IE56907B1 - Bleaching detergent liquors incorporating non-linear aliphatic peroxycarboxylic acid precursors and compositions for use therein - Google Patents

Description

This invention relates to the field of ooddisable stain removal, especially but ncfc solely to the zcnoraal of ooddisable stains from fabric» and is particularly concerned with the removal of these stains using peroxygen bleaches at tesperatuxee 4®0*c such as are encountered in domestic washing and laundering operations.

The remnwml of ooddisable stains firam either hard surfaces or fabrics ty means of peroxygen bleaches at temperatures less than 60*C is a well known technique and customarily involves the use of organic peroxy acids, the most commonly used peroxy acid is peracetic acid, normally generated in situ in tha 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 atoms ln the acyl group have also been disclosed and taught for this purpose and CB-A-864,798, Canadian Patent No. 635,620, US Patent Nos, 4100095, 4119660, 4126573 and European Published Application No. 0068547 all relate to the formation, stabilisation or use of such materials.

Recently, as described in European Application No. 0068547, it has been fotnd 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. Thus for removal of fugitive dyestuffs in bulk solution, a 'hydrophilic' bleach species is satisfactory, whereas for stains on solid surfaces a bleaching species 10 showing more hydrophobic character, and hence 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 & Gianfranco I* Spadini, on November 1st 1983 entitled Bleaching Gospoeitions, and Patent Specification No. entitled Detergent Additive Product conpoeitions are disclosed Which incorporate a Cg-C10 acyloxy cospcwd capable of forming a ^10 aliphatic peroxy acid on reaction with alkaline hydrogen peroxide, the Cg-Cjg acyl being linear in nature.

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

It has new been fouri that certain branched chain 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 oosplete inorganic peroxy bleach-containing detergent composition or as part of a 35 laundry additive product added to an aqueous solution of an inorganic peroxy bleach-containing detergent ersprmition.

According to ene aspect of the invention therefore there is provided an aqueous laundry bleaching liquor having a bland odour cosprisiftg a source of alkaline hydrogen peroxide in an amount to give a level of available oxygen of from 50 to 350 ppm together with a non-linear aliphatic, aryl aliphatic or alkanyl aliphatic peroxycarbaxylic acid precusor in an amount to give from 1 to 50 ppm of the peroxycarboxylic acid upon reaction with said alkaline hydrogen per oxide source, said precusor having the general formula: RU O io therein the group: is an organic moiety of non-linear structural configuration, at least one of R11 and R111 being hydrogen, tbe other R11 and R111 being independently selected from hydrogen and Cj-C^ alkyl groups, the group: r^o R1-C- a) and ?*2 wherein R2 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 from: - ooyi - CSOjM - CXJjM - V+l*2Wwherein M is H, alkali metal, alkaline earth metal, anmoniun or substituted anmoniun and Q is a halide or methosulphate.

These leaving groups have a pKa in the range from 6 to 13 more preferably in the range from 7 to 11, most preferably from 8 to 10.

Preferred leaving groups are those of formula a) above in which x is O and Y is selected from -SO^M and -ΟΟ^Η therein M is alkali metal, preferably sodium.

Preferably the grotp: R1- Cis a Cy<^ alkyl grotp and preferred oonpounds are alkali metal, amsoniim or substituted ammonium 2-ethyl hexanoyl oxybenzene sulphonates and 3,5,5-trimethyl hexanoyl oxybenzene sulphonates, with sodium being the preferred cation.

According to another aspect of the invention, detergent conposi tions are provided conprising a conpound, as above IO defined, in combination with a surfactant which nay he anionic, nonionic, cationic or zwitterionic or a mixture thereof and a source of alkaline hydrogen peroxide. In a preferred form of this aspect of the invention, the surfactant is a mixture which is primarily anionic in character with nonionic and, in a highly preferred form, cationic oonponents. Also in a preferred form of the invention, the molar ratio of the hydrogen peroxide present to tiie defined oospomd is at least 1.5:1.

In a further aspect of the invention, laundry additive products are provided in which a conpound, as hereinabove defined, is enclosed in a container such as a bag or pouch of synthetic polymeric film material which is formed with a water frangible closure to permit release of its contents on immersion in an alkaline aqueous laundry liquor containing a source of hydrogen peroxide. Another form of this aspect of the invention conprises a oonpomd as defined above in water-releasable conhinaticn with a flexible non-particulate substrate in a ocnpoundxsdbstrate weight ratio of front l:10to 30:1. In both of these additive conpositions other detergent 3q oonponents, such as surfactants, builder salts and chelating agents, may be present.

The invention also embraces bleaching conpositions comprising an aliphatic percarboxylic acid of formula R-GOOCH where R is a C^-C^. allyl grotp which is branched in at least the 2- and/or 3-position with respect to the carbonyl carbon atom, there being a linear alkyl chain of 5 or more carbon atoms extending free and including the carbonyl carbon in combination with a stabilising agent.

Other aspects of the invention cceprise a method of 5 forming an aqueous laundry liquor having a bland odour ty the addition of laundry additive coRpositions as defined above to aqueous solutions containing a source of alkaline hyirogen peroxide and laundry liquors formed ty such a method or by the dissolution of a detergent or bleaching ooBposition IO containing a oospotnd as defined above.

The aoapowds found to be useful ae organic peroxyacid bleach precursors have the formula R11 O I * C - C - L •ill wherein the groqp: R111 is an organic moiety of non linear structural configuration, K11 and R111 being independently selected fron hydrogen and C1-C4 alkyl groups, the group: R11 0 ’ M R -e- cR111 being the acyl moiety of a carboxylic acid having a logP*^ of from 1.9 to 4.1, wherein pocL i® the partition coefficient of the carboxylic acid between n-octanol and water at 21 *C, and L is a leaving grotp the conjugate acid of which has a pKa in the range from 6 to 13.

R1 is an organic moiety uhich can have a variety of forms. Thus R1 may be aliphatic in nature and way be linear, cycloaliphatic or branched. Alternatively R1 may be arcmatic, alkyl aromatic or aryl aliphatic. R1 may alao include heteroatoms such as oxygen, nitrogen and halogen provided these are not in the backbone of the group i.e. they mist be pendant frcm the hydrooartyl structure. Groups subject to oxidative attack euch as aldehyde groups should not be present and tha moiety should preferably be free of «saturation other than that of arcmatic character.

Preferably R1 ia a hydrooartyl moiety.

The effects of structure on the tydrcphobicity of organic coapounds as represented ly their partition coefficients between octanol and water are described ty A Leo et al in Chemical Reviews, 71, pp 525-616 (1971). The authors provide numerical values for the change in LogP^^ («here is the partition coefficient between n-octanol and water) associated with the incorporation of usurious substituents into a range of structures. This permits a value for LogPq^ to be predicted for ary structure.

All of the ocmpounds display surface activity but this property is not very marked for coapounds in which the group R1* -CCR^^R11,1)- contains less than 8 carbon atoms and only those coapounds in which R1-C(RU‘RU'1')- contains more than 10 carbon atoms display detergent characteristics. Hydrocarbyl group branching confers increased solubility relative to linear coapounds of the same muter of carbon atoms and this increased solubility is associated with a decrease in surface activity relative to the corresponding linear coopound· This effect also holds true for the aliphatic peroxy acids produced cn perhydrolysis of the coapounds. However, it has now surprisingly been found that aqueous liquors containing non linear aliphatic peroxy θ carboxylic acids in which non linearity occurs particularly on the 2and/or 3-carbon atoms with respect to the carbonyl oar ben, have a less intense odour of more aesthetically acceptable character than those containing the corresponding linear aliphatic peraxyacids. The latter characteristically have intense, pungent, and aesthetically unattractive odours which are difficult to mask using conventional detergent fragrances.

The existence of non linearity cn carbon atoms further removed from the carbonyl carbon than the 3-carban atom position also appears to be beneficial but to a lesser extent and little or no odour benefit is seen far non linearity commencing at 5- or higher carbon atom positions relative to the carbonyl carbon. Accordingly, branching an 4- and higher carbon atoms is not believed to be so critical to the odour forming capability of the compound. The reason for this difference in behaviour between branched and linear aliphatic peroxy acids ia not well understood and does not appear to be predictable.

The introduction of non linearity into the organic group AA111)- also affects the rate of perhydrolysis of the precursor in alkaline hydrogen peroxide solutions.

Substitution and, in particular, di substitution of an alkyl group on the 2-carbon causes a lowering in the rate of perhydrolyais of the precursor because it hinders the approach of perlydroxyl ion and is believed to reduce the effectiveness of the percarboxylic acid as a bleach. Non linearity cn the 2-carbon is thus less preferred than on the 3-carbon where e.g. di alkyl substitution has much lees effect cn the perhydrolysis of the conppund whilst still providing an aliphatic peroxy acid of improved odour.

One preferred fon of the groups R11 ι I wherein R^1 and RU1 are as previously defined, is thus the grotp: R1V RU 1 R— C — c — wherein iV •ill IV V R and R are each independently selected fron lydrogen and C^C4 alkyl groups and the grotp: τ1’ F R — C- C — RV conprises a Cg-C_- alkyl group in which at least cne of IO and R are alkyl, there being a linear chain of five or more carbon atans extending from and including ths carbonyl carbon. Preferably R11 and R.m are hydrogen atoms.

Branched chain allyl grap-oontaining precursors in which there iano more than a single branch cn ths 2-carbcn but at least one on ths 3-carbon perhydrolyse at an adequate rate (i.e. >80% conversion within approximately 5 minutes) but still produce an odour «fan 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 corresponding linear alkyl precursors under the same conditions.

A preferred runber of carbon atoms in the alkyl group: R1V RU » I R-C-C — Rv RU1 is from 7 to 9 carbon atoms with a linear chain of from 5 to IO 8 carbon atoms and with R^v and/or Ry comprising a side chain i.e. in the 3-oarbon position with respect to the carbonyl carbon atom.

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

Structures in accordance with the invention far the group R11 O R1-^ — CR111 where R is aliphatic include: CH- 0 I 3 · CH3- C~CH2-CK-CH2-C 3,5,5 trimethyl hexsnoylCH.

CH.

CHo(aL·),- ch - c I CH, 12 CH2 ethyl hexanoyl i CH (ch2)3 -eethyl hexanoylCH. ch3 H I C - (CH ) I o II 6-methyl heptanoylCH, 0 I « CH, - (CH,)- - C - C 3 2 5, neodecanoylOf the above the 3,5,5 trimethyl hexanoyl structure is the most preferred for odour and rate of perhydrolysis with the -methyl hexanoyl 6-methylheptanoyl and neodecanoyl structures being lees preferred for odour and the neodecanoyl and 2-ethyl hexanoyl being less preferred for the rate of perhydrolysis.

Structures in accordance with the invention for the group T“ ? c— c— Where R1 incorporates a cyclo aliphatic or aromatic functionality include <αφ3οcyclchexyl butyroyl -pbenyl valeroyl 3-phenyl propionoyl propionoyl structures are the most preferred, having a virtually bland odour and an acceptable rate of perhydrolysis.

The leaving grotp L must be capable of displacement from the bleach precursor as a consequence of the nucleophilic attack cn the bleach precursor ty perfcydroxyl anion generated ty alkaline lydrogen peroxide. This, the perhydrolysis reaction, results in the formation of the percarboxylic acid. Generally, for a grotp to be a suitable leaving grotp it must exert an electron withdrawing effect within the precursor molecule as this facilitates the nucleophilic displacement ty the perhydraxyl anion.

Suitable leaving grope far this purpose have conjugate acid forms, the pKa of which should lie within ths range fron to 13. pKa values above 13 make the electron withdrawal effect so snail as to be ineffective in promoting nucleophilic attack by perhydroxide anion, an exaaple of such a leaving group being - OCH^. ρΚ® values below 6 reflect such a large electron withdrawal effect aa to make the molecule reactive to a wide variety of materials including e.g. water. Certain aliphatic anhydrides fall into this class. Preferred leaving groupe have a pKa in the range from to 11, more preferably from 8 to 10.

However for the purposes of the present invention the leaving group 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 grape such as sulphcnaraide grotps, 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 bs practicable in a laundry detergent liquor.

The leaving grotps L fowd to be useful in compounds of the present invention are those having the formula a) - 0 o II / \\ (CH2)XY b) - N - C - R2 Y I 4 therein is an alky] groip containing from 1 to 4 carbon atoms; x is 0 or an integer from 1 to 4 and Y is selected from: -SQjM - OSOjM - CJOjM - H+dtpjQ - N(S2)2-M> therein M is H, alkali netal. alkaline earth netal, amnoniun or sihetituted ammonium and Q is halide cr methoeulphate.

The preferred leaving group L has the formula a) in which x is 0, and Y is a sulphonate, carboxylate or dimethyl amine oxide radical· The position of the solubilising grop Y on the bensene ring in fornula a) is not critical in that o -, m - and p-positiona provide operable species· Nevertheless polar and steric factors make the o-substituted material most difficult to aynthesise and of least value in that steric hindrance impedes the approach of perhydroxyl ion. In the preferred eabodiment of leaving group 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 fora.

Synthesis of the compounds used in the invention can be illustrated generally ty a sequence of reactions in which a CyC^ acid or acid chloride is formed in which the acyl group has tha required branched structure and the subsequent reaction of this with a conpound of formula a) above «herein the free bond is satisfied by a hydrogen atom.

The C7~£x7 acid or acid chloride starting material, in which , the acyl group has a linear chain of at least 5 carbon atone extending from 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 CKD syntheses can be used in which alpha-olefins are reacted with carbon monoxide and water in the presence of aobalt catalysts to form a mixture of acids of which 60-65% have either 2-methyl or 2-ethyl branching.

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 tesperature and pressure.

The dimerisation of isobutene or the codimerisation of n-butene and isobutene 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-butyraldehyde and thence to 2-ethyl hexanoic acid ty aldol condensation of the aldehyde followed by hydrogenation of the aldol condensation product and final oxidation.

Manufacture of the acid reactant used in the preparation of sodiw 3,5,5-tr imethyl hexanoyl oxybenzene sulphonate, a preferred coapomd in accordance with the invention, involves the condensation of two moles of butene to form di Isobutene followed by aarbonylation to produce the aldehyde and subsequent oxidation to form the isononanoic acid. Thia ie then converted into the acid chloride in known maimer. The acid chloride is refluxed with sodiisn phenol sulphonate in a nitrogen current at 100-150*C for 10-20 hours to form the sodium 3,5,5-trimethyl hexanoyl bsrassne sulphonate.

Alternatively, the isononanoic acid can be traneesterified, refluxing at 160-180’C with sodium phenol sulphonate and acetic anhydride in the presence of a smal l amount of sodium acetate catalyst, thereafter volatilising the by-product acetic acid and precipitating the sulphonate salt product from an organic solvent. A similar reaction procedure starting with n-nonanoic acid is disclosed and claimed in Patent Specification No. ίύοί+ί’ . 'The conpounds themselves axe the subject of the claims of parent Patent Specification No. 5 ΙΟ Similar procedures to the above are also enployed in the synthesis of sodiun 2-ethyl hexanoyl axybenzene sulphonate.

The analogous acyl axybenzene carboxylate salts are also preferred conpounds useful as peroxyacid bleach precursors. Synthesis of these materials is similar to that of the sulphonate salts in that the add chloride is refluxed with p-hydroxybenzoic acid to produce the acyloxybenmoic acid product which can be recovered ty addition of petroleum ether to precipitate the acid.

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

The following two compounds are useful as organic peroxyacid bleach pre20 cursors · 1) Synthesis of sodium 3,5,5-trimethyl hexanoyloxybenzene sulphonate Zsononancyl chloride of purity 95.8% and molecular weight 176.5 (supplied hy Akmo W, Queens Rood Hersham, Surr^, Bigland) and sodium phenol sulphonate of purity £99.5% and PWt 196 (supplied hy BCH Chemicals Ltd, Boole, Dorset, Bigland) were used as the starting materials in the reaction.

CH-CH- — I CH - CH- I «3’ o 19.62 gne of finely powdered, anhydrous sodiua phenol sulphonate (1/lOth mole) and 22.06 gn of Akzo ieononanoyl chloride (weight 1/lOth mole + 25% excess) were weighed into a 500 ml conical fla£k containing 250 mis of chlorobenzene. The flask wee fitted with a magnetic stirrer, a 2-way head carrying a Nj 988 inlet (leading to the base of the flask) and a reflux condenser (+ CaCl^ tube) and wes surrounded by an oil-bath. The flask was heated with stirring to 120*C and with N2 gaa passing through the flask, was maintained at that teaperature overnight (20 hours). The heating wes then turned off and the flask contents allowed to cool to room tenperature. The contents were then washed with 3x1 litre dietfyl ether, filtering between each wash (a Silverscn stirrer waa used for agitation). The resulting white solid was dried in a vacuum oven (no heat) after which the product was ground into a fins powder and dried again in the vacuum oven.

Yield: 27.40 gms (81.5% yield) NMR analysis showed 81.4% required coapowd. 2) Synthesis of aodiimi 2-ethyl hexanoyl oxybenzene eulphonate Anhydrous sodium phenol sulphonate (58.85g; 0.3 mole) was added to a stirred mixture of acetic anhydride (36.75g; 0.36 mole), 2-ethylhexanoic acid (129.8g; 0.9 mole) and sodium acetate (3g). The resultant white suspension was stirred inder 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 up in a distillation mode. The pot tenperature was gradually increased to 260*C during 1.5 hours; the still-head tenperature rose to 131°C. The contents of the reaction pot were then allowed to cool overnight to axfcient tenperature 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 oxybenzene eulphonate was 88.3g, 91.3* of theory.

Purity (ty cat. SO3 determination) » 93.4*.

A second aspect of the invention relates to detergent oppositions incorporating the oonpounds* as defined above, primarily as peroxyacid bleed*! precursors, (the so-called low tenperature bleach actiwtors). Such detergent conpositions oonprise an organic surfactant, a oonpowd as hereinbefore defined and a source of alkaline hydrogen peroxide and are normally particulate in physical farm.

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

Suitable synthetic anionic surfactants are water-soluble salts of alkyl benzene sulphonates, alkyl sulphates, alkyl polyethoxy ether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha-sulpho-carboocylates and their esters, alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkyl phenol polyethoocy ether sulphates, 2-acyloocy alkane-l-sulphonatee, 4q and beta-alkyloxy alkane sulphonates.

A particularly suitable class of anionic surfactants includes water-soluble salts, particularly the alkali metal, anoniin and alkanolaanonium salts of organic sulphuric reaction products having in their molecular structure an 5 alkyl or alkaryl groip containing from 8 to 22, especially from about 10 to about 20 carbon atoms and a sulphonic acid or sulphuric acid ester groip. (Included in the term alkyl is the altyl portion of acyl groipe). Exanples of this group of synthetic detergents *hich form part of the detergent IO ooepositions of the present invention are the sodlun and potassium alkyl sulphates, especially those obtained by sulphating the higher aliphatic alcohols <Όθ_^θ) produced by reducing the glycerides of tallow or coconut oil and sodium and potassium alkyl bensene sulphonates, in which 15 the alkyl group contains from 9 to 15, e^ecially 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 ty alkylation with straight chain 20 «hlnroparaffins (using aluminiisn trichloride catalysis) or straight chain olefins (using hydrogen fluoride catalysis). Especially valuable are linear straight chain alkyl benzene sulphonates in wtiich the average of the alkyl group is 11.8 25 carbon atcBB, abbreviated as θ IAS, and C12-C15 methyl branched alkyl sulphates.

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

Other useful anionic detergent conpounds herein include the water-soluble salts cr esters of alpha-sulphonated fatty acids containing from 6 to 20- carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l-sulphanic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atone in tha alkane moiety; alkyl ether sulphates containing from 10 to 18, especially 12 to 16, carfipn atoms in the alkyl group and from 1 to 12, especially 1 to 6, more e^iecially 1 to 4 moles of ethylene oxide; water-soluble salts of olefin sulphonates containing from 12 to 24, preferably 14 to 16, carbon atoms, especially those aade by reaction with sulphur trioxlde followed by neutralization under conditions such that any sultones present are tydrolysed to the corresponding hydroxy alkane sulphonates; vater-soluble salts of paraffin sulphonates containing from 8 to 24, especially 14 to 18 carbon atoms, and beta-alkylaxy alkane sulphonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety· The alkane chains of the foregoing non-soap anionic surfactants can ba derived from natural sources such as coconut oil or tallow, or can be nude synthetically as for exanple using the Ziegler or Oso processes. Water solubility oan be achieved by using alkali metal, asanoniusn or alkanolanmoniiat cations; sodium is preferred. Suitable fatty acid soaps can be selected from the ordinary alkali metal (sodium, potassium), annonium, and alkyl ol amnnniusi salts of higher fatty acids containing from 8 to 24, preferably from io to 22 and especially from 16 to 22 carbon atoms in tha alkyl chain. Suitable fatty acids can be obtained from natural sources such as, for instance, from soybean oil, castor oil, tallow, whale and fish oils, grease, lard and mixtures thereof . The fatty acids also can bs synthetically prepared (e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process). Resin acids are suitable such as rosin and those resin acids in tall oil. Naphthenic acids are also suitable. Sodium and potassium soaps can be ssde ty direct saponification of the fats and oils or by the neutralization of the free fatty acids uhich are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from 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 5:1 to 1:5, preferably froa 5:1 to 1:2, more preferably from 3:1 to 2:3. Especially preferred ia a ltl 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 sodlua; and either an alkyl sulphate having from 12 to 18, preferably 14 to 16 carbon atoms in the alkyl radical or an alkyl ethoxy sulphate having from 10 to 20, preferably 10 to 16 oarbon atoms in the allyl radical and an average degree of ethaxylation of 1 to 6, having an alkali metal cation, preferably sodium.

The nonionic surfactants useful in tha present invention are condensates of ethylene oxide with a h^rophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HL£) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5. The hydrophobic moiety may be aliphatic cr aromatic in nature and tha length of the polyoxyethylene group which is condensed with any particular hydrophobic group oan be readily adjusted to yield a water-soluble cospound having the desired degree of balance betweeii hydrophilic and hydrophobic Exasples 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 cr branched chain configuration, with ethylene oxide, the eaid ethylene oxide being present in amounts equal to 3 to 30, preferably 5 to 14 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such conpounds may be derived, for exanple, from polymerised prcpylene, di-ieobutylene, octene and nonene. Other exanples include dodecylphenol condensed with 9 moles of ethylene oxide per mole of phenol; dinonylphenol condensed with 11 moles of etlylene oxide per mole of phenol; nonylphenol and di-isooctylphenol oxide. with 13 moles of ethylene 2. The condensation product of primary or secondary aliphatic alcohols having from 8 to 24 carbon atoms, in 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 oosprises between 9 and 18 carbon atoms and is ethoxylated with between 2 and 9, desirably between 3 and 8 moles of ethylene oxide per mole of aliphatic alcohol. The preferred surfactants are prepared from primary alcohols which are either linear (such as those derived from natural fats or, prepared ty the Ziegler process from ethylene, e.g. myristyl, oetyl, stearyl alcohols), or partly branched such ae the Lutensols, Dobanols and Neodola which have about 25% 2-methyl branching (Lutensol being a Trade Name of BASF, Dobanol and Neodol being Trade Names of Shell), or Syzperonics, which are understood to have about 50% 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 Liquichimica. Specific exaaplee of nonionic surfactants useful for the purposes of the invention include Dobanol 45-4, Dobanol 45-7, Dobanol 45-9, Dobanol 91-2.5, Dobanol 91-3, Dobanol 91-4, Dobanol 91-6, Dobanol 91-8, Dobanol 23-6.5, Synperonic 6, Synperonic 14, the condensation products of coconut alcohol with an average of between 5 and 12 moles of ethylene oxide per mole of alcohol, the 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 linear alkyl ethoxylates are also suitable in the present oonpositions, especially those ethoxylates 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.

Useful nonionic surfactants also include those in which ethylene oxide la condensed with a lydrophobic base formed by the condensation of propylene oxide with propylene glycol wherein the molecular weight of the hydrophobic portion generally falls in the range of 1500 to 1800. such synthetic nonionic detergents are available on the market under the Trade Name of Plutonic sqpplied ty Wyandotte Chemicals Corporation.

Especially preferred nonionic surfactants for use herein are the C^-C^ primary alcohol ethoxylates containing 3-8 moles of ethylene oxide per mole of alcohol, particularly the C12^15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol.

Cationic surfactants suitable for use herein include quaternary amnonlum surfactants and surfactants of a semi-polar nature, for exaaple amine oxides. Suitable quaternary anmoniim surfactants are selected from mono Cg-C^g, preferably M-alkyl or alkenyl ammoniimi surfactants wherein remaining N positions are substituted fay methyl, hydroxyethyl or hydroxypropylgroups. Suitable amine oxides are selected from mono preferably C^g-C^ N-alkyl or alkenyl amine oxides and prcpylene-1,3-diamina dioxides wherein the remaining N positions are again substituted hy methyl, hydroxyethyl or hydroxypropyl groups.

The detergent coepositians oan comprise from l%-70% by weight of surfactant, but usually the surfactant ia present in an amount of from 1% to 20%, more preferably from 5-15% by weight. Mixtures of surfactant tapes are preferred, particularly anionic-cationic mixtures. Particularly preferred mixtures are described in British Patent No. 2040987 and EP-A-O 087 914.

A source of hydrogen peroxide can be provided ty any of the caunercially available inorganic peroxygen bleaches and also by certain hydrogen peroxide adducts.

Suitable inorganic peroxygen bleaches include sodium perborate mono and tetra hydrate, sodiiaa percarbonate, sodium persillcate and the clathrate ^Na^SO^ s : iNaCl. A separate source of alkalinity ia required for clathrate materials and for stability reasons this should preferably be kqpt physically separated from the hydrogen peroxide source by e.g. enrobing or encapsulating the latter. The hydrogen peroxide source will normally be present in an amount of from 1* to 40*, more preferably fron 5* to 35* ty weight of the conposition and will most frequently be present in an amount of from 10* to 30* fay weight.

In preferred embodiments of this aspect of the invention the levels of hydrogen peroxide source and precursor conpound are arranged so that the molar ratio of hydrogen peroxide yielded fay the source to precursor Preferred detergent conpositions, in accordance with the invention, will include those components commonly included in heavy duty laundry detergents such as suds sippreesing agents, detergent builders, chelating agents, sail suspending and anti redspoeition agents, optical brightening agents, enzymes, colours and perfumes.

Suds suppressors useful in the detergent conposition aspect cf the invention, particularly conpositions used in laundering fabrics, are represented by materials of the silicone, wax, vegetable and hydrocarbon oil and phosphate ester varieties. Suitable silicone ends controlling agents include polydimethylsiloxanes having a molecular weight in the range from 200 to 200,000 and a kinematic viscosity in the range from 20 to 2,000,000 nm2/s (cSt), preferably from 3000 to 30,000 un2/s (cSt), and mixtures of siloxanes and hydrophobic silanated (preferably trimethylsilanated) silica having a particle size in the range from 10 raillimicxaneters to 2 millimicraneters 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 from 4,000-10,000, and a penetration value of at least 6, measured at 77C by ASTM-D1321, and also paraffin waxes, synthetic waxes and natural waxes, suitable phosphate esters include mono- and/or di-C^g-C^ alkenyl phosphate esters, and the corresponding mono- and/or di alkyl or alkenyl ether phosphates containing ip to 6 ethoxy groups per molecule.

Suds suppressors axe normally included at levels of from 0.01% to 5% by weight of the coaposition, dependent on the type of suds suppressor used, more acmmonly 0.1% to 2% by weight.

A highly preferred coaponent of detergent conpoeitians in accordance with the invention is one or more detergent builder salts which nay comprise up to 90% of the conpositicn, more typically from 10% to 70% by weight thereof. Suitable detergent builder salts useful herein can be of the polyvalent inorganic and polywlent organic types, or mixtures thereof. Non-limiting examples of suitable water-soluble, inorganic alkaline detergent builder salts include the alkali metal carbonates, borates, phosphates, pyrophosphates, tripolyphosphates and bioarbanates.

Exaiples of suitable organic alkaline detergency builder salts are water-soluble polycarboaylates such as the salts of nitrilotriacetic acid, lactic acid, glyoollic acid and ether derivatives thereof as disclosed in BE -A- 821,368, 821,369 and 821,370; succinic acid, malonic acid, (ethylenedioxyjdiacetic acid, maleic acid, diglyoollic acid, tartaric acid, tartraiic acid and fumaric acid; citric acid, aconitic acid, dtraoonic acid, carboocymethyloxysuccinic acid, lactaxysuccinic acid, and 2-oxy-l, 1,3-propane tricarboxylic acid; oxydisuccinic acid, 1,1,2,2-ethane tetracarboxylic acid, 1,1^ 3,3-propane tetracarbaxylic acid and 1,1,2,3-propane tetracarboxylic acid; cyclopentane cis, cis,cia-tetraoarboxylic acid, cyclopentadiene pentaoarboxylic acid, 2,3,4,5-tetrahydrofuran-cis, ds, cis-tetracarboxylic acid, 2,5-tetratydrofuran-cis-dicarboxylic acid, 1,2,3,4,5,6-hexane-hexacarbaxylic acid, mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB -A- 1,425,343.

Mixtures of organic and/or inorganic builders can be used herein. One such mixture of builders is disclosed in GA-A-75&.038,' e.g. a ternary mixture of sodium tripolyphoephate, trisodiue nitrilotriacetate, and triscdium ethane-l-hydroxy-1,1-diphoqphonate.

A further class of builder salts is the insoluble alumino silicate type which functions by cation exchange to remove polyvalent mineral hardness and heavy metal lens from solution. A preferred builder of this type has the IO formulation Na^AlOjJ^SiO^y.xf^O wherein 2 and y are integers of at least 6, the molar ratio of z to y is in the range frcm 1.0 to 0.5 and x Is an integer from 15 to 264. CGspositions incorporating builder salts of this type form the subject of Fautent* AJo. -* EE-A-2,433,485 published February 6, 1975 and EE-A-2,525,778 published January 2, 1976.

An alkali metal, cr alkaline earth metal, silicate oan also be pronent, prefexsibly in an amount of from 3% to 15%. Suitable silicate solids have a molar ratio of SiO^alkali metal^O in the range fron 1.0 to 3.3, more preferably frcm 1.5 to 2.0.

Chelating agents that con be incorporated include citric acid, nitrilotriacetic and ethylene diamine tetra acetic acids and their salts, organic phosphonate deriwtives such as those disclosed in Diehl US Patent NO. 3,213,030 issued 19 October, 1965; Roy US Patent Nd. 3,433,021 issued 14 January, 1968; Gedge US Patent No. 3,292,121 issued 9 January, 1968; and Bersworth US Extent Nd. 2,599,807 issued 10 Jbne, 1952, and carboxylic acid builder salts such as those disclosed in Diehl US Patent Nd. 3,300,067 issued 7 March, 1967.

Preferred chelating agents include nitrilotriacetic acid (N1A), nitrilotrimethylene phosphonic acid (N3MP), ethylene diamine tetra methylene phosphonic acid (HUM*) and diethylene triamine penta methylene phosphonic acid (DETPMP), and these are incorporated in amounts of frcm 0.1% to 3%, more preferably 0.2% to 2% ty weight of the coepoeition.

Antiredeposition end soil suspension agents suitable herein include cellulose derivatives such as msttylcellulose, carboxymethylcellulose and hydrcocyethyloellulose, and homoor co-polymeric poiyoarboxylic acide or their salts in which the poiyoarboxylic add oonprisss at leaet two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are disclosed in GB-A-1,596,756. Preferred polymers include copolymers or salts thereof of maleic anhydride with ethylene, methylvinyl ether, acrylic acid or methacrylic acid, the maleic aritydride constituting at leaet 20 sole percent of the copolymer.

These polymers are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidisable soils In the presence of transition metal ispuritiee.

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 McCarty et al issued July 7, 1970 and January 5, 1971, respectively. Ehotoactivators are discussed in BPnA-57088, highly preferred materials being zinc phthalocyanine tri- and tetrar-aulphonatas.

Anionic or nonionic optical brighteners are also preferred ingredients of detergent oonpoeitions in accordance with the invention, being normally present at levels af from 0.01* to 1* by weight, more preferably at levels of from 0.02* to 0.5* by wei£tt.

Anionic fluorescent brightening agents are well-known materials, exanples of which are disodiun 4,41 -bis-( 2-diethanolamino4-anilino-s-tr iazin-6-ylaaino) stilbene-2:2'disulphcnate, disodiw 4,4'-bie-(2-«orpholino-4anilino-s-tr iazin-6-ylamino) stilbene-2:2' -disulphcnate, dieodium 4,4'-bie-(2,4-dianilino-e-triazin-6-ylawino) stilbene-2:2'-di-sulphanate, disodiun 4,4'-bis-(2anilino-4-(N-methyl-lf-2-hydraxyethylamino)-s-triazin-6-ylamino) stilbene-2,2'-di-sulphonate, disodiun 4,4'-bis-(4-phenyl -2,1,3-triazol-2-yl)-stilbene-2,2 '-disulphcnate, disodiun 4,4' -bis(2 '-anilino-4-( l-metlyl-2-lydroxyethylamino)-s-triazin6-ylamino)stilbene-2,2adisulphonate, sodiua 2(stilbyl-4(naptho-V,2':4,5)-1,2,3-triazole-2 -sulphonate and di-sodiua 4,4 * -bie( 2-sulphonato etyryl)biphenyl.

Other fluorescers to which the invention oan be applied include the 1,3-diaryl pyrazolines and 7-alkylaminocouurins.

A preferred fluorescer is the anionic material available from Ciba Geigy S.A. under the trade name Tinopal CBS and mixtures thereof with materials available under the trade names Tinopal EMS and Blankaphor Ffi&f, the latter being sold ty Parbenfabriken Bayer AG.

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

Thus the precursor may bs formed into particulates by spray cooling, prilling, marumerising, agglomeration or granulation, either alone or together with a carrier material which ray be organic cr inorganic in type. Suitable inorganic materials include clays and other natural and synthetic aluminosilicates, aa well as hydratable salts such as phoephates, carbonates and sulphates. Suitable organic materials include ethoxylated alc£*h°l8 31x1 ^cyl phenols, polyethylene glycols of MWT 4,000-10,000, C12^1S fatty acids and esters thereof with monohydric and polytydric alcohols. In one preferred method of manufacturing the precursor, disclosed in Patent Specification No. r 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 then the carrier is a waxy organic solid such as an ethoxylated alcohol or ester and a highly preferred example, eaploying a glyceryl mono fatty acid ester carrier is disclosed in £P-A-O 123 423.

In another method of manufacturing the preferred alkali metal C?-C^ branched chain acyl oxybenzene sulphonate phenol sulphonate precursors, one of the reaction components e.g. alkali metal phenol sulphonate or fatty acid Is employed in a greater excess than is necessary to achieve the desired completeness of reaction. The excess reactant is used as a binder naterial for the reaction product which is taken from the reactor and, without saturate crystallisation or solvent extraction steps, is oompacted to form particulates which can be added directly to the detergent conposition.

Preferred methods of making a particulate from a mixture of precursor and an organic carrier or builder are disclosed in the Applicants' EP-A-O 106 624 and Patent Specification No.

Particulates incorporating the precursors useful in 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 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.

A further aspect of the invention relates to detergent additive products incorporating aliphatic peroxy acid precursors whose carboxylic acid analogues have a logger of from 1.9 to 4.1. Such additive products are intended to supplement or boost the performance of conventional detergent conpoeitions and may contain any of the components of such compositions, although they will not comprise all of the components present in a fully formulated detergent composition. 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 peroxide may be included in the product.

Additive products in accordance with this aspect of the present invention may conprise the conpound alone in combination with a carrier such as a compatible particulate substrate, a flexible non particulate substrate or a container. Exanples of oonpatible particulate substrates include inert materials such as clays and other aluminosilicates including zeolites both natural and synthetic in origin. Other cospatible particulate carrier materials include hydratable inorganic salts such as phosphates, carbonates and sulphates.

Additive products enclosed in bogs or containers are manufactured such that the containers prevent egress of their contents when dry but are adapted to release their contents cn immersion in an aqueous solution.

A convenient execution of this form of the additive product comprises a particulate solid conpound as hereinbefore defined enclosed in a container. Usually the container will be flexible, such as a bag or pouch. The bag may be of fibrous construction coated with a water iapermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678. Alternatively it may 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 European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure comprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water inpermeable polymeric film such as polyethylene or polypropylene· An alternative form of the additive product oosprises a oospound as hereinbefore defined in water releasable conbination with a non particulate flexible substrate in a weight ratio of 1:10 to 30zl.

Additive products of this Specification No . If· 5 ?! also in the previously mentioned GB-A-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 under the conditions of the wash to te recovered from the machine at the end of the laundry cycle. Structures which are water disintegratable, i.e. that break down in aqueous media to insoluble individual fibres or particles, are considered lees satisfactory for the purposes of the present invention.

Hbter soluble materials include certain cellulose ethers, alginates, polyvinyl alcohol and water soluble polyvinyl pyrrolidone polymers, which can be formed into non-woven and woven fibrous structures. Suitable water insoluble materials include, but are not IO restricted to, natural and synthetic fibres, foams, sponges and films.

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

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

A highly preferred execution of this type of additive product utilises a flexible sheet so as to make it compatible with the movement of the fabrics in the washing machine and to facilitate its handling during manufacture of the product. Preferably the sheet is water pervious,i.e. water can pass from 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 weave natural or synthetic fibre of low fibre cowt/unit length, euch as is used for surgical dressings, or of the type known as cheese cloth. Loading limitations on sheet type substrates limit the amount of precursor oospound that can be applied to the sheet and, in practice, the weight ratio of precursor compound:sheet substrate normally lies within the range from 1:2 to 10:1.

Variations on the above sheet substrate product forms are also oontemplated for the purposes of the present invention. For exanple, laminated sheet products can be employed in which a central layer is inpregnated and/or coated with a oonpoaition incorporating the bleach precursor and then one or more outer layers are applied to produce a fabric-like aesthetic effect. The layers may be sealed together as as to remain attached during use or may separate cn contact with water to facilitate the release of the coated or inpregnated material.

An alternative laminate form oonpriaes one layer embossed or deformed to provide a series of pouch-like containers into each of which the bleach precursor and optionally other detergent cosponenta are deposited in measured amounts, with a second layer overlying the first layer and sealed thereto in those areas between the pouch-like containers there the two layers are in contact. The bleach precursor and any accanpanying oonponents may be deposited in particulate, paste or molten form and the laminate layers should prevent egress of the contents of the pouch-like containers prior to their addition to water. Tbe layers may separate or may remain attached together on contact with water, the only requirement being that ths structure should permit rapid release of the contents of the pouch-like containers into solution. Tbe number 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.

As stated above, suitable materials 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 present invention emprises an absorbent foam like aaterial in the form of a sheet. The term 'absorbent foam-like aaterial' ie intended to enooepass three dimensional absorptive materials such as 'gas blown foams', natural sponges and composite fibrous based structures such as are disclosed in US Patent Noe. 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 ly reticulation· Fbeums of this type are deecribed in detail in Dulle US Patent No. 3794029. A preferred exaaple of this foam type cosprises a hydrophilic polyurethane foam of density 0.036 y/αη3 with a cell count of between 8 and 40 cells per cm, preferably fran 24 to 32 per cm available from the Scott Paper Ooepazy, Eddystone, Pennsylvania USA., inder the Registered Trade Mark Hydrofoam. Preferred sheets of this type of material have thicknesses in the range from 3 to 5 nm.

Preferred sheet substrates for use in this type of additive product are apertured and non apertured non woven fabrics which oan generally be defined as adhesively bonded fibrous or filamentous products, having a web or carded fibre structure (where the fibre strength is suitable to allow carding) or comprising fibrous mats, in which the fibres or filaments are distributed haphazardly or in random array (i.e. an array of fibres in a carded web Wherein partial orientation of the fibres is frequently present as well as a completely haphazard distributional orientation) or substantially aligned. The fibres or filaments oan be 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 clothe oan provide substrates possessing a variety Of desirable traits. For exanple, the absorbent capacity of the cloth can be increased, decreased, or regulated by respectively using a hydrophilic binder-resin, a hydrophobic binder-resin or a mixture thereof in the fibre bonding step. Moreover, the hydrophobic binder-resin, tfen used singly cr as the predominant conpound of a hydrcphcbic-hydrophilic mixture, provides non-woven cloths tAich are especially useful as substrates when the pracursar^stibstrate confeinaticns disclosed herein are used in an automatic washer.

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

Preferably, the non-woven cloth is water-laid or air-laid and is xade from cellulosic fibres, particularly from regenerated cellulose or rayon, which are lubricated with standard textile lubricant. Preferably the fibres are from 4 to 50 na in length and are from 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 bonded together with hydrophobic or substantially hydrophobic binder-reein, particularly with a nonionic eelf-crosslinking acrylic polymer or polymers. Conveniently, the cloth conpriees 70% fibre and 30% binder-resin polymer by weight and has a basis weight of from 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 normally in a pattern and are formed during lay-down of the fibres to produce the substrate. Exesplary apertured non-woven subetrates are disclosed in US Patent Noe. 3,741,724, 3,930,086 and 3,750,237.

A suitable diamond patterned apertured substrate is obtainable from Chicopee Manufacturing Co., Milltown, New Jersey, USA under the Code No. 9C 650 WFX 577 and cosprising a polyester-wood pulp mixture having a basis weight of 50 g/m and approximately 13 apertures per square cn· Another preferred exasple of an apertured non-woven substrate, also arellable from Chicopee Manufacturing Co., under the Code No. AK 30 M, 1379 oonprises a regenerated oelluloee sheet of 0.33 Teac fibres banded with Ehoplex BA 8 binder (fibrexbindsr ratio 70x30) having a basis weight of 40 g/m and 17 apertures/αη . A highly preferred square patterned apertured substrate of similar conpositicn but fibrexbinder ratio of 80x20 and basis weight 35 g/m2 is also available from Chicopee BV Holland.

In general, apertured fabrics for the purposes of the 2 invention have from 10 to 20 apertures/αη , preferably 12-18 2 aperturee/cm · The sixe and shape of the substrate Sheet ie a natter of choice and is determined principally fcy factors associated with the convenience of its use. Thue the sheet should not be ao small as to become trapped in the crevioee of the machine or the clothes being washed or ao large as to be awkward to package and dispense from the container in which it is sold. For the purposes of the present invention sheets 2 2 ranging in plan area from 130 cm to 1300 cm are acceptable, the preferred area lying in the range of from 520 on2 to 790 ce2.

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

More usually, additive products in accordance with the invention oontain other detergent ingredients in addition to the hereinbefore defined ocmpounds.

The type and level of such optional materials is constrained only by the requirements of unreactivity towards the precursor, and, where a substrate is utilised as the, cr a carrier, by the loading limitations of the substrate. This inposes a maximal weight ratio of optional ingredients to substrate of about 10:1, and in the case of coated sheet substrates of about 8:1. As described in more 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 qaatially separate therefrom, i.e. is disposed at a substrate location that is free or substantially free of the other reactant materials.

One factor determining the acceptable level of 15 incorporation of an optional ingredient is its physical characteristics i.e. whether it is liquid or solid and if solid whether it is crystalline cr waxy and of high cr low melting cr softening point.

Highly desirable optional components are solid, water soluble or water dispersible organic processing aids of a waxy nature having a ifct in the range 30-80’C. The 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-hygrosocpic solids that are mixed with the precursors and melted to provide mixtures having a viscosity of ip to 30,000 centipoises at 30 50 *C.

Typical solids are c^4-c^q primary and secondary alcx*ol8 and fatty acids and ethoxylates thereof containing from 15 to 80 ethylene oxide groups per mole of alcohol, sorbitan esters of cjj“^20 acids and polyethylene glycols of Hfot 4,000-10,000. As stated hereinbefore, preferred materials are those of low hygroscopicity particularly the saturated fatty acids.

The fatty acids and polyethylene glycols of MWt 4,000-8,000, are particularly effective when used in amounts such that the weight ratio of compounds spcocessing aid lies in the range 20:1 to 1:2 particularly 4:1 to 1:1.

In addition to the foregoing optional conponents that are of primary value in incorporating the precursor onto, euid rele&ping it from, the substrate, conventional detergent ingredients can be incorporated into the composition provided that they are not reactive towards oospounds as hereinbefore defined. Thus, surfactants, suds modifiers, ctelating agents, anti-redepoeition and soil suspending agents, optical brighteners, bactericides, anti-tarnish agents, enzymatic materials, fabric softeners, antistatic agents, perfumes and bleach catalysts can all be introduced into a wash liquor by means 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 which the cospoeitions conprise a peroxy bleach precursor compound as hereinbefore defined disposed cn a substrate of either particulate or non particulate form, the substrate is preferably absorbent and the composition is impregnated therein.

Application of the precursor can be carried out in any convenient manner, and many methods are known in the art. As the preferred acyloxybenzene sulphonate or carboxylate precursors are solid at temperatures in excess of 15O*C, one fora of application is by solution in organic solvents which are volatilised after application, whilst another employs a slurry or suspension of the finely divided solid in water or other liquid madia.

Preferred compositions in accordance with the invention are substantially anhydrous and thus incorporation on the substrate is best aooosplished by utilisation of a non aqueous liquid mediums.

A highly preferred embodiment of the invention utilises a processing aid and/or other optional ingredients in molten fora as the liquid medium in which the finely divided precursor is dispersed.

Where the substrate conprises a non-sheet like reticulated foam article, direct impregnation of the article by a liquid medium incorporating the dispersed precursor, either alone or with other caaponents of the foraulation can 3H be used, employing methods known in the art and described in more detail hereinafter. Where the substrate comprises a non-woven material cr a foam article of sheet-like form, it is preferred to mix the bleach precursor with a compatible mn-hygrosoopic material of melting point <60*C, euch as the processing aids hereinbefore described to provide a waxy solid in which the bleach precursor is present in the form of a solid solution and/or as a dispersed phase. The melting point range and waxy nature of polyethylene glycols of IO molecular weight >4000 make them useful for this purpose.

Where nonionic surfactants fen oonponents of the oonposition, their physical properties may permit their use as, or as part of, a liquid medium in thich the precursor aid other solid oonponents are incorporated.

As previously indicated, materials reactive towards the peroxy bleach precursor oonpounds cf 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 bleaches which either contain water or hydrogen peroxide in hydrogen bonded form, such as sodium perborate monohydrate and tetrahydrate, sodiua peroarbonate, eodiun persilicate or eodium perpynphoqhate, and also urea-hydrogen peroxide addition products, are materials which are sufficiently reactive to require this spatial separation.

Where the precursor and the inorganic peroxygen bleach are incorporated in physically separate locations on the same non particulate sheet substrate, a convenient method of application is the deposition of the respective melts, suspensions or solutions as discrete bands of material on the substrate. This can be achieved using a divided extrusion head or by applying the malt or suspension to separate webs of substrate which axe subsequently joined longitudinally. Preferably the bleach is applied as a dispersion of solid particles in a molten processing aid (as hereinbefore described) at a tenperature in the range 40* to 60’C. Using this technique, bleach:substrate weight ratios of up to 15:1 can be obtained. This level of loading is attainable with cellular substrates but substrates of fibrous character tend to be limited in practice to bleachxsubstrate weight ratios of no nore than 8x1. Furthermore, loading limitations imposed by the substrate surface area required for the incorporation of the precursor may limit the amount of bleach to lees than than this and bleachxsubstrate weight ratios in the range 5x1 to 1x2 are normally enplayed. Provision must also be made far the separation of the bends or areas of bleach and the corresponding bands or areas of precursor during transport and/or storage· This is achieved hy interposing layers of material between the layers of substrate or by producing patterns of deposited material that are not coincident on stacking of the substrate.

A preferred method of making the particulate substrate fonts of detergent additive product is ly applying a quay of the composition as a solution, dispersion, or molten suspension, cn 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 method 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 ty the nip of two horizontal rolls arranged side by side and rotating in opposite directions such that the nip is formed ty surfaces having approximately the same velocity in a downward direction. Molten material is qiread on one of the rolls and transferred to a continuous web of substrate whose speed is the same as that of the roll and which contacts the roll over a limited length of its periphery· The impregnated substrate is then contacted by a smoothing and qxreading roll having a direction of rotation such that its contact surface is moving in the opposite direction to that of the substrate. The rolls enplayed in this technique are fabricated in metal and are heated to maintain the impregnating mixture in the liquid phase.

A further aspect of the present invention oanprises a bleaching conposition conposed of a precursor conpound as hereinbefore defined in conhination with a source of hydrogen peroxide in the form of an alkali metal inorganic peroxy salt or a hydrogen peroxide clathrate or conposed of the peroxy acid derived from the precursor cospound in combination with a stabilising agent.

In tiie embodiment oosprising a mixture of the precursor and a source of alkaline hydrogen peroxide it is very desirable that the two components be isolated from each other in order that a reaction does not occur prior to use.

Althou^i a reaction can be prevented ty making an anhydrous mixture of the two components, the maintenance of such a mixture in the anhydrous state is very difficult under normal storage conditions. A preferable technique is to separate the conponents physically, ty coating one or both with inert materials that dissolve or disperse in aqueous media, ty incorporating each in separate or Gospartmsntal packaging, or by fixing each aonponent to separate locations on a non particulate substrate. Each of these separation techniques is well known in the art and does not form part of the present invention.

Bleaching oonpoeitions of this type contain from 30% to 95% by weight of the hydrogen peroxide source and 70% to 5% kyweight of the precursor canpound as hereinbefore defined; more generally from 50% to 90% of hydrogen peroxide source and from 50% to 10% of precursor cospound, moot preferably from 75% to 90% of hydrogen peroxide source and from 25% to 10% of precursor canpound.

Where the peroxy acid derived frcm the precursor erspnund is enployed in the bleaching composition, it can be used in conjunction with a stabilising agent such as quinoline, quinaldic acid, picollnic acid or dipicolinic acid or a derivative thereof, preferably together with a polyphosphate' salt. Stabilising agents of this type are disclosed in Sprout USP 2,838,459, Sennewald et al USP 3,442,937, and Cam USP 3,192,255. A preferred system enploys a mixture of β-hydroxy quinoline and an acid pyrophosphate salt in a ratio of from 1:1 to 5:1. The stabilising agents are incorporated at a level of from 0.005% to 1.0% by weight of the conpoeition.

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

The present invention alao embraces the formation of aqueous bleaching liquors ty means of the reaction of a source of alkaline hydrogen peroxide with additive products containing precursors of an aliphatic peroxy acid whose carboxylic acid analogue has a log p^^. of fran 1.9 to 4.1 particularly with the C6^16 branched alkyl groqo-eontaining precursor compounds specifically deecribed above, or by neans of the addition of the above-described detergent or bleaching conpositions to an aqueous medium. Aqueoue bleaching liquors in accordance with this aspect of the invention develop low intensity or bland odours which are ooopatible with, and/or are capable of being masked by, the perfuse oonpoeitions conventionally used in detergent products. Aqueous bleaching liquors containing the most highly preferred compounds in accordance with the invention are virtually odourless whereas the analogous linear alkyl chain materials have a pmgent odour which is aesthetically undesirable.

In addition to the non lir**—y precursor —of the present invention, products and oonpoeitions made in 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-C^Q acyi oxybenzene sulphonate or carboxylate with peracetic acid precursors are preferred, exasples of such peracetic add precursors including tetra acetyl ethylene diamine, tetra acetyl methylene diamine, tetra acetyl glyoouril, sodium p-acetoxybenzene sulphonate, penta acetyl glucose and octa acetyl lactose. However, the invention alao contemplates blends of branched Cg-C10 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 acyl oxybenzene sulphonate precursors with other peroxyacid precursors it has been found that the Cq-^q acyl oxybenzene sulphonate should preferably be present in an amount to provide a level of at least 2 ppm and preferably at least 5 ppm available oxygen in the wash liquor, in order that the benefit of the peroxy acid can be realised. Generally the weight ratio of the Cg*Cj£ acyl oxybenzene sulphonate precursor to the other peroxy acid (e.g. peracetic acid) precursor should be euch as to provide a Cg-C^o aliphatic peroxy acidsperacetic 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 washing conditions, blends in which the acyl oxybenzene sulphonate delivers from 5 to 15 ppm available oaygen in the wash liquor are preferred.

Tbe level of usage of the precursor will naturally be dependent on a number of factors e.g. the size of the fabric load in the machine, the level of bleaching performance desired, the amount of perhydroxyl ion in the wash solution, the bleaching efficacy of the organic peroxy species derived from ths 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 from 50 ppm to 350 ppm by weight for heavy duty laundry purposes. However, when using organic peroxy bleaches a level of available oxygen provided ty the organic peroxy oospound may lie in the range from 1 ppm to 50 ppm, levels of from 1.5 ppm to 16 ppm being epprcpriate under conventional US washing conditions while levels of from 20 ppa to 50 ppm are more ccsmonly 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 enployed For a machine 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.

Cj2 LAS Sodiin linear C]^ alkyl benzene sulphonate C13 LAS Sodium linear Cjj alkyl benzene sulphonate ASC TAS C14/15 AS c12/l4 AS TAEn c14imab c14 Tfnns 15 Cx^lMkB A 45E7 A 23 B6.5 Soap PBS TAED PAG AOBS ISONOBS ISONOBA SiOBS Silicate Sulphate OTP Zeolite A 40 Diaodiun salt of ec -sulphonated stearic acid Sodiin tallow alcohol sulphate Sodium Cx4-Cj5 alkyl sulphate Sodium Cx2~Cl4 alkyl sulphate Tallow alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol C^4 alkyl trimethyl annonium bronide C£4 alkyl triraethyl ammonium methyl sulphate Οχ2 alkyl trimethyl ammonium bromide A C14-15 pr inaxy alcohol condensed with 7 moles of ethylene oxide.

A Cx2-Ci3 primary alcohol condensed with 6.5 moles of ethylene azide.

Sodium salt of 80/20 mixture of tallow and coconut fatty acids.

Polyethylene glycol (Wt normally follows) Tetraacetyl ethylene diamine Penta acetyl glucose Sodium ρ-acetoxy benzene sulphonate Sodium 3,5,5 trimethyl hexanoyl oxybenzene sulphonate Sodium 3,5,5 triraethyl hexanoyl oxybenzoic acid Sodium 2-ethyl hexanoyl oxybenzene sulphonate Sodiua silicate having an SiO2:N*2O ratio of 1.6 Anhydrous sodium sulphate Sodium tripolyphosphate Sodium aluminosilicate of foraula H&12 (ALQ2 «SiO2 ) 12271^20.

Carbonate Anhydrous sodium carbonate CMC Sodivn carboxymathyl cellulose Silicone Goapoundx 85% polydimethyl siloxane 15% silica Silicone Prill 5 MA/AA WBft Conprising 0.14 parts by weight of an 85:15 by weight mixture of silanated silica and silicone, granulated with 1.3 parts of sodiua tripolyphosphate, and 0.56 parts of tallow alcohol condensed with 80 molar proportions of ethylene oxide Copolymer of 1:4 maleic/acrylic acid, average molecular weicfeit about 80,000.

Ifaleic antydride/vinyl methyl ether copolymer, believed to have an average molecular weight of 240,000. This material was prehydrolyeed with NaCH before addition.

Perborate Sodium perborate tetrahydrate of nominal formula NaBO2.3K2O.H2Q2 Perborate monohydrate Anhydrous sodium perborate bleach of eapirical formula N4B02-H292 Enzyme : Mixed proteolytic and and amylolytic enzyme sold by Novo Industrie AS.

EOTA Sodium ethylene diamine tetra acetate ΝΈΑ Sodium nitrilotriaoetate· Bricpxtener 1 Disodium 4,4*-bie(2-morpholino-4anilino-s-triazin-6-ylanino) stilbene-2z2 '-diaulphonate.

Bri^itener 2 Diaodium 4,4a-bis(2-sulphonato styryl)biphenyl DETPMP Diethylene triamine pentaf methylene phosphonie acid), marketed by Monsanto under the Trade name Dequest 2060 EOTMP H2O2 Clathrate Mixed Suds Suppressor Ethylenediamine tetra (methylene phoephonic acid), marketed by Monsanto, under the Trade name Dequeet 2041 A clathrate of 4^38¾ s 2H2Q2 2 IMaCl % paraffin wax ipt 5ifc, 17% hydrophobic silica, 58% paraffin oil.

EXMT£ 1 Preparation of sodium 3,5,5 trimethyl hexanoyl oocyfaenzene sulphonate 100 gms of dehydrated sodiun phenol sulphonate and 117 gms (30% molar excess) of ieononanoyl chloride* (ex Akzo BV, Hrt 176.5) were weighed into a 2 litre conical flask. The 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 mis chlorobenzene were added and the resulting suspension was stirred. 5 gms of tetrabutylammonium bromide (supplied by Aldrich Chemical Go. Inc., Milwaukee, Wisconsin 53233, USA) were added as catalyst and the resulting suspension was stirred and heated to 120*C with nitrogen passing throu^i the flask. Heating was continued with nitrogen passing, for 19.5 hours.

The reaction mixture was then cooled to room temperature, poured into 3 litres of diethyl ether and well washed using a Silversan stirrer. The solid material was filtered off by Buchner filtration and the resulting solid was washed with 2x2 litres of ether, filtering off after each wash. The resulting solid was dried over in a vacuum desiccator, was powdered in a coffee grinder and re-dried in a varan desiccator over PnO^· The yield was 140 gms and NMR analysis showed the solid to comprise 92% sodium 3,5,5 trimethyl hexanoyl oxybenzene sulphonate and 8% sodium phenol sulphonate.

«This is the ocmmcn term used in the trade to describe 3,5,5trimethyl hexanoyl chloride.

EXAMPLE 2 Preparation of sodium 3,5,5 trimethyl hexanoyl oxybenzoic acid The same apparatus was used as in Exanple 1. 74.5 g of p-hydroxybenzoic acid was mixed with lOOg of 3,5,5-tr imethyl hexanoyl chloride (5% molar excess) and 3.7 g of tetrabutyl ammonium bromide catalyst. The mixture waa stirred and heated to 100*0 in a current of nitrogen for 2 hours. The resultant white, porous, solid mass wes cooled, broken ip under petroleum ether (tp 40-60*0, filtered, washed and dried. The product, 126 g (84%) was found ty NMR analysis to be 95% 3,5,5-trimethyl hexanoyl axybenzoic acid and 5% p-hydraxy benzoic acid.

EXftMRUSS 3-8 Detergent compositions incorporating a coepound in accordance with Example 1 have the following percentage formulations: 3 4 5 6 7 8 Cu IAS - 6.0 4.7 - - 6.0c13 “S 4.0 - - 9.0 8.0 -C14/15 8.0 6.0 7.0 3.0 - 6.0 A45E7 - 2.0 2.1 2.5 - 2.0 c14ttm 2.0 2.0 2.1 - 1.5 2.0 ΊΜΑΒ - - - 1.5 - - SIP 24.0 24.0 18.0 32.0 24.0 12.0 i«/AA 1.5 1.7 - - 1.5 3.0 MUSA - - 1.0 0.5 0.5 - Silicate 10.0 5.0 7.5 5.0 7.5 5.0 Carbonate 5.0 10.0 5.0 - 2.5 10.0 HUMP 0.25 0.3 0.1 0.1 0.1 0.2 Perborate 18.0 21.0 24.0 24.0 18.0 21.0 Peroxy acid precursor 3.0 3.0 5.0 3.0 3.0 8.5 Silicone Prill 3.0 4.0 4.0 2.5 2.0 4.0 Brightener 1 0.25 0.25 0.20 0.25 0.25 0.20 Enzyme 0.4 0.3 0.4 0.25 0.30 0.30 Sulphate 9.0 5.0 12.0 6.4 15.35 15.0 Moisture + Misc. --To 100— Typically a spray dried base powder is made containing the anionic and cationic surfactants, STP, inorganic salts, brightener, copolymer and EBCMP and then the remaining ingredients are incorporated ty spray on to the base powder of nonionic, dry mixing (perborate) or via prill addition (peroxy acid precursor, silicone and enzyme).

An additional comparative formulation 4A was «Me vp in accordance with Exaaple 4 except that the peroxy acid precursor had the structural formula 0^(0^).70- 0Formulations 4 and 4A ware each made ip into a 0.2* by weight aqueous solution at 60*C, and both formulations displayed a rate of perhydrolysis that was ^95% conplete after 2 IO minutes. However, whilst formulation 4A had a strong bleachy odour, formulation 4 was virtually odourless· Application of perfume by spray on to both formulations prior to making up the aqueous solutions did not mask the solution odour of formulation 4A, whilst providing the expected pleasant odour to the solution of formulation 4.

BOWLES 9-14 The following formulations represent exanples of the detergent conposition aspect of the invention. 9 10 U 12 13 14 LBS 4 8 8 - 7 5C14/15 4 - - 9 -- 3 TAS — - 4 3 - -C12/l4ftS - - - - 2 - Cu TMAB - 2 2 — 2 - Dobanol 45-E-7 4 6 5 6 5 10 ^11 - 0.5 - - 2 - TAW 0.5 - 6 - - - Silicate 5 6 3 7 4 10 Mixed Suds Suppressor 2 - - 2 - 2 Silicone Prill - - 2 3 - 0.5 MHBft - - 0.8 1.5 - 1 MA/AA 2 1 - - 1.2 - Brightener 1 0.3 0.2 0.4 0.3 0.2 0.2 cemr 0.3 - - - - 0.2 ΕΒΠΜΡ - - 0.4 - - - Sodiun Perborate 12 15 16 18 10 15 Engine 0.6 1 - - - 0.8 Sodium Tripolyphoephate 30 28 25 32 28 30 Magnesium Sulphate - 0.5 - - - 0.5 ISCNQBS 2.5 4 - - 3 - BSBS - - 2 - 5 ISONOBA - - 1.5 6 - - Sodium Sulphate, Moisture -To 100 and Miscellaneous EXRMELES 15-20 Laundry additive products incorporating precursor conpounds in water releasable combination with a sheet substrate are prepared having the oanpositions shown below in parts by weight: 16 17 IS 19 20 IS0M0BS 7.6 5.2 10.5 8.4 4.2 5.2 PAG ee - 2.5 4.0 - rani - 3.6 - - - - AOBS - - - - - 3.0 A4SE7 5.0 5.0 5.0 5.0 5.0 5.0 PEG 8000 5.0 7.0 8.0 8.0 6.0 6.0 c14tmab - 2.0 - - 2.0 - c14imws - - - 2.0 - 2.0 EDOMP 0.5 0.5 0.5 0.5 0.5 0.5 MUBA 0.3 0.3 0.3 0.3 0.3 0.3 Silioone Goqxsund 0.25 0.25 0.25 0.25 0.25 0.25 Brightener 2 0.1 0.1 0.1 0.1 0.1 0.1 Perfume 0.1 0.1 0.1 0.1 0.1 0.1 Substrate 2.8 2.8 2.8 2.8 2.8 2.8 The substrate in earh instance ie a square patterned apertured non-wovei λ sheet. of si; BB 23 X 35 cm and basis weight 2.8 g, formed of 100% unbleached crijped rayon fibres (80% fibre, 20% polyacrylate binder), lh the case of Exaiples 15 and 17 the products are made ty forming a melt of the TOG and A 45E7 at approximately 80*C, dispersing the other ocmponente (except the perfume) therein and applying the resultant slurry to the substrate from an applicator roll with which the substrate is brought into contact. Additional rolls are ueed to spread the slurry before it is cooled to ambient toperature to solidify the ocmpoeition. Perfume is then sprayed on to the iipregnated substrate to produce the final product.

Exaiples 16 and 18-20 uae a similar procedure except that the product is applied to the sheet via a divided extruder head instead of an applicator roll, the division permitting the cationic surfactant, together with 1.0 part of A45E7 and 2.0 parte of PEG 8000 from the formulation to be applied as a separate stripe.

EXAMPLE 21 SO A bleaching conposition in the form of the aliphatic peroxy acid derivative of the conpound of Exanple 1 ooeprises: 3,5,5-trimethyl peraxytiexanoic acid 18.2* Boric acid 67.8* B-hydroxyquinoline 0.05* Disodium dihydrogen pyrophosphate 0.05* Minors, including 10* sodium sulphate 13.9* 100.00 BCAMPLZS 22-26 The following formulations aze further detergent oonpoeitions accordance with one aspect of the invention. 22 23 24 25 26 LAS 4 8 - 7 -C14/15 4 - - - - TAS - 4 - 2 — ASC - - 15 - 20 Soap - 2 10 - 25 Dobanol 45-E-7 4 5 6 5 10 TAED 1 1 - 1 - Silicate 5 3 7 4 10 Mixed Suds Suppressor 2 - - - .2 Silicone Prill - 2 3 - 0.5 Ml/DA - 0.8 1.5 - 1 OTA - 2.5 - 2.5 5 Brightener 1 0.3 0.4 0.3 0.2 0.2 DETOMP - - - - 0.2 EDIMP 1 - - 1 - Sodium Perborate 12 16 18 10 15 Enzyme 0.6 - - - 0.8 Zeolite A 30 25 - 10 - Carbonate 10 5 15 20 - Sodium citrate - - 10 - 5 ISQNOBS 3 4 - 3 - BOBS - - - - 5 ISCNQBA — — 6 — - Sodium Sulphate, Moisture -TO 100 and Miscellaneous Rl

Claims (6)

CLAIMS 1. I R - OR 11 O A. QCt of from 1.9 to 4.1, wherein P^ L is the partition coefficient of the carboxylic acid between n-octanol and water at 21°C, and 1« is a leaving group selected from: a) cap, and O II b) - N - C - Rj wherein Rg 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 from: -SOjM - csoy* - a>^t - W+tRj)^- NfRjJyO wherein M is H, alkali metal, alkaline earth metal, anraniusn or substituted ammonium and Q Is a halide or methosulptiate, the conjugate acid of said leaving group L having a pKa in the range from 6 to 13.

1. An aqueous laundry bleaching liquor having a bland odour cooprisidg a source of alkaline hydrogen peroxide in an amount to give a level of available oxygen of from 50 to 350 ppm together 5 with a non-linear aliphatic, aryl aliphatic or alkanyl aliphatic peroxycarbaxylic acid precursor in an anount to give frcm 1 to 50 ppn of the peroxycariDoxylic acid upon reaction with said alkaline hydrogen per oxide source, said precursor having the general fornula: R 11 O R 1 - C— &-I, Jui wherein the group: R 11 is an organic moiety of nonr-linear structural configuration, at least one of R 11 and R 11 * being hydrogen, the other R 11 and r 1u being independently selected from hydrogen and Cj-C* 15 alkyl groups, the group:

2. An aqueous laundry bleaching liquor according to claim 1 wherein the group R in the peroxycarboxylic acid precursor is a hydrocarbyl moiety.

3. An aqueous laundry bleaching liquor according to either one of claims 1 and 2 wherein ccnprises the groip: RR 1V I cwherein R 1V and R V are each independently selected from hydrogen and alkyl groups* and the group : R 1V R 11 I I R- C - Cir R 111 conprises a C^-C^ 6 alkyl group in which at least one R 11 , R 111 , R 1 and R V are C^-C^ alkyl, there of being a linear alkyl chain of five or more carbon atone extending from and including the carbonyl carbon.

4. An aqueous laundry liquor according to any one of claims 1-3 wherein the group: is a Cg-Cjj group wherein and R 1 ^ 1 axe hydrogen 5. An aqueous laundry liquor according to claim 4 wherein: R 11 R^-Ck lU IO is a C 7 -C g grap. 6. An aqueous laundry liquor according to any one of claims 1-5 wherein the conjugate acid of leaving group L has a pKa in the range fron 7 to 11. 7. An aqueous laundry liquor according to claim 6 wherein L has the formula a) in which Z is Η, x is 0 and Y is -SOyt or ~0θ2 Μ ' 8. An aqueous laundry liquor according to claim 7 in which the group r u q • M R,- C - CJll is either 2-ethyl hexanoyl or 3,5,5 trimethyl hexanoyl. 9. A solid laundry bleaching composition adapted to form an aqueous laundry bleaching liquor haying a bland odour comprising a non-linear aliphatic, aryl aliphatic or alkanyl aliphatic per15 axyacid precursor having a general fornula as recited in any one of claims 1-8 together with an alkali metal inorganic perhydrate salt or a hydrogen peroxide clathrate. 10. A solid bleaching composition according to claim 9 further canprising an organic detergent surfactant. 2o 11· A solid detergent composition according to claim 10 wherein the organic surfactant is selected from anionic, nonionic and cationic surfactants and mixtures thereof and the source of hydrogen peroxide comprises an alkali metal perborate or percarbonate or a hydrogen peroxide clathrate, the molar ratio of 25 said alkaline hydrogen peroxide to the precursor being at least 1.5:1. 12. A solid detergent conpoeition according to either one of claims 10 and Π which further includes a peroxyacetic acid precursor in an amount such as to provide a non linear aliphatic peroxyacid:peracetic acid weight ratio in the range of from 3:1 5 to 1:5« 13. A solid detergent composition according to claim 12 wherein the peracetic acid precursor is selected from tetraacetyl ethylene diamine, tetraacetyl methylene diamine, tetraacetyl glycouril, sodium p-acetoxybenzene sulphonate, pentaacetyl glucose, IO octaacetyl lactose and mixtures thereof. 14. A laundry additive product adapted for addition to an aqueous laundry liquor containing a source of alkaline hydrogen peroxide, said product conprising a conpoeition incorporating a non linear aliphatic, aryl aliphatic or alkanyl aliphatic peroxycarboxylic 15 acid precursor having a general foraula as recited in any cue of claims 1-8 enclosed within a container which allows access of water to the interior thereof on imnersion in the liquor. 15. A laundry additive product, according tc claim 14 wherein the container is water isepermsable and is provided with a water 2o frangible closure· 16. A laundry additive product according to either one of claims 14 and 15 wherein the container comprises a flexible pouch or bag made of synthetic polymeric film material. 17. A laundry additive product according to either one of claims 15 25 and 16 wherein the water frangible closure comprises a water soluble adhesive. 18. A laundry additive product adapted for addition to an aqueous laundry liquor containing a source of alkaline hydrogen peroxide, said product oonprising a coaposition incorporating a non-linear aliphatic, aryl aliphatic or alkanyl aliphatic peroxyacid precursor having a general formula as recited in ary one of claims 1-8, in water releasable caribinatian with a non particulate flexible substrate, the weight ratio of said precursor to said substrate being in the range of fron 1:10 to 30:1. 19. A laundry additive product according to claim 18 wherein the substrate is a laminated sheet. 20. A laundry additive product according to either one of claims 18 and 19 wherein said substrate is formed of non woven fibrous material and the weight ratio of said precursor to said substrate is in the range 1:2 to 10:1. 21. A laundry additive product according to any one of claims 14-20 which further includes a peroxyaoetic acid precursor in an amount such as to provide a non linear aliphatic peroxyacid: peracetic acid weight ratio in the range of from 3:1 to 1:5. 22. A laundry additive product according to any one of claims 14-21 wherein the cooposition incorporates one or more of an organic surfactant, a detergent builder salt or a chelating agent. 23. A method of forming a laundry bleaching liquor having a bland odour conprising the step of adding a product in accordance with any one of claims 14-22 to an aqueous liquor containing a source of alkaline hydrogen peroxide in an amount of from 50 to 350 parts per million. 24. An aqueous laundry bleaching liquor having a bland odour according to claim 1 substantially as described. 25. A laundry detergent bleaching conposition adapted to form an aqueous laundry bleaching liquor according to claim 10 substantially as described with reference to Exanples 3-14 and 22-26.

5. 2

6. A laundry additive product according to claim 14 adapted for addition to aqueous laundry liquor containing a source of alkaline hydrogen peroxide substantially as described with reference to Examples 15-20.