peroxy acid precursor (the so-called bleach activator). However, peroxyacids containing more than 2 carbon atone in the 15 acyl group have also been disclosed and taught for this purpose and BP 864,796, Canadian Patent No. 635,620, US Patent Nos. 4100095, 4119660, 4126573 aid European Puhlished Application No. 0068547 all relate to the formation, stabilisation or use of such materials.

Recently, as described in European Published Application No. 0068547, it has been fouid that selection of the chainlength of the aliphatic moiety of the peroxy acid permits the peroxy acid to be concentrated in the area where stain removal is required, ttus for removal of fugitive dyestuffs in bulk solution, a 'hydrophilic' bleach species is satisfactory, whereas for stains en solid surfaces a bleaching species showing more hydrophobic character, and hance a tendency to migrate to the solid-liquid interface, may be more beneficial.

In the commonly assigned US Patent No. 4412934 issued to Stanley Y Chung & Gianfranoo L Spadini, cn November 1st 1983 entitled "Bleaching Compositions", and Rutertt No. 6S"(>H entitled "Detergent Additive Product" cenpositiens are disclosed whicii incorporate a Cg-C^g acyloxy txiupouiid capable of farming 3 'V^IO aliphatic peroxy acid on reaction with alkaline hydrogen peroxide, the c8-c1q acyl group being linear in nature.

Although compositions prepared in accordance with these last named disclosures provide superior stain removal performance to prior art products employing peracetic acid or its precursors, it has been found that, under certain conditions, odours produced in the wash solution fcy these products are aesthetically unattractive.

It has now been found that certain non-linear aliphatic peroxy acid precursors, when added to aqueous liquors containing a source of alkaline hydrogen peroxide, provide effective bleaching of oxidisable stains, particularly at temperatures at or below 60 °C without generating aesthetically unattractive odours. The precursor compounds can be added to such liquors on their own, or added to water as part of a ccnplete inorganic peroxy hleach-containing detergent composition or as part of a laundry additive product added to an -aqueous solution of an inorganic peroxy bleach-containing detergent composition. Such conpositions and additive products are described and claimed in Patent Specification No. StTO-f 4 According to the invention therefore there is provided a non linear aliphatic peroocycarbaxylic acid precursor ■ adapted to for* a non linear aliphatic peroxy acid in aqueous alkaline hydrogen peroxide solution wherein the precursor has the general fornulai R11 0 R1- C- S-L i111 Wherein the groups R11 R1- O- V11 is an aliphatic hydrocarbyl organic moiety of non linear 10 structural configuration, at least one of R11 and R111 being hydrogen, the other of R11 and R1*1 being independently selected, from hydrogen and Cl-C4 alkyl groups, the group: Rll0 R1- C- A- A1U containing at least five carbon atoms in a linear chain 15 extending from and including the carbonyl carbon and being the acyl moiety at a carbcayllc acid having a XogP^ of frca 1.9 to 4.1, Wherein P^ is the partition coefficient of the carboocylic acid between n-octanol and water at 21 *C, and L is a leaving groqp having the formula 0 1 b) - N - C - Rj ®2 wherein R2 is an alkyl group containing frcn 1 to 4 carbon atom; x is 0 or an integer fzcn 1 to 4 and Y is selected frcni - SDjM - 080^ - OOjM - N+(R2)3Q" " iKRjjf-JO wherein M is H, alkali metal, alkaline earth metal anmoniim or substituted annonium; and Q is halide or methosulphate, the conjugate acid of said leaving group L having a pKa in the range from 6 to 13. these leaving groups have a pKa more preferably in the range from 7 to ii, nest preferably fzar. S to 10.

Preferred leaving gxoqps are those of formula a) above in vriiich x is O onr! Y is se-lcctod frun -SO^M and -OOjH wherein M is an alkali netol preferably sodium. 6 Preferably the groupi K11 R1- 0- ia a C^-Cg allyl group and preferrad compounds are alkali net&l. anaoniua or substituted assoniua 2-etlyl hexanoyl cxybenzene sulphcnatea and 3,5,5-trieethyl hexanoyl cnybenzene sulphonates, with sodiim being the preferred cation.

The coepowds found to toe useful as organic perooyacid bleoch precursors haw the fonaula R11 O R1 C - I-L IP* wherein the 9x0191 is an aliphatic hydrocarbyl organic moiety of non Hmar structural configuration, at least one of R11 and R111 being hydrogen, the other of R11 and R111 being independently selected from hydrogen and C.-C 1 4 alkyl groups, the group: R11 0 R^-O- O- *n containing at least five carbon atcns in a Unpar chain extending from and including the cartanyl carbon and 20 being the acyl noiety of a carbcocylic acid having a lcgP^ of fvcn 1.9 to 4.1, wherein PQct is the partition coefficient of the carbcxyllc acid between n-octanol and water at 21 "C, and L it 1 leaving groif> the conjugate acid of Which has a pXs in the range froa 6 to 13.

R1 is an aliphatic hydrocarbyl organic moiety which can be linear, branched or cyclic.

The effects of structure on the hydrcphobicity of organic compounds as represented by their partition coefficients between octanol and water are described ty A Leo et al in Chemical Review, 71, pp 525-616 (1971). *n« authors provide lunerical values for the change in LogPg^, (where is the partition coefficient between n-octanol and water) associated with the inoorpotation of various substituents into a range of structures. This permits a value for ^OCT to be predicted for any structure.

All of the compounds display surface activity hut this property is not very narked for compounds in which the group X 11 111 R -C(R Tt"^)- contains less than 8 carbon atcms aru only those aoqpounds in which R1-C(R*V'^)- contains more than 10 carbon atcms display detergent characteristics. Hydrocarbyl group branching confers increased solubility relative to linear compounds of the sane nunfcer of carbon atoms and this increased solubility is associated with a decrease in surface activity relative to the corresponding linear compound. This effect also holds true for the aliphatic peroxy acids produced on perhydzolysis of the ccapounds. However, it has now surprisingly been found that aqueous liquors containing non linear aliphatic peroxy 8 caxboxylic acids in which non linearity preferably occurs on the 2-and/ar 3-carbon atoms with respect to the carbonyl carbon have a less intense odour of more aesthetically acceptable character than those containing the corresponding linear 5 aliphatic peroxyacids. The latter characteristically have intense, pungent, and aesthetically unattractive odours which are difficult to mask using umventional detergent fragrances.

The existence of nan linearity cn carbon atoms further removed from the carbonyl carbon than the 3-carbon atom position is less, 1Q beneficial for nonr-cyclic aliphatic moieties where little or no odour benefit is seen for non linearity counencing at 5- or higher carbon atom positions relative to the carbonyl carbon. Accordingly, brandling an 5- and higher carbon atoms where the group 0 r1—ca^R111)-!;- is a non-cyclic aliphatic acyl group is not believed to be critical to the odour forming capability of the ooopound. The reason for this difference in behaviour between branched and linear aliphatic peroxy acids is not well understood and does not 20 appear to be predictable.

The introduction of non linearity into the organic grcxp also affects the rate of pezhydrolysis of the precursor in alkaline hydrogen peroxide solutions.

Substitution and, in particular, di substitution of an alkyl gzoiqs on the 2-carton causes a lowering in the rate of perhydrolysis of the precursor because it hinders the approach of perhydroxyl ion and is believed to reduce the effectiveness of the percarboxylic acid as a bleach. Conpounds in accordance with the invention should therefore have at least one hydrogen atom on the 2-caxbon atom. Non linearity on the 2-carbc*i is less preferred than on the 3-caxhon where ejg. di alkyl substitution has much less effect on the perhydrolysis of the compound whilst still providing an aliphatic peroxy acid of inproved odour. 9 One preferred form of the groq»: R11 R1- C- wherein R1* and RU1 are as previously defined, is thus the group: R1V R11 I i R— C— C— wherein RV R1U R1V and RV are each independently selected from hydrogen and Cj-Cg alkyl grofs and the gxoqpi •rf R— C- C — RV R111 is a Cc-C,, alkyl group in which at least one of 11 111 iv "v R" R and R are C^-C^ alkyl, there being a linear chain of five or more carbon atcns extending tram and including the carbonyl carbon. Preferably R11 and R1^"1 are each a hydrogen atom.

Branched chain alkyl gzwp-ocntaining precursors in irtiich there is no more than a single branch on the 2-caxban but at least one on the 3-carbon perhydrolyse at an adequate rate (i.e. 3»80% conversion within approximately 5 minutes) but still produce an odour Mhen dissolved in an aqueous alkaline solution of hydrogen peroxide. However this odour is of a more acceptable type and level than that produced by the 5 corresponding linear alkyl precursors under the same conditions.

A preferred nunber of carbon atcns in the alkyl group: R1V R11 I I R—C C — RV RU1 is from 7 to 9 carbon atcns with a linear chain of from 5 to 10 8 carbon atoms and with Rjy and/or Ry comprising a side chain i.e. in the 3-carbon position with respect to the carbonyl carbon atom.

The most preferred R groip structures of this type are Cy-Cg radicals in which there is a single methyl side 15 chain in the 3-carbon atom position and the alkyl group is terminated by a tertiary butyl moiety.

Structures in accordance with the invention for the group where R^ is aliphatic include: 0 K C— 3,5,5-trimethyl hexanoyl CH.

I CH,— C - CH- - CH - CH, I 2 CH, CH-i 0 1 CH,(CH.)CH - C - 2-ethyl hexanoyl- 3 2 3, cm i2 ch3 11 h 0 I I chj— c - (ch2)3 - c- S-meChyl hexanoyl- h 0 1 1 CH3 - c - (C«2)4 c - 6-methyl heptanoy1- Of the above,the 3,5,5-trimethyl hexanoyl structure is the most preferred for odour and rate of perhySrolysis with the 5 5-methyl hexanoyl and 6-nethylheptar>oyl structures being less preferred for odour and the 2-ethyl hexanoyl being less preferred for the rate of perhydrolysis • An exatple of a structure in accordance with the invention for the group where R* incorporates a cyclo aliphatic or aromatic functionality Is (CH_),C- cyclchexyl butyrcyl "Hie leaving groip L must be capable of displacement from the bloacii precursor eis a consequence of the nuclecphilic attack on the bleach precursor by perhydroxyl anion generated fcy alkaline hydrogen peroxide. This, the perhydrolysis reaction, results in the formation of the percarbaxylic acid. Generally, for a groip to be a suitable leaving group it must exert an electron withdrawing effect within the precursor molecule as this facilitates the nuclecphilic displacement by the perhydroxyl anion.

Suitable leaving groups for this purpose have conjugate acid farms, the pKa of Which should lie within the range from 6 to 13. fKa values above 13 make the electron withdrawal effect so small as to be ineffective in promoting nucleophilic attack by perhydrcocide anion, an exanple of such a leaving group being - 00^. pKa values below 6 reflect such a large electron withdrawal effect as to make the molecule reactive to a wide variety at materials including e.g. water. Certain aliphatic anhydrides fall into this class. Preferred leaving groups have a pKa in the range from 7 to 11, more preferably from 8 to 10.

However for the purposes of the present invention the leaving gz«q} must also confer a degree of solubility on the precursor molecule so that it partitions between the aqueous phase and any organic phase present. Certain leaving groups such as sulphanamide groups, having conjugate acid forms of the appropriate pKa, do not provide sufficient aqueous solubility to the precursor molecule and therefore do not give a sufficient rate of perhydrolysis to be practicable in a laundry detergent liquor.

The leaving groups L found to be useful in oonpounds of the present invention are those having the formula or O I b) - N - C - R-> I ch2 13 wherein r2 is an alkyl group containing frcn 1 to 4 carton atcns; x 1b 0 or an integer fron 1 to 4 and Y is selected front - SO3M - 090_M - OOJt - k+(R2)3Q* - "(Vf* Wherein M is H, alkali metal, alkaline earth '-metal amoniun substituted anaoniim; and Q is halide or methosulphate.

Ilie preferred leaving group L has the foraula a) in Which x is 0, and Y is a suljiicnate or carbaxylate.

The position of the aolubilising group Y on the benzene ring in formula a) is not critical in that o -, m - and Impositions provide operable species. Nevertheless polar and steric factors make the o-substituted material most difficult to synthesise and of least value in that steric hindrance impedes the approach of perhydroxyl ion. In the preferred enfcodiment of leaving grotp L, where Y is a sulphonate radical, the precursor will normally be isolated in the form of its alkali metal salt because of the difficulty of handling the acid form.

Synthesis of the aospounds of the invention can be illustrated generally by a sequence of reactions in which a C7~C17 acid or acid chloride is formed in which the acyl group has the required brarxiied structure and the subsequent reaction of this with a compound of formula a) above therein the free bond is satisfied by a hydrogen atom.

The C?-C17 acid or acid chloride starting material, in which the acyl group has a linear chain of at least 5 carbon atcns extending frcn and including the carbonyl carbon and including a branch in at least the 2- and/or 3-carbon position, is prepared by methods known in the art.

Thus modified CWO syntheses can be used in vtfiich alpha-olefinB are reacted with carbon monoxide and water in the presence of cobalt catalysts to form a mixture of acids of which 60-65% have either 2-methyl or 2-ethyl brandling. If branched olefins are used as the starting material, the resulting acids are completely branched. Branched olefins themselves, having chain lengths up to C^., are produced by polymerising propylene or butene using a phosphoric acid catalyst under conditions of high tenqperature and pressure. The dimetrisation of iaobutene or the cedimerisation of n-butene and iaobutene leads to a highly branched isononanoic acid Which is a preferred starting material. The olefin source for another preferred starting material, 2-ethyl hexanoic acid, is propylene. Which is converted to n-butyr aldehyde and thence to 2-ethyl hexanoic acid by a Idol condensation of the aldehyde followed by hydrogenation of the aldol condensation product and final oxidation. ftenufacture of the acid reactant used in the preparation of sodiun 3,5,5-trimethyl hexanoyl axybenzene sulphonate, a preferred oonpound in accordance with the invention, involves the condensation of two moles of butene to form di iaobutene followed by carbcnylation to produce the aldehyde and subsequent oxidation to font the isononanoic acid. This is then converted into the acid chloride in known manner. The acid chloride is refluxed with sodiun phenol sulphonate in a nitrogen current at 100-150*C for 10-20 hours to form the sodium 3,5,5-trimethyl hexanoyl benzene sulphonate. Alternatively, the isononanoic acid can be transesterified, refluxing at 160-180"C with sodium phenol sulphonate and acetic anhydride in the presence of a small amount of sodium acetate catalyst, thereafter volatilising the by-product acetic acid and precipitating the sulphonate salt product frcn an organic solvent. A similar reaction procedure starting with n-nonanoic acid is disclosed and claimed in Patent Specification No. Siti+oS- IS Similar procedures to the above are also employed in the synthesis of sodiun 2-ethyl hexanoyl axybenzene sulphonate.

The analogous acyl axybenzene carbaxylate salts are also preferred oonpounds useful as peroxyacid bleach precursors. Synthesis of these materials is similar to that of the sulphonate salts in that the acid chloride is refluxed with p-hydraxybenzoic acid to produce the acylaxybenzoic acid product Which can be recovered by addition of petroleum ether to precipitate the acid.

Sodium 3,5,5-trimethyl hexanoyl axybenaoate and sodiun 2-ethyl hexanoyl axybenzoate are preferred members of this class of compounds. Although the above compounds are described in terms of their sodiun salts, other alkali metal and alkali earth metal cations and ammonium and substituted quaternary ammonium salts such as tri Cj-C^ alkanol anmoniun salts can also be enployed.

This suspect of the invention is illustrated in the following description of the preparation of two canpocnds useful as organic peroxyacid bleach precursors. 1) Synthesis of sodium 3,5,5-trimethyl hexanoyloxybenzene sulphonate Isononancyl chloride of purity 95.8% and molecular weight 176.5 (supplied by Akzo BV, Queens Road Hersham, Surrey, England) and sodium phenol sulphonate of purity £99.5% and MWt 196 (stpplied by BEH Chemicals Ltd, Poole, Dorset, England) were used as the starting materials in the reaction.

T3 (Hj-C-a^-CH-CHj-C-Cl + HD- I "3 ®3 CH- > CHj — C - CHj — CH — CHj — C — 0 -A -^SOjNa + HCl CH3 CH3 ° 16 19.62 gas of finely powdered, anhydrous sodiun phenol sulphonate (1/lOth mole) and 22.06 gms of Akzo isononanoyl chloride (weicpit 1/lOth mole + 25% excess) Mere weic^ied into a 500 al conical flask containing 250 5 mis of chlorobenzene. The flask was fitted with a magnetic stirrer, a 2-way head carrying a U2 gas inlet (leading to the base of the flask) and a reflux condenser (+ CaCJLg tifce) and was surrounded by an oil-bath. The flask was heated with stirring to 120*C and with H2 gas 10 passing through the flask, was maintained at that temperature overnight (20 hours). The heating was then turned off and the flask contents allowed to cool to room temperature. The contents were then washed with 3x1 litre diethyl ether, filtering between each wash (a IS Silverson stirrer was used for agitation). The resulting white solid was dried in a vacuus oven (no heat) after which the product was ground into a fine powder and dried again in the vacuum oven.

Yield: 27.40 gas (81.5% yield) NMR analysis showed 81.4% required conpound. 17 2) Synthesis of sodim 2-ethyl hexanoyl omybenzene sulphonate Anhydrous sodiun phenol sulphonate (58.85q; 0.3 role) Mas added to a stirred mixture of acetic anhydride (36.75g; 0.36 Hole), 2-ethylhexanoic acid (129.Sg; 0.9 mole) and 5 sodiun acetate (3g). The resultant White suspension was stirred under nitrogen and heated to 160"C under reflux; vigorous boiling occurred and was maintained for 4.5 hours.

At this point the nitrogen lead was transferred from the 10 condenser top to a spare inlet on the flanged-top of the reaction vessel and the condenser was set ip in a distillation node. The pot tanperature was gradually increased to 260*C during 1.5 hours; the still-head temperature rose to 131"C. The contents of the reaction 15 pot were then allowed to cool overnight to antoient tegperature before being washed with 3 x 1.5 litres diethyl ether, filtering between washes, and then being dried.

The yield of sodium 2-ethyl hexanoyl axybenzene 20 sulfiionate was 88.3g, 91.3% of theory.

Purity (by cat. SQj determination) - 93.4%.

Bie compounds of the invention, as defined above, are employed in detergent compositions primarily as peroxyacid bleach precursors, (the so-called low temperature bleach activators). Such detergent compositions 25 ccnprise an organic surfactant, a conpound as hereinbefore defined and a source of alkaline hydrogen peroxide and are normally particulate in physical form.

A wide range of surfactants can be used in the present laundry acnpositions. A typical listing of the classes and 30 species of these surfactants is given in U.S.P. 3,663,961 issued to Harris on May 23, 1972.

Suitable synthetic anionic surfactants are water-soluble salts of alkyl benzene sulphonates, alkyl sulphates, alkyl polyethaxy ether sulphates, paraffin sulphonates, 35 alpha-olefin sulphonates, alpha-sulpho-oarbaxylates and their esters, alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkyl phenol polyethaxy ether sulphates, 2-acylcay alkane-l-sulfhonates, and beta-alky laxy alkane sulphonates. 18 A particularly suitable class of anionic surfactants includes fcrater-aoluhle salts, particularly the alkali natal, aancniim and alkanolanncniian salts of organic sulphuric reaction products having in their molecular structure an 5 alkyl or alkazyl group containing from 8 to 22, especially from about 10 to about 20 carbon a teas and a sulphonic acid or sulphuric acid ester groip. (Included in the tern "alkyl" is the alkyl portion of acyl groips). Examples of this gxoip of synthetic detergents which form part of the detergent ig oenpasitions of the present invention are the sodiun and potassium alkyl sulphates, especially those obtained by sulphating the higher aliphatic alcohols (Cg.^g) produced by reducing the glycerides of tallow or coconut oil and sodiun and potassium alkyl benzene sulphonates, in whicii IS the alkyl grotp contains fro 9 to 15, especially 11 to 13, carbon atoms, in straight chain or branched chain configuration, e.g. those of the type described in U.S.P. 2,220,099 and U.S.P. 2,477,383 and those prepared from alkylbenzenes obtained by alkylation with straight chain 20 cjiloroparaffins (using aluminium trichloride catalysis) or straight chain olefins (using hydrogen fluoride catalysis). Especially valuable are linear straight chain alkyl benzene sulphonates in which the average of the alkyl group is 11.8 25 carbon atoms, abbreviated as g US, and C^-Cjj methyl branched alkyl sulphates.

Other anionic detergent compounds herein include the sodium c^o-i8 glyceryl ether sulphonates, especially those ethers of higher alcohols derived from tallow and 30 coconut oil; sodium coconut oil fatty acid nonoglyceride sulphonates and sulphates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulphate containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl groips contain 8 to 12 carbon atoms.

Other useful anionic detergent compounds herein include the vrater-solutale salts or esters of alpha-sulphonated fatty acids containing from 6 to 20 carbon atcns in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l-sulpihanic acids 19 oantalning frcn 2 to 9 carbon a tans in the acyl group and from 9 to 23 carbon atcns in the alkane moiety; alkyl ether sulphates containing frcn 10 to IB, especially 12 to 16, carbon atcns in the alkyl group and frcn 1 to 12, especially 5 1 to 6, more especially 1 to 4 moles of ethylene oxide; water-soluble salts of olefin sulphonates containing frcn 12 to 24, preferably 14 to 16, carbon atcns, especially those ■ade by reaction with sulphur trioncide followed ty neutralization under conditions such that any. sultones 10 present are hydrolysed to the corresponding tydroxy alkane sulphonates; water-soluble salts of paraffin sulphonates containing frcn 8 to 24, especially 14 to IB carton atcns, and beta-alkylaxy alkane sulphonates containing frcn 1 to 3 carbon atoms in the alkyl group and frcn 8 to 20 carbon atcns 15 in the alkane moiety.

ITie alkane chains of the foregoing nan-soap anionic surfactants can be derived from natural sources sudi as coconut oil or tallow, or can be made synthetically as far exanple using the Ziegler or Oxo processes. Water solubility 20 can be achieved fcy using alkali metal, aamcniua or alkanolanmonium cations; sodiun is preferred. Suitable fatty acid soaps can be selected frcn the ordinary alkali metal (sodiun, potassiun), ammonium, and alkylolasnonium salts of higher fatty acids containing frost 3 to 24, preferably fross 25 10 to 22 and especially frcn 16 to 22 carbon atoms in the alkyl chain. Suitable fatty acids can be obtained from natural sources audi as, for instance, fron soybean oil, castor oil, tallow. Whale and fish oils, grease, lard and mixtures thereof. The fatty acids also can be synthetically 30 prepared (e.g., fcy the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Trcpsdi process). Resin acids are suitable aadti as rosin and those resin acids in tall ail. Naphthanic acids are also suitable. Sodium and potassiun soaps can be Bade by direct 35 saponification of the fats and oils or fcy the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodiun and potassium salts of the mixtures of fatty acids derived frcn tallow and hydrogenated fish oil.

Mixtures of anionic surfactants are particularly suitable herein, especially mixtures of sulphonate and sulphate surfactants in a weight ratio of from 5tl to 1:5, preferably from 5:1 to 1:2, more preferably from 3:1 to 2:3. Especially 3 preferred is a 1:1 mixture of an alkyl benzene sulphonate having from 9 to 15, especially 11 to 13 carbon atoms in the alkyl radical, the cation being an alkali metal, preferably sodium; and either an alkyl sulphate having from 12 to IS, preferably 14 to 16 cartoon atoms in the alkyl radical or an alkyl 10 ethoxy sulphate having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6, having an alkali metal cation, preferably sodium.

The nonionic surfactants useful in the present invention IS are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilie balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5. ISe hydrophobic moiety may be aliphatic or aromatic in 20 nature and the length of the polyoxyethylene group tiiich is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrqokilic and hydrophobic elements.

Examples of suitable nonionic surfactants include: 1. the polyethylene oxide condensates of alkyl phenol, e.g. the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched chain configuration, 30 with ethylene oxide, the said ethylene oxide being present in amounts equal to 3 to 30, preferably 5 to 14 moles of ethylene oxide per mode of alkyl phenol. The alkyl substituent in such conpounds may be derived, for exaiiple, from polymerised propylene, di-ieobutylene, 35 octene and nonene. Other exanples include dodecylphenol condensed with 9 moles of etlylene oxide per mole of phenol; dinonylphenol condensed with 11 moles of ethylene oxide per mole of phenol; nonylphenol and V 31 di-isooctylphenol condensed with 13 Boies of ethylene aside. 2. Ihe condensation product of primary or secondary aliphatic alcohols having frcn 8 to 24 carbon atoms, in 5 either straight chain or branched chain configuration, with from 2 to 40 moles, preferably 2 to 9 moles of ethylene oxide per mole of alcohol. Preferably, the aliphatic alcohol comprises between 9 and 18 carbon atoms and is ethoxylated with between 2 and 9, desirably 10 between 3 and 8 moles of ethylene oxide per nole of aliphatic alcohol. The preferred surfactants are prepared from primary alcohols which are either linear (audi as those derived from natural fats or, prepared by the Ziegler process from ethylene, e.g. myristyl, cetyl, IS stearyl alcohols), or partly branched such as the Lutensols, Dobanols and Neodols Which have about 25% 2-methyl branching (Lutensol being a Trade Name of BASF, Dobanol*and Neodol being Trade Names of Shell), or Synperonica, which are understood to have , about 50% 20 2-methyl branching (Synperonic*is a Trade Name of I.C.I.) or the primary alcohols having more than 50% branched chain structure sold under the Trade Name Lial by Liquichimioa. Specific esaqoles of nonionic surfactants useful for the purposes of the invention include Dobanol 25 45-4, Dobanol 45-7, Dobanol 45-9, Dcbanol 91-2.5, Dcbanol 91-3, Dobanol 91-4, Dobanol 91-6, Dobanol 91-8, Dobanol 23-6.5, Sjyrperonic 6, Synperonic 14, the condensation products of coconut alcohol with an average of between 5 and 12 moles of ethylene aside per mole of alcohol, the 30 coconut alkyl portion having from 10 to 14 carbon atoms, and the condensation products of tallow alcohol with an average of between 7 and 12 moles of ethylene oxide per mole of alcohol, the tallow portion comprising essentially between 16 and 22 carbon atoms. Secondary 35 linear alkyl ethaxylates are also suitable in the present compositions, especially those ethaxylates of the Tergitol series having from 9 to 15 carbon atoms in the alkyl group and up to 11, especially from 3 to 9, ethoxy residues per molecule.

* Trade Mark 22 Useful nonionic surfactants also include those in which ethylene oxide is condensed with a hydrophobic base fanned by the condensation of propylene cwide with propylene glycol Wherein the molecular weight of the hydrophobic portion 5 generally falls in the range of 1500 to 1800. Such synthetic nonionic detergents are available an the market under the Trade Name of "Plutonic"'supplied by Wyandotte Chemicals Corporation.

Especially preferred nonionic surfactants far use herein 10 are the Cg-C^. .primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alochol, particularly the primary alcchols containing 6-8 moles of ethylene oxide per mole of alcohol.

Caticnic surfactants suitable for use herein include IS quaternary ammonium surfactants and surfactants of a seal-polar nature, for example amine oxides. Suitable quaternary ammonium surfactants are selected from mono Cg-Clfi, preferably C^-C^ N-alkyl or alkenyl anmonium surfactants wherein remaining N positions are 20 substituted by methyl, hydraxyethyl or hydraxyprapyl groups. Suitable amine oxides are selected from mono Cg-C^g, preferably C^g-Cj^ N-alkyl or alkenyl amine oxides and pcopylene-1,3-diamine dioxides therein the remaining tl positions are again substituted by methyl, hydroxyethyl or 25 hydroxypropyl groins.

The detergent oonpositions can comprise from l%-70% by weight of surfactant, but usually the surfactant is present in an amount of from 1% to 20%, more preferably from 5-15% by weight. Mixtures of surfactant types are preferred, 30 particularly anionio-aationic mixtures. Particularly preferred mixtures are described in British Patent No. 2040967 and Patent Specification No. Wf*3 ■ A source of hydrogen peroxide can be provided by any of the commercially available inorganic peroxygen bleaches and 35 also ty certain hydrogen peroxide adducts.

Suitable inorganic peroxygen bleaches include sodium perborate nano and tetra hydrate, sodiun percaxbonate, sodium persilioate and the clathrate 4Ha2S04 i : * Trade Mark 33 lNaCl. A separate source of alkalinity is required for clathrate materials and far stability reasons this should preferably be kept physically separated frcn the hydrogen peroxide source by e.g. enrobing or encapsulating the 5 latter. Hie hydrogen peroxide source will normally be present in an anoint of frcn 1% to 40%, more preferably from 5% to 35% ty weight of the composition and will most frequently be present in an amount of frcn 10% to 30% by weight. in preferred embodiments of this aspect of the invention the levels of hydrogen peroxide source and precursor canpound are arranged so that the molar ratio of hydrogen peroxide yielded by the source to precursor compound is greater than 1.5:1, normally at least 2.0. Under the usage conditions 15 encountered in domestic European laundry practice, this molar ratio is generally greater than 5.0:1 and most preferably is greater than 10:1.

Preferred detergent compositions, in accordance with the invention, will include those components commonly included in 20 heavy duty laundry detergents such as suds suppressing agents, detergent builders, chelating agents, soil suspending and anti redeposition agents, optical brightening agents, enzymes, colours and perfumes.

Suds suppressors useful in the detergent ocnposition 25 aspect of the invention, particularly conpositions used in laundering fabrics, are represented fcy materials of the silicone, wax, vegetable and hydrocarbon oil and phosphate ester varieties. Suitable silicone suds controlling agents include polydimethylsilnxanes having a molecular weight in 30 the range from 200 to 200,000 and a kinematic viscosity in the range from 20 to 2,000,000 nan /s (est), preferably from 3000 to 30,000 an /s (cSt), and mixtures of silaxanes and hydrophobic silanated (preferably trimethylsilanated) silica having a particle size in the range from 10 millimicrometers to 35 20 millimlcrometers and a specific surface area above 50 m /g. Suitable waxes include microcrystalline waxes having a melting point in the range from 65"C to 100*C, a molecular weight in the range frcn 4,000-10,000, and a penetration value 24 of at least 6, measured at 77"C by ASTM-D1321, and also paraffin waxes, synthetic waxes and natural waxes. Suitable jiwsphate esters Include mono- and/or di-C^-C^ alkyl or alkenyl phosphate esters, and the corresponding mono- and/or 5 di alkyl or alkenyl ether phosphates containing ip to 6 ethogcy groins per molecule.

Suds sifgaressors axe normally included at levels of from 0.01% to 5% by weight of the composition, dependent on the type of suds si^presaor used, mare cormanly 0.1% to 2% by 10 weight.

A highly preferred component of detergent compositions in accordance with the invention is one or more detergent builder salts whidi nay comprise iqp to 90% of the composition, more typically fvon 10% to 70% by weight IS thereof. Suitable detergent builder salts useful herein can be of the polyvalent inorganic and polyvalent organic types, or mixtures thereof. Non-limiting exangales of suitable water-soluble, inorganic alkaline detergent builder salts include the alkali metal carbonates, borates, phosphates, 20 pyrophosphates, tripolyphosphates and bioarbonates.

Exanples of suitable organic alkaline deter gency builder salts are water-aoluhle polycarboxylates sucJi as the salts of nitrilotriacetic acid, lactic acid, glycollic acid and ether derivatives thereof as disclosed in BE -A- 821,368, 821,369 25 and 821,370; succinic acid, malonic acid, (ethylenedioxyjdiaoetic acid, maleic acid, diglycollic acid, tartaric acid, tartzcnic acid and funaric acid; citric acid, aconitic acid, citraccnic acid, carboocymethyloocysuocinic acid, lactacysuccinic acid, and 2-axy-l,1,3-propane 30 tricarboxylic acid; otcydisuccinic acid, 1,1,2,2-ethane tetracarboxylic acid, 1,1,3,3-propane tetraoarbaxylic acid and 1,1,2,3-propane tetraoarbaxylic acid; cyclcpentane cis, cis,cia-tetracarboxylic acid, cyclcpentadiene pentacarboxylic acid, 2,3,4,5-tetrahydrofuran-cis, cis, cia-tetracarboxylic 35 acid, 2,5-tetrahydrofuran-cis-dicarboxylic acid, ' 1,2,3,4,5,6-hexane-hexaoarbaxylic acid, mellitic acid, pyzanellitic acid and the phthalic acid derivatives disclosed in C$ -A- 1,425,343.

Mixtures of organic and/or inorganic builders can be used herein. One such mixture of builders is disclosed in CA-A-755,038, e.g. a ternary mixture of sodium tripolyphosphate, trisodiun nitrilotriacetate, and trisodium ethane-l-hydroxy-1, 1-diphoephonate.

A further class of builder salts is the insoluble alunino silicate type Which functions by cation exchange to remove polyvalent mineral hardness and heavy metal ions from solution. A preferred builder of this type has the formulation Na^AlOj^CsiOjJy.xHjO wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5 and x is an integer frcn 15 to 264. Compositions incorporating builder salts of this type form the subject of G&-A-l,429,143 published torch 24, 1976, EB-A-2,433,485 published February 6, 1975 and EE-A-2,525,778 published January 2, 1976.

An alkali metal, or alkaline earth metal, silicate can also be present. The alkali metal silicate is preferably from 3% to 15%. Suitable silicate solids have a molar ratio of SiOj/alkali metaljO in the range from 1.0 to 3.3, mare preferably from 1.5 to 2.0.

Chelating agents that can be incorporated include citric acid, nitrilotriacetic and ethylene diamine tetra acetic acids and their salts, organic phosphorate derivatives such •is those disclosed in Diehl US Patent No. 3,213,030 issued 19 October, 1965; Bay US Patent No. 3,433,021 issued 14 January, 1968; Gedge US Patent No. 3,292,121 issued 9 January, 1968; and Bersworth US Patent No. 2,599,807 issued 10 June, 1952, and oarbaxylic acid builder salts such as those disclosed in Diehl US Patent No. 3,308,067 issued 7 March, 1967.

Preferred chelating agents include nitrilotriacetic acid (NXA), nitrilotrimethylene phosphoric acid (N1MP), ethylene diamine tetra methylene phosphonic acid (H2DP) and diethylene triamine penta methylene phosphonic acid (EETPMP), and these are incorporated in amounts of from 0.1% to 3%, more preferably 0.2% to 2% ty weight of the composition. 2 6 Antiredepositian and soil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carbaxymethylcellulcxse and hydraxyethylcel lulose, and homo-car co-polymeric palyaarbaxylic acids or their salts in Which 5 the polyoarbaxylic acid acwprisea at least two carbaxyl radicals separated from eacii other by not more than two carbon atcns. Polymers of this type are disclosed in O-A-1,596,756. Preferzed polymers include copolymers or salts thereof of naleic anhydride with ethylene, methylvinyl 10 ether, acrylic acid or methacrylic acid, the naleic anhydride constituting at least 20 sole percent of the copolymer.

These polymers are valuable for inproving Whiteness maintenance, fabric aah deposition, and cleaning performance an clay, proteinaoeous and axidizable soils in the presence IS of transition metal impurities.

Enzymes suitable for use herein include those discussed in U.S.P. 3,519,570 and U.S.P. 3,533,139 to MoCarty and MoCarty et al issued July 7, 1970 and January 5, 1971, respectively. Photoactivators are discussed in EF-A-57088, 20 hi<£ily preferred materials being zinc phthalocyanine tri- and tetra-sulphonates.

Anionic or nonionic optical brighteners are also preferred ingredients of detergent compositions in accordance with the invention, being normally present at levels of from 25 0.01% to 1% by weight, more preferably at levels of from 0.02% to 0.5% by weight.

Anionic fluorescent brightening agents are well-known materials, examples of Which are disodiun 4,4'-bis-(2-diethanolaiiino~4-anilirx>-s-triazin-6-ylaiiiino) 30 stilbene-2:2'disulphcrate, disodiun 4,4'-bis-(2-inorpholino-4-anilino-s-triazin-6-ylamino )st±lbene-2:2'-dlsulFhonate, disodiun 4,4" -bis- (2,4-dianilino-B-triazin-6-ylamino) stilbene-2:2'-di-sulphcnate, disodiun 4,4'-bis-(2-ani 1 ino-4- (N-methyl-N-2-hydroxyethylamino) -8-triazin-6-ylamino) 35 stilbcnc-2,2'-di-Bulphonate, disodiun 4,4'-bia-(4 phenyl -2,1,3-triazal-2-yl)-stilbene-2,2'-disulphonate, disodiun 37 4,4 • -his( 2' -ani lino-4-( 1-methyl-2-hydraxyethylami no) -s-tr iazin-6-ylamino)stilbene-2,21disulphonate, sodium 2(stiIfcyl-4"-(naptho-1',2':4,5)-l,2,3-triazole-2"-sulphonate and di-sodium 4,4'-bis(2-sulphonato styryl)biphenyl.

Other fluorescers to Nhich the invention can be applied include the 1,3-diaxyl pyrazolines and 7-alkyLaminocoumarins.

A preferred fluorescer is the anionic material available frcn Ciba Geigy S.A. under the trade name Tinopal CBS (Trade Marie) and mixtures thereof with materials available under the trade names Tinopal BG arid Blankcphar MBBN* (Trade MariO , the latter being sold by FazbenfabrUcen Bayer AG.

The non-linear aliphatic peroxy acid precursors of the present invention are normally employed at levels of from 1% to 15% by weight more preferably at from 1% to io% and most frequently at from 2% to 5% ty weight of a detergent composition. They can be incorporated into a detergent composition in a number of ways, most if not all of which are intended to minimise any reaction between the precursor and other cenponents during storage prior to use.

Thus the precursor may be fanned into particulates by spray cooling, prilling, marunerising, agglomeration or granulation, either alone or together with a carrier material Which may be organic or inorganic in type. Suitable inorganic materials include clays and other natural and synthetic aluminosilioates, as well as hydratable salts such as phosphates, oarbonates and sulphates. Suitable organic materials include ethoxylated Cj^-C^g alcohols and alkyl phenols, polyethylene glycols of MOT 4,000-10,000, C12-C1B fatty and esters thereof with monohydric and polyhydric alcohols. In one preferred method of manufacturing the precursor, disclosed in ' Patent Spptij No. , the liquid reaction product containing the precursor is blended with the carrier material under an inert gas atmosphere before being processed further to form the particulate material to be added to the detergent. This technique is particularly suitable when the carrier is a waxy organic solid such as an ethoxylated alcohol or ester and a highly preferred example, employing a glyceryl mono C1Q-C14 fatty acid ester carrier is disclosed in the Applicants' Published European Application No. 0 123 423.

In another method of manufacturing the preferred alkali metal C^-Cg branched chain acyl axybenzene sulphonate phenol sulphonate precursors, one of the reaction components e.g. alkali metal phenol sulphonate or fatty acid is enployed 5 in a greater excess than is necessary to achieve the desired completeness of reaction. The excess reactant is used as a binder material far the reaction product Which is taken from the reactor and, without separate crystallisation or solvent extraction steps, is acopacted to form particulates Which can lO be added directly to the detergent composition.

Preferred methods of making a particulate from a mixture of precursor and an organic carrier or builder are disclosed in the Applicants' Patent Specification No. <&?££> aid Published European Application No. 0 106 634.

Particulates incorporating the precursors of the present invention are normally added to the spray dried portion of the detergent composition with the other dry-mix ingredients such as enzymes, inorganic peroxygen bleaches and suds suppressors. It will be appreciated however that the 20 detergent composition to which the precursor particulates are added may itself be made in a variety of ways such as dry-mixing, agglomeration extrusion, flaking etc, such ways being well known to those skilled in the art and not forming part of the present invention.

The peroxy acid precursors of the present invention can also be irKXjrporated into detergent additire products. Such additive products are Intended to si^ppiement or boost the performance cf conventional detergent compositions and may contain any of the conponents of such compositions, although they will not comprise all of the 30 conponents present in a fully formulated detergent canposition. Additive products in accordance with this aspect of the invention will normally be added to an aqueous liquor containing a source of (alkaline) hydrogen peroxide, although under certain circumstances a source of alkaline hydrogen 35 peroxide may be included in the product. aft Additive products in accordance with this aspect of the present invention may emprise the compound alone in combination with a carrier gudi as a compatible particulate substrate, a flexible non particulate substrate or a container. Examples of conpatible 5 particulate substrates include inert materials audi as clays and other alianirosilicatee, including zeolites both natural and synthetic in origin. Other compatible particulate carrier materials include hydratable inorganic salts such as phosphates,. carbonates and sulphates.

Additive products enclosed in bags oar containers are manufactured such that the containers prevent egress of their contents when dry but are adapted to release their contents on imnersicn in an aqueous solution.

A convenient execution of this form of the additive product 15 ccnprises a particulate solid compound as hereinbefore defined enclosed in a container. Usually the container will be flexible, such as a bag or pcuch. The bag may be of fibrous construction ooated with a water impermeable protective material so as to retain the contents, such as is disclosed in European published Patent 20 Application Mo. 0018678. Alternatively it nay be formed of a water insoluble synthetic polymeric material provided with an edge seal or closure designed to npture in aqueous media, as disclosed in Superman published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure 25 comprises a water soluble adhesive disposed along end sealing one edge of a pouch formed of a water upermaable polymeric film such as polyethylene or polypropylene.

An alternative farm of the additive product apprises a compound as hereinbefore defined in water releasable combination with a non 30 particulate flexible substrate in a weight ratio of 1:10 to 30:1. Additive products of this type ,caJtoP».

Specification Not . Ir-fttVlf- and)l2040983B and in British Published Patent Application No. 2,125,453.

The substrate may itself be water soluble or water insoluble and 35 in the latter case it should possess sufficient structural integrity 3 0 under the conditions of the wash to be recovered frcn the machine at the end of the Laundry cycle. Structures Which ate water disintegratable,i.e. that break down in aqueous media to insoluble individual fibres or particles, are considered less satisfactory for 5 the purposes of the present invention.

Kater soluble materials include certain cellulose ethers, alginates, polyvinyl alcohol and water soluble polyvinyl pyrrol idone polymers. Which can be formed into non-woven and woven fibrous structures. Suitahle water insoluble materials include, but ace not 10 restricted to, natural and synthetic fibres, foams, Ranges and films.

The substrate may have any one of a number of physical farms such as sheets, blocks, rings, balls, rods or tubes. Such forms should be amenable to unit usage fcy the consumer, i.e. they should 15 be capable of addition to the washing liquor in measured amounts, audi as individual sheets, blocks or balls and unit lengths of rods or tubes. Certain of these substrate types can also be adapted for single or multiple uses, and can be provided with loadings of organic peroxy acid precursor tg> to a precursor: substrate ratio of 20 30:1 ty weight.

One such article ccnprises a sponge material releasably enclosing enough organic peroxy ccmpound precursor to provide bleaching action during several washing cycles. This multi-use article can be made by impregnating a sponge ball or block with 25 about 20 grams of the precursor and any adjuncts therewith. In use, the precursor leaches out through the pares of the sponge into the wash liquor and reacts with the inorganic peroxy bleach. Such a filled sponge can be used to treat several loads of fabrics in conventional washing machines, and has the advantage that it can 30 remain in the washer after use.

A highly preferred execution of this type of additive product utilises a flexible sheet so as to mate it compatible tilth the movement of the fabrics in the washing machine and to facilitate its handling during manufacture a£ the product. Preferably the sheet is 35 water pervious„i.e. water can pass frcn one surface of the sheet to the opposite surface and, for film type substrates, perforation of the sheet is desirable. The most preferred form of the substrate is a sheet of woven or non-woven fabric or a thin sheet of cellular plastics material. Woven fabric sheets can take the form of a plain 40 weave natural or synthetic fibre of low fibre 31 oouit/unit length, audi as is used for surgical dressings, or of the type known as cheese cloth. Loading limitations an sheet type substrates limit the amount of precursor compound that can be applied to the sheet and, in practice, .the weight 5 ratio of precursor coapoundisheet substrate normally lies within the range from li2 to 10:1.

Variations an the above sheet substrate product farms are also contemplated for the purposes of the present invention. For example, laminated sheet products can be eqslqyed in Which a central layer is impregnated and/or ooated with a composition incorporating the bleach precursor and then one or more outer layers are applied to produoe a fabric-lite aesthetic effect. The layers may be sealed together as as to remain attached during use or may separate IS an contact with water to facilitate the release of the coated or inpregnated material.

An alternative laminate form ccnprises one layer embossed or deformed to provide a series of pouch-like containers into each of which the bleach precursor euid optionally other 20 detergent cuuponents are deposited in measured amounts, with a second layer overlying the first layer and sealed thereto in those areas between the pouch-like containers where the two layers are in contact. The bleach precursor and any accompanying components amy be deposited in particulate, 25 paste or molten farm and the laminate layers should prevent egress of the contents of the pouch-like containers prior to their addition to water. The layers may separate or may remain attached together on contact with water, the oily requirement being that the structure should permit rapid 30 release of the contents of the pouch-like containers into solution. The nmfcer of pouch-like containers per unit area of substrate is a matter of choice, but will normally vary between 500 and 25,000 per square metre. 33 As stated above, suitable naterials' Which can be used as a substrate in the invention herein include, among others, sponges, paper, and woven and non-woven fabrics.

A suitable sponge like material that can be used in the 5 present invention comprises an absorbent foam like naterial in the form of a sheet. The tern 'absorbent foam-like material' is intended to encompass three dimensional absorptive materials such as 'gas blown foams', natural sponges and composite fibrous based structures such as are 10 disclosed in US Patent Nbs. 3311115 and 3430630. A particularly suitable material of this type is a hydrophilic polyurethane foam in Which the internal cellular walls of the foam have been broken ty reticulation. Foams of this type are described in detail in Dulle US Patent No. 3794029. A 15 preferred example of this foam type comprises a hydrophilic polyurethane foam of density 0. 036 g/cm^ with a cell count of between 8 and 40 cells per cm, preferably from 24 to 32 per cm available from the Scott Paper Conpaiy, EHdystone, Pennsylvania USA., under the Registered Trade Mark 20 "Hydrofoam". Preferred sheets of this type of material have thicknesses in the range frcn 3 to 5 am.

Preferred sheet substrates for use in this type of additive product are apertured and non apertured non woven fabrics Which can generally be defined as adhesively bonded 25 fibrous or filamentous products, having a web or carded fibre structure (where the fibre strength is suitable to allow carding) or ocnprising fibrous mats, in which the fibres or filaments are distributed haphazardly or in randan array (i.e. an array of fibres in a carded web wherein partial 30 orientation of the fibres is frequently present a£ well as a ccapletely haphazard distributional orientation) or substantially aligned. The fibres or filaments can be 33 natural (e.g. wool, silk, wood pulp, jute, heap, cotton, linen, sisal, or ramie), synthetic (e.g. rayon, cellulose, ester, polyvinyl derivatives, polyolefins, polyamides, or polyesters) or mixtures of any of the above.

The choice of binder-resins used in the manufacture of non-woven cloths can provide substrates possessing a variety of desirable traits. For example, the absorbent capacity of the doth can be increased, decreased, or regulated by respectively using a hydrophilic binder-resin, a hydrophobic 10 binder-resin or a mixture thereof in the fibre bonding step. Moreover, the hydrophobic binder-resin, when used singly or as the predominant conpcxind of a hydrophobic-hydrophilie mixture, provides non-woven cloths Whicdi are especially useful as substrates When the precursor-substrate 15 confcinaticns disclosed herein are used in an autcraatic washer.

When the substrate herein is a bonded non-woven cloth made from fibres, deposited haphazardly or in random array on the screen, the conpositians exhibit excellent strength in all directions and are not prone to tear or separate when 20 used in the washer.

Preferably, the non-woven cloth is water-laid or air-laid and is made from cellulosic fibres, particularly from regenerated cellulose or rayon, which are lubricated with standard textile lubricant. Preferably the fibres are from 4 to 50 inn in length and are from 0.15 to 0.55 Tex (1.5 to 5 denier) (Denier is an internationally recognised unit in yarn measure, corresponding to the weight in grams of a 9,000 meter length of yarn). Preferably the fibres are at least partially orientated haphazardly, particularly substantially haphazardly, and are adhesively banded together with hydrophobic or substantially hydrophobic binder-resin, particularly with a nonionic self-crosslinking acrylic polymer or polymers. Conveniently, the cloth ccnprises 70% fibre and 30% binder-resin polymer by weight and has a basis 2 weight of frcm 10 to 100, preferably from 24 to 72 g/m .

Apertured non-woven substrates are also useful for the purposes of the present invention, the apertures, which extend between opposite surfaces of the substrate are 34 normally in a pattern and! are formed during lay-down of the fibres to produce the substrate. Exeaplary apertured non-woven substrates are disclosed in US Patent Nos. 3,741,724, 3,930,086 aid 3,750,237.

A suitable diamond patterned apertured substrate is obtainable frcn Chiccpee Manufacturing Co., Milltown, New Jersey, USA under the Code Mb. SK 650 WX 577 and oonprising a polyester-wood pulp mixture having a basis weight of 50 2 g/m and approximately 13 apertures per square cm. 10 Another preferred example of an apertured non-woven substrate, also avai lable frcn Chiccpee Manufacturing Co., under the Code No. AK 30 ML 1379 canprises a regenerated cellulose sheet of 3.0 denier fibres bonded with Hhcplex HA 8 binder (fibreibinder ratio 70<30) having a basis weic£it of 40 2 2 IS g/m aid 17 apertures/can . A highly preferred square patterned apertured substrate of similar ocnposition but 2 fibreibinder ratio of 80:20 and basis weight 35 g/m is also available from Chiccpee BV Holland.

In general, apertured fabrics for the purposes of the 2 invention have from 10 to 20 apertures/cm , preferably 12-18 . 2 apertures/cm .

The size and shape of the substrate sheet is a matter of dxxice and is determined principally by factors associated with the convenience of its use. Thus the sheet should not 25 be so small as to become trapped in the crevices of the machine or the clothes being washed or so large as to be awkward to package and dispense frcm the container in which it is sold. For the purposes of the present invention sheets 2 2 ranging in plan area frcn 130 can to 1300 cm are acceptable, the preferred area lying in the range of from 520 2 2 cm to 780 cm .

Additive products in particulate substrate form can comprise powders, flakes, chips, tablets or noodles which may be used as-is or may themselves be enclosed in containers for addition to an aqueous liquor.

Hare usually, additive products in accordance with the invention contain other detergent ingredients in addition to the hereinbefore defined compounds. 3 S The type and level of sudi optional materials is constrained only by the requirements of unreactivity towards the precursor, and, where a substrate is utilised as the, or a carrier, by the loading limitations of the substrate, niis inposes a maximun weight ratio of optional ingredients to substrate of about 10:1, and in the case of ooated sheet siftstrates of about 8:1. As described in sore detail hereinafter, materials that are capable of reaction with the precursor can be incorporated in additive products of the present invention but it is essential that the precursor is spatially separate therefrca, i.e. is cUqposed at a substrate location that is free or substantially free of the other reactant materials.

One factor determining the acceptable level of incorporation of an optional ingredient is its physical characteristics i.e. whether it is liquid or solid and if solid whether it is crystalline or waxy and of high or low melting or softening point.

Hi^ily desirable optional conponents are solid, water soluble or Mater dispersible organic processing aids of a waxy nature having a Mpt in the range 30-80°C. TTie most preferred processing aids have a softening point greater than 40°C and a melting point less than 80*C to permit their easy processing.

The preferred processing aids serve as pLasticisers or thickeners in the incorporation of the precursors into or onto the substrate and ideally are non-hygrosccpic solids that are mixed with the precursors and melted to provide mixtures having a viscosity of ip to 30,000 centipoises at 50 "C.

Typical solids are C^-C^ primary and secondary alcohols and C^-C^q fatty acids and ethaxylates thereof containing frcm 15 to 80 ethylene oxide groips per mole of alcohol, aorbitan esters of ci2~C20 *att¥ "cid* and polyethylene glycols of Mwt 4,000-10,000. As stated hereinbefore, preferred materials are those of low hygrosocpicity particularly the C14-C1g saturated fatty acids.

The Cjg'Cjg fatty acids and polyethylene glycols of Mft 4,000-8,000, are particularly effective When used in amounts such that the weight ratio of compounds :processing aid lies in the range 20:1 to 1:2 particularly 4:1 to 1:1. 36 In addition to the foregoing optional components that are of primary value in incorporating the precursor onto, and releasing it from, the substrate, conventional detergent ingredients can be incorporated into the composition provided 5 that they are not reactive towards compounds as hereinbefore defined. Thus, surfactants, suds modifiers, chelating agents, anti-redeposition and soil suspending agents, optical brighteners, bactericides, anti-tarnish agents, enzymatic materials, fabric softeners, antistatic agents, perfuses and 10 bleadi catalysts can all be introduced into a wash liquor by maans of the additive products of the present invention, subject to the constraints imposed by the loading limitations of the substrate.

In detergent additive products in thich the compositions 15 comprise a peroxy bleach precursor compound, as hereinbefore defined, disposed on a substrate of either particulate or non particulate farm, the substrate is preferably absorbent and the composition is iiqaregnated therein.

Application of the precursor can be carried out in any 20 convenient manner, and many methods are known in the art. As the preferred acyloxybenzene sulphonate or carbcxylate precursors are solid at tenperatures in excess of 150*C, one form of application is by solution in organic solvents which are volatilised after application, whilst another employs a 25 slurry or suspension of the finely divided solid in water or other liquid media.

Preferred oonpositlons are - - substantially anhydrous and . thus incorporation on the substrate is best accomplished by utilisation of a non 30 aqueous liquid medium.

A highly preferred embodiment utilises a processing aid and/or other optional ingredients in molten farm as the liquid meditm in Whidi the finely divided precursor is dispersed.

Where the substrate ccnprises a non-sheet like reticulated foam article, direct impregnation of the article by a liquid mediun incorporating the dispersed precursor, either alone or with other components of the formulation can 37 be used, employing methods known in the art and described in nore detail hereinafter. Where the substrate ccaprisea a non-woven material or a foam article of sheet-like form, it is preferred to nix the bleach precursor with a ocapatible 5 non-hygroscopic material of melting paint <,80*C, such as the processing aids hereinbefore described to provide a waxy solid in which the hieach precursor is present in the farm of a solid solution and/or as a dispersed phase. The melting point range and waxy nature of polyethylene glycols of 10 molecular weight .>4000 make then useful for this purpose.

Where nonionic surfactants farm components of the composition, their physical properties may permit their use as, or as part of, a liquid medium in Which the precursor and other solid components are incorporated. 15 As previously indicated, materials reactive towards the percocy bleach precursor compounds of the invention can be incorporated in detergent additive products containing them provided that the precursor and the reactive material are spatially separated from one another. Inorganic peroxygen 20 bleaches Which either contain water or hydrogen peroxide in hydrogen bonded farm, 3Uch as sodium perborate ncnohydrate and tetrahydrate, sodium percarbonate, sodium persilicate or sodium perpyrophoephate, and also urea-hydrogen peroxide addition products, are materials which are sufficiently 25 reactive to require this spatial separation.

Where the precursor and the inorganic peroxygen bleach are incorporated in physically separate locations en the same non particulate sheet substrate, a convenient method of application is the deposition of the respective melts, 30 suspensions or solutions as discrete bands of material on the substrate. This can be achieved using a divided extrusion head or by applying the melt or suspension to separate webs of substrate which are subsequently joined longitudinally. Preferably the bleach is applied as a dispersion of solid 35 particles in a molten processing aid (as hereinbefore described) at a tesperature in the range 40* to 60*C. Using this technique, bleachisubstrate weight ratios of ip to 15:1 can be obtained, this level of loading is attainable with 38 cellular substrates but substrates of fibrous character tend to be limited in practice to bleach:substrate weight ratios of no more than 8:1. Furthermore, loading limitations infxjsed by the substrate surface area required for the 5 incorporation of the precursor may limit the amount of bleadi to less than than this and bleach:substrate weight ratios in the range 5:1 to 1:2 are normally enplcyed. Provision must also be made for the separation of the bands or areas of bleach and the corresponding bands or areas of precursor 10 during transport and/or storage, litis is achieved by interposing layers of material between the layers of substrate or by producing patterns of deposited material that are not coincident an stacking of the substrate.

A preferred method of making the particulate substrate 15 forms of detergent additive product is by applying a spray of the canposition as a solution,dispersion,or molten suspension, on to a moving bed of particulate substrate in a rotating drum or pan fluidised bed, or a rotating blade mixer of the Schugi or Patterson-Kelly type.

In a preferred netted of making sheet substrate additive products in accordance with the invention, the precursor(s), dissolved or dispersed in a molten processing aid, are held In a trough formed by the nip of two horizontal rolls arranged side by side and rotating in opposite directions such that 25 the nip is formed by surfaces having approximately the same velocity in a downward direction. Molten material is spread on one of the rolls and transferred to a continuous web of substrate whose speed is the sane as that of the roll and whicii contacts the roll over a limited length of its 30 periphery. The inpregnated substrate is then contacted by a smoothing and spreading roll, having a direction of rotation such that its contact surface is moving in the opposite direction to that of the substrate. The rolls enplcyed in this technique are fabricated in metal and are heated to 35 maintain the impregnating mixture in the liquid phase.

Bleaching ccnposi.ti.ans can also be formulated aonprising a precursor aanpound as hereinbefore defined in oonbinaticn with a source of hydrogen peroxide in the form of an alkali metal inorganic pero>^ salt or a 40 hydrogen peroxide clathrate.or ccnposed of the peroxy 39. acid derived from the precursor compound in combination with a stabilising agent.

In the embodiment ccnprising a mixture of the precursor and a source of alkaline hydrogen peroxide it is very 5 desirable that the two components be isolated from each other in order that a reaction does not occur prior to use. Although a reaction can be prevented fcy making an anhydrous mixture of the two components, the maintenance of such a mixture in the anhydrous state is very difficult under normal 10 storage conditions. A preferable technique is to sq>arate the components physically, ty coating one or both with inert materials that dissolve or disperse in aqueous media, fcy incorporating each in separate or Departmental packaging, or fcy fixing each component to separate locations on a non 15 particulate suhstrate. Each of these separation techniques is well known in the art and does not form part of the present invention.

Bleaching compositions of this type contain fron 30% to 95% by weight of the hydrogen peroxide source and 70% to 5% 20 fcy weight of the precursor compound as hereinbefore defined; mare generally from 50% to 90% of hydrogen peroxide source and from 50% to 10% of precursor compound, most preferably from 75% to 90% of hydrogen peroxide source and from 25% to 10% of precursor compound.

Where the peroxy acid derived fron the precursor compound is employed in the bleaching composition, it can be used in conjunction with a stabilising agent such as quinoline, quinaldic acid, picolinic acid or dipicolinic acid or a derivative thereof, preferably together with a polyphosphate 30 salt. Stabilising agents of this type are disclosed in Sprout USP 2,838,459, Sennewald et al USP 3,442,937, and Cann USP 3,192,255. A preferred system employs a mixture of 8-hydroxy quinoline and an acid pyrophosphate salt in a ratio of from 1:1 to 5:1. The stabilising agents are incorporated 35 at a level of from 0.005% to 1.0% fcy weight of the composition.

In addition, exotherm control agents are also preferred components of solid bleaching compositions incorporating 40 organic peroxy acids, preferred examples of such agents including boric acid as disclosed in Hutchins et al USP 4,100,095, or hydrated inorganic salts as disclosed in Nielsen USP 3,770,816.

Hie present invention also finds utility in the fomation of aqueous bleaching liquors fcy means of the reaction of a source of alkaline hydrogen peroxide with additive products oantalning precursors of an aliphatic peroxy acid those cartxaxylic acid analogue has a log Pqqj of fron 1.9 to 4.1 10 particularly with the Cg-C^g branched alkyl grcxp-containing precursor compounds specifically described above, or fcy means of the addition of the above-described detergent or bleaching aonpositicns to an aqueous medium.

Aqueous bleaching liquors in accordance with this aspect of 15 the invention develop low intensity or bland odours which are compatible with, and/or are capable of being masked by, the perfume compositions conventionally used in determent products. Aqueous bleaching liquors containing the most highly preferred compounds in accordance with the invention 20 are virtually odourless whereas the analogous linear alkyl chain materials have a pungent odour which is aesthetically undesirable.

In addition to the non linear precursor conpounds of the present invention, products and compositions made in 25 accordance with the invention may optionally contain any of the organic peroxy add bleach precursors known in the art. A detailed disclosure of such precursors is provided in British Patent Specification No. 2040983. For the purposes of the present invention, blends of branched Cg-C10 acyl 30 axybenzene sulphonate or carkxaxylate with per acetic acid precursors are preferred, examples of such peracetic acid precursors including tetra acetyl ethylene diamine, tetra acetyl methylene diamine, tetra acetyl glyoouril, sodium p-acetoxybenzene sulphonate, penta acetyl glucose, and octa 35 acetyl lactose. However, the invention also contemplates blends of branched Cg-C^ carbon chain-containing precursors with e.g. peroxybenzoic and peroxyphthalic acid precursors where different combinations of bleaching properties are required.

In blends of the preferred branched Cg-C^ acyl axybenzene sulphonate precursors with other peroxyacid precursors it has been found that the Cg-C^ acyl axybenzene sulphonate should preferably be present in an amount to provide a level of at least 2 ppn and preferably at least 5ppm available oxygen in the wash liquor, in order that the benefit of the Cg-C^Q peroxy acid can be realised. Generally the weight ratio of the Cg-C^g acyl axybenzene sulphonate precursor to the other peroxy acid (e.g. peracetic acid) precursor should be such as to provide a C8-C10 aliphatic percocy acid xperacetic acid molar ratio in the range from 3:1 to 1:5 preferably 2:1 to 1:3 most preferably from 1.8:1 to 1:2. Under European Mashing conditions, blends in whidi the Cg-C^Q acyl axybenzene sulphonate delivers frcn 5 to 15 jpn available oxygen in the Mash liquor are preferred.

The level of usage of the precursor will naturally be dependent on a nunfcer of factors, e.g. the size of the fabric load in the machine, the level of bleadiing performance desired, the amount of perhydroxyl ion in the wash solution, the bleaching efficacy of the organic peroocy species derived fron the precursor and the efficiency of conversion of the precursor into that peroxy species. It is conventional with inorganic peroxy bleaches to provide a level of available oxygen in solution fron 50 ppm to 350 ppn by weight for heavy duty laundry purposes. However, when using organic peroxy bleaches a level of available oxygen provided by the organic peroxy compound may lie in the range frcn 1 ppm to 50 ppn, levels of from 1.5 ppn to 16 ppn being appropriate under conventional US washing conditions while levels of frcn 20 ppn to 50 ppn are more commonly used under European washing conditions. This level of available oxygen should be attained within the normal wash cycle time i.e. within 5-25 minutes depending on the particular wash cycle being employed.

For a maciiine having a liquid capacity in use of 20 to 30 litres, such a level of available oxygen requires the delivery of from 1 gr to 20 gr of organic peroxy conpound percursor assuming quantitative conversion.

Various aspects of the invention are illustrated in the following Exanples in Which all parts and percentages are by weight unless otherwise specified. 43 BOWIE 1 Preparation of aoditm 3,5,5 trimethyl hexanoyl axybenzene 100 gum of dehydrated sodium phenol sulphonate and 117 S gms (30% molar excess) of isononanoyl chloride* (ex Akzo BV, IVt 176.5) were weighed into a 2 litre conical flask. Hie flask was fitted with magnetic stirrer and carried a 2-way head fitted with an Airflux condenser and a nitrogen inlet tube leading to the base of the flask. 500 ails chlorobenzene 10 uere added and the resulting suspension was stirred. 5 gms of tetrabutylanmonium bromide (si^plied by Aldrich Chemical Co. Inc., Milwaukee, Wisconsin 53233, USA) were added as catalyst and the resulting suspension Has stirred and heated to 120°C with nitrogen passing through the flask. Heating IS was continued with nitrogen passing, for 19.5 hours.

The reaction mixture was then cooled to room tenperature, poured into 3 litres of diethyl ether and well washed using a Silverson-stirrer. The solid material was filtered off by Buchner filtration and the resulting solid was washed with 20 2x2 litres of ether, filtering off after each wash. The resulting solid was dried over PjOg in a vacuum desiccator, was powdered in a coffee grinder and re-dried in a vacuum desiccator over P2°5" The yield was 140 gms and (MR analysis showed the solid to comprise 92% sodium 3,5,5 25 trimethyl hexanoyl axybenzene sulphonate and 8% sodium phenol sulphonate.

*This is the ojimun term used in the trade to describe 3,5,5 trinethyl hexanoyl chloride.

EXAMPLE 2 Preparation of sodium 3,5,5 trimethyl hexanoyl oxybenzoic acid Hie same apparatus was used p-hydraxybenzoic acid was mixed as in Example 1. 74.5 g of with lOOg of 3,5,5-trimethyl 43 hexanoyl chloride (5% nolar excess) and 3.7 g of tetrabutyl amoniun bromide catalyst. The mixture mbs stirred and heated to 100"C in a current of nitrogen for 2 hours. The resultant white, porous, solid mass was cooled, broken iqp 5 under petroleix ether (bp 40-60"C), filtered, washed and dried. The product, 126 g (84%) was found fcy NMR analysis to be 95% 3,5,5-trimethyl hexanoyl axybenssoic acid and 5% p-hydruxy benzoic acid.

Claims (14)

CLAIMS 44

1. A non linear aliphatic peroxyoarboxylic acid precursor adapted to form a non linear aliphatic peroxy acid in aqueous alkaline hydrogen peroxide solution , the percursor havii*) the yt>iK?ral formula: ■, R11 O 1 1 « R C C-L im wherein the grotp: R11 X I 10 R—C— i111 is an aliphatic hydrocarbyl organic moiety of non lineeir structural configuration, at least one of R11 and R11'1 being hydrogen, the other of R11and R111 being independently selected fron hydrogen and Cj-C^ alkyl groiqps, the group: 15 R11 O containing at least fiw carbon atoms in a linear chain extending from and including the cazfconyl carbon and being the acyl moiety of a oarboxylic acid having a logPQct of from 1.9 to 4.1, wherein PQct is the partition 20 coefficient of the carboxylic acid between n-octanol and water at 21*C, and L is a leaving groip selected from: a) - 0 -^"^(CH^Y and O II 25 b) - N - C - R_ I 45 wherein R, is an alkyl group containing from 1 to 4 carbon atoms, x is 0 or an integer from 1 to 4 and Y is selected frcm: - SOjM 5 - CSO-jM - CO^ - n+<V3q_ - wherein M is H, alkali metal, alkaline earth metal anmonium or 10 substituted anmonium and Q is a halide or methosulphate, the conjugate acid of said leaving group L having a pKa in the range fron 6 to 13.

2. A non linear aliphatic peroxycarbaxylic acid precursor according to claim 1, wherein R1 ccnprises the group: R1V 15 R- C- kV wherein R*V and RV are each independently selected frcm hydrogen and C^-C^ alkyl groips, and the group : R1V R11 I I R- C - C- kV R111 is a C,-Clc alkyl . groip in Whidi at least one of 11 111 l\r V 20 R , R , R and R are Cx-C4 alkyl, there being a linear alkyl chain of five or more carbon atoms extending from and including the carbonyl carbon. 46

3. A non linear aliphatic peroxycarboxylic acid precursor according to eitlior of claims 1 or 2, wherein: R11 rf-O- i:; a qruup wheruin R*' .uxl R*"'' arc euiii a hydnx(iMi atom.

4. A non linear aliphatic peroxycarboxylic acid precursor according to claim -3, wherein: R11 R^-C- Am is a groip. 10

5. A compound according to any one of claims 1-4, wherein the conjugate Kid of leaving gxoqp L has a pKa in the range from 7 to 11.

6. A ccnpound according to Claim 5, wherein the pKa is in the range from 8 to 10. 15 7. A compound according to claim 5 or 6, wherein L has the formula a) given in Claim 1 in which x is 0 and Y is -SO^M or wherein

M is as defined in Claim 1.

8. An alkali metal ammonium or tri C^-C^ alkanolaitnonium 2-ethyl hexanoyl oxybenzene sulphonate. 20

9. An alkali metal ammoniun or tri C^-C^ alkanolammonium 3,5,5-trimethyl hexancyl oxybenzene sulphonate.

10. 2-Ethyl hexanoyl axybenzoic acid or an alkali metal, alkaline earth metal, ammonium or tri 25 alkanolamnonium salt thereof. 47

U. 3. 5, S-Trimntliyl. hexanoyl oxybenzoic acid or <ui alkali metal, alkaline earth metal, anrnoniun or tri C^-C^ alkanol amoniiai salt. Uiert»f.

12. a non-linear aliphatic peroxycarboxylic acid precursor according to claim 1, substantially as hereinbefore described with particular reference to the accompanying Examples.

13. A process for preparing a non-linear aliphatic peroxycarboxylic acid precursor according to claim 1, substantially as hereinbefore described with particular reference to the accompanying Examples.

14. A non-linear aliphatic peroxycarboxylic acid precursor according to claim 1, whenever prepared by a process claimed in claim 13. F. R. KELLY & CO., AGENTS FOR THE APPLICANTS.