IE883364L - Bleaching detergent liquors - Google Patents

Description

& «S* o 7 2 This invention relates to the field of ooddiaable stain removal, especially taut net solely to the rami of oxidisable stains from fabric* and is particularly uoncamad with the renoval of these stains using- peroxygen bleaches at 5 teqperatuns 4 60*C sudi as are encountered in denes tic washing and laundering operations.

Ihe reaowl of oaddlsable stains ficon either hard surfaces or fabrics by means of peroocygan bleacftee at tenperatures less than 60°C is a wall known technique and custonarily involves the 10 use of organic percsy acids, the oast canonly used penaxy acid is pscaoetic 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 atoms in the 15 acyl group lave also been disclosed and taught far this purpose and GB-A-864,798, Canadian Patent No. 635,620, US Patent Nos. 4100095, 4119660, 4126573 and European Published Application Mb. 0068547 all relate to the foarnation, stabilisation or use of such materials.

Recently, as described in European Application No. 0068547, it has been fiowd that selection of the chainlength of the aliphatic noiety of the peray acid permits the peraxy acid to be concentrated in the area Whsce stain renoval is requited, Thus for renoval of fugitive dyestuffs in bulk solution, a 'hydrcphilic' bleach species is satisfactory, whereas for stains on solid surfaces a bleaching species 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 Ho. 4412934 issued to Stanley y Chung & Gianfranoo L Spadiai, on November 1st 1983 entitled "Bleaching Compositions", and Patent Specification No. Stcentitled "Detergent Additive Product" compositions are disclosed which incorporate a Cg-CjQ acyloxy coopowd capable of farming a aliphatic peroxy acid on reaction with alkaline hydrogen peroxide, the Cg-Cjg aoyl groif> being linear in nature.

Although compositions prepared in accordance with these last named disclosures provide stperior 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 now been fomd that certain branched chain aliphatic peraxy acid precursors. When added to aqueous liquors containing a source of alkaline hydrogen peroxide, provide effective bleaching of axidisabla 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 addsd to water as part of a conplete inorganic peraxy bleach-containing detergent composition or as part of a laundry additive product added to an aqueous solution of an inorganic peroxy bleach-containing detergent composition. 4 According to one aspect of the invention therefore there is provided an aqueous laundry bleaching liquor having a bland odour conprisilfg a source of alkaline hydrogen peroxide in an amount to give a level of available oxygen of from SO to 350 ppm together with a non-linear aliphatic, oryl aliphatic or alkanyl aiiptialic per-axycarbaxylic 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: R1- RU O f A* Jill wherein the groqp: R11 R1- <j- is an organic moiety of non-linear structural configuration, at least one of R11 and R111 being hydrogen, the other R11 and R1U being independently selected from hydrogen and C^-C^ alkyl groups, the group: R^O r1- o- i-Jm being the acyl moiety of a carboxylic acid having a logP^ of fro* 1.9 to 4.1, wherein P , is the partition coefficient of the carboxylic acid between n-octanol and water at 21"C, and L is a leaving group selected from: O -(/ WCH^Y and b) - N - C - Rj r Y wherein R2 is an alkyl group containing from 1 to 4 cartoon atoms, x is 0 or an integer from 1 to 4 and Y is selected from: " - CSOjM - aoji - - wherein M is H, alkali natal, alkaline earth metal, amoniun or substituted ammonium and Q is a halide or methosulphate- These leaving groups have a pRa in the range from 6 to 13 more preferably in the range from 7 to 11, most preferably from 8 to 10.

Preferred leaving groqps are those of formula a) above in which x is 0 and Y is selected from -SO^M and -OOjH vfaerein M is alkali metal, preferably sodium.

Preferably the grotpi R11 R1- C- A111 is a Cy-Cg alkyl grotp and preferred oonpounds are alkali metal, amaoniun or substituted aanoniun 2-ethyl hexanoyl oxybenasene sulphonates and 3,5,5-trimethyl hexanoyl oxybenzene sulphonates, with sodium being the preferred cation.

According to another aspect of the invention, detergent conpositicns are provided canprising a oonpound, as above defined, in combination with a surfactant which may be anionic, nonicnic, oaticnic 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 viiich is primarily anionic in character with nonicnic and, in a highly preferred form, cationic components. Also in a preferred form of the invention, the molar ratio of the hydrogen peroxide present to the defined ocnpcxmd is at least l.Sil.

In a further aspect of the invention, laundry additive products are provided in which a ccapound, as hereinabove defined, is enclosed in a container such as a bag or pouch of synthetic polymeric film material vAiich is formed with a ' water frangible closure to permit release of its contents on immersion in an alkaline acinous laundry liquor containing a source of hydrogen peroxide. Another font of this aspect of the invention ccaprises a acnpawd as defined above in wnter-releasable examination with a flexible non-particulate substrate in a ccnpound: substrate weight ratio of from 1:10 to 30:1. In both of these additive compositions other detergent components, such as surfactants, builder salts and chelating agents, may be present.

The invention also emhraces bleaching ccnpoeitions comprising an aliphatic perearbaxylic acid of fonmila R-OOOCH where R is a C^-C^ alkyl grotp which is branched in at least the 2- and/or 3-position with respect to the carbonyl 7 carbon atcn, there being a linear alkyl chain of 5 or more carbon atcan extending fran and including the oarbonyl carbon in ccebinatian with a stabilising agent.

Other aspects of the invention ccaprise a Method of 5 fanning an aqueous laundry liquor having a bland odour by the addition of laundxy additive compositions as defined above to aqueous solutions containing a source of alkaline hydrogen peroxide and laundry liquors fornsd by such a Method or by the dissolution of a detergent or bleaching ooopositicn 10 containing a coapoixid as defined above.

The ooepoinds found to be useful as organic peroxyacid bleach precursors have the formula R11 O R1 C - C - L R111 Wherein the group: R111 is an organic moiety of nan linear structural configuration, K11 and R111 being independently selected fran hydrogen and Cj-C4 alkyl groups, the groups R11 0 1 ' " R-C- C- R111 2o being the acyl moiety of a carbaxylic acid having a l°9poct of from 1.9 to 4.1, Wherein PQct is the partition coefficient of the carboocylic acid between n-octanol and water at 21 *C, and L is a leaving grtxp the conjugate acid of which has a pKa in the range from 6 to 13. 8 R1 is an organic Moiety whlcJi can have a variety of foxns. Thus R1 say be aliphatic in nature and nay be linear, cycloaliphatic or branched. Alternatively R1 may be arcnatic, alkyl arcnatic or aryl aliphatic. R1 may 5 also include hetexoatoas such as oxygen, nitrogen and halogen provided these are not in the backbone of the grocp i.e. they ■ust be pendant frcn the hydrooarbyl structure. Groups subject to oxidative attack, audi as aldehyde groins should not be present and the moiety should preferably be free of 10 unsaturatian other than that of arcnatic character.

Preferably is a hydrooarbyl moiety.

The effects of structure an the hydrophDbicity of organic coqoowds as represented ty their partition coefficients between octanol and water are described ty A Leo et al in IS Qienical Reviews, 71, pp 525-616 (1971). The authors provide numerical values for the dhange in IxxjPq^ (Where pqct is the partition coefficient between n-octanol and water) associated with the incorporation of various subetituenta into a range of structures. This permits a value for 20 LogP^^p to be predicted for any structure.

All of the ocxpounds display surface activity but this property is not vexy narked for compounds in which the gran? R^ -CCR11*111)- contains less than 8 carbon atoms and only those cospounds in which H^-CfR^R111)- contains 25 m>re than 10 carbon atcns display detergent characteristics. Hydrocarbyl group brandling confers increased solubility relative to linear cospounds of the sane number of carbon atooa and this increased solubility is associated with a decrease in surface activity relative to the corresponding 30 linear conpound. This effect also holds true for the aliphatic peraxy acids produced cn perhydrolysia of the conpounds. However, it has now surprisingly been found that aqueoun liquors containing ran linear aliphatic peraxy 9 oarboxylic acids in Mhich nan linearity occurs particularly on the 2-and/or 3-oarban a tans with respect to the carbcnyl carbon, have a less intense odour of more aesthetically acceptable character than those containing the corresponding linear 5 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 on carbon atone further removed from the carbonyl carbon than the 3-carbon atom ID position also appears to be beneficial but to a lesser extent and little or no odour benefit is seen for nan linearity commencing at 5- or higher carbon atom positions relative to the carbonyl carbon. Accordingly, brandling on 4~ and higher carbon atoms is not believed to be so critical to the 15 odour fanning capability of the canpound. The reason for this difference in behaviour between branched and linear aliphatic peraxy acids is not well understood and does not appear to be predictable.

The introduction of nan linearity into the organic groif> also affects the rate of perhydrolysis of the precursor in alkaline hydrogen peroxide solutions.

Substitution and, in particular, ui substitution of an alkyl group on the 2-carbon causes a lowering in the rate of perhydrolysis of the precursor because it hinders the 25 approach of perhydroxyl ion and is believed to reduce the effectiveness of the per oarboxylic acid as a bleach. Don linearity on the 2-carbon is thus less preferred than on the 3-carbon where e.g. di alkyl substitution has much less effect an the perhydrolysis of the coappund whilst still 30 providing an aliphatic peraxy acid of iiproved odour.

One preferred for* of the groups R11 R1- C- wherein R^ and RU1 are as previously defined, is thus the group: R1V R11 | I R — C — C — wherein .V „111 R R IV V R and R are aach independently selected front hydrogen and C^-C^ alkyl groipe and the groip: f f R— C- C — RV comprises a Cg-C^. alkyl grcxp in which at least one of 10 RUR111RlV and R are C^-C4 alkyl, there being a linear chain of five or nore carbon atoas extending fron and including the carbonyl carbon. Preferably R11 and are l^drogen atone.

Branched chain alkyl grmp-containing precursors in which 15 there is no nore than a single branch on the 2-carbon but at least one on the 3-carbon perhydrolyse at an adequate rate (i.e. >80% conversion within approximately 5 minutes) but still produce an odour vrfien dissolved in an aqueous alkaline solution of hydrogen peroxide. However this odour is of a more acceptable type and level than that produoed by the corresponding linear alkyl precursors under the sane conditions.

A preferred number of carbon atoms in the alkyl groups R1V RU I i R—C C — RV RU1 is frcm 7 to 9 carbon atoms with a linear chain of from S to 8 carbon atoms and with R^v and/or Ry 6c(prising a side chain i.e. in the 3-carbon position with respect to the carbonyl carbon atom.

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

Structures in accordance with the invention far the group K11 O i ■ M R~ —C —C — R111 where R1 is aliphatic include: CM, 0 I • CH-— C-CH, - CH-CH, - C— 3,5,5 trimethyl hexanoyl- 3 I 2 I 2 CHj CH3 CH.(CH-) CH - C - 2 ethyl hexanoyl- "2'3 I CH, I2 CH3 12 Cay C - (CH2)3 - C- 5-methyl hexanoyl- CH, H 0 ' I CHj C - (CHj)^ C - 6-nethyl heptanoyl-CHj CH, 0 I I CHj - (CH2)5 - C - C - neodecanoyl- CHj Of the above the 3,5,5 trimethyl heanyl structure is the most preferred for odour end rate of perhydrolysis with the 5-methyl hexanoyl 6-methylheptanoyl end neodecanoyl structures being less preferred far odour and the neodeoancyl and 2-ethyl hexanoyl being less preferred for the rate of perhydrolysis. Structures in accordance with the invention far the group R11 0 R1— C— C— where R^ incorporates a cyclo aliphatic or arcnatic functionality include 0 1 (CHjJ^C- cyclchexyl butyroyl 0 (I -(OijJjO- 5-pfrvenyl valeroyl ^ n -(CHjJjC- 3-phenyl propionoyl c* Q Of the above, the 5-phenyl valeroyl and the 3-pherryl IS propioncyl structures are the most preferred, having a virtually bland odour and an acceptable rate of perhydrolysis.

Hie leaving groig> L Bust be capable of diaplacgacnt from the bleach precursor as a consequence of the nucleophilic by alkaline hydrogen peroxide, litis, the pertydrolysis reaction, results in the formation of the percarboxylic Kid. Generally, for a groq? to be a suitable leaving groq? it oust exert an electron withdrawing effect within the precursor molecule as this facilitates the nucleophilic displacement by the perhydroxyl anion.

Suitable leaving groqpe for this purpose have conjugate acid forms, the pKa of which should lie within the range from 6 to 13. pKa values above 13 make the electron withdrawal effect so small as to be ineffective in promoting nucleophilic attack by perhydraxide anion, an exaqple of such a leaving group being - OCH^. pKa 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 groups have a pKa in the range fron 7 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 gzocps such as sulphonamide groqps, having conjugate acid fonts 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 groqos L foind to be useful in coqpounds of the present invention are those having the formula attack on the bleach precursor by perhydroxyl anion generated O II b) - N - C - R2 I 4 wherein is an alky] groqs containing from 1 to 4 carbon atoms; x is 0 or an integer fron 1 to 4 and Y is selected from: -Sty - OSOgM - cOjM - N+ wherein M is H, alkali metal, alkaline earth metal, anncniun or 10 substituted ammonium; and 0 is halide or nethosulphate.

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 groip Y on the benzene 15 ring - in formula a) is not critical in that o -, m - and p-positions provide operable species. Nevertheless polar and sterlc factors make the o-substituted material most difficult to synthesise and of least value in that steric hindrance Impfrien the approach of perhydroxyl ion. In the preferred 20 esfeodiment of leaving 9EOtp 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 compounds used in the invention can be 25 illustrated generally by a sequence of reactions in Mhidi a acid or acid chloride is fanned in which the acyl group has the required branched structure and the subsequent reaction of this with a compound of formula a) above wherein the free bond is satisfied by a hydrogen atom. 30 Hie Cy-Cjj acid or acid chloride starting material, in Which , the acyl group has a linear chain of at least 5 carbon atoms 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 alpharolefins 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-msthyl or 2-ethyl branching. If branched olefins are used as the starting material, the resulting acids are completely branched. Branched olefins themselves, having diain lengths up to C^, are produced by polymerising propylene or butene using a phosphoric acid catalyst under conditions of high temperature and pressure. The diaerisaticn of isobutene or the codimarisatian of n-butene and isobutene leads to a highly branched isancnanoic acid whidi 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 by aldol condensation of the aldehyde followed by hydrogenaticn of the aldol oondenaation product and final oxidation.

Manufacture of the acid reactant used in the preparation of sodiiai 3,5,5-trimethyl hexanoyl cocybenzana sulphonate, a preferred coapowd in accordance with the invention, involves the condensation of two mules of butane to for® «Ji Isobutene followed by aarbonylation to produce the aldehyde and subsequent oxidation to form the isononanoic acid. This is then converted into the acid chloride in known manner. The acid chloride is re fluxed with sodiw phenol sulphonate in a nitrogen current at 100-150*C for 10-20 hours to fan the sodiimi 3,5,5-trimethyl hexanoyl benzene sulphonate.

Alternatively, the isononanoic add can be transesterified, refluxing at 160-180*C with sodium phBnol 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 from an organic solvent. A similar reaction procedure starting with n-nonanoic acid is disclosed and claimed in Patent Specification No. *SboLt'X . 'The impounds themselves are the subject of the claims of parent Patent Specification No. 3b90k t 6 Similar procedures to the above are also oplayed in the synthesis of sodium 2-ethyl hexanoyl oocybenzene sulphonate.

The analogous acyl oocybenzene oartxaxylate salts are also preferred compounds useful as peroxyacid bleach precursors. Synthesis of these materials is sinilar to that of the sulphonate salts in that the acid chloride is refluxed with p-ftydraxybenzoic acid to produce the acyloxybensaoic acid product which can be recovered by addition of petroleum ether to precipitate the acid.

Sodium 3,5,5-trimethyl hexanoyl oaybenzoate and sodium 2-ethyl hexanoyl axybensaoate are preferred members of this class of compounds. Although the above compounds are described in terns of their soditm salts, other alkali metal and alkali earth metal cations and ammiim and substituted quaternary ammonias salts such as tri C2~C3 alkanol anonium salts can also be egployed.

The following two compounds are useful as organic . peroxyacid bleach precursors . 1) Synthesis of sodium 3,5, 5-trinethyl hexanoyloxybenzene sulphonate Isononanoyl chloride of purity 95.8% and oolecular weight 176.5 (sipplied by Akao BV, Queens Road Hersham, Surrqr, Bigland) and sodiun phenol sulphonate of purity £99.5% and (Wt 196 (supplied by BEH Chemicals Ltd, Poole, Dorset, Bigland) were used as the starting materials in the reaction.

CHj - C - CHj - CH - CHj - C - CI + HO- I I ®3 <*3 O 1 ®3 CH3 CH3 O 17 19.62 gas of finely powdered, anhydrous sodium phenol sulphonate (1/lOth mole) and 22.06 gu of Akao iaonananoyl chloride (weight l/10th mole + 25% excess) were weighed into a 500 al conical flask containing 250 5 als of chlorobenzene. Hie flask was fitted with a ■agnatic stirrer, a 2-way head carrying a Nj gas inlet (leading to the base of the flask) and a reflux condenser (+ CaClj tube) and was surrounded by an ail-bath. The flask was heated with stirring to 120*C and with N2 gas 10 passing through the flask, was maintained at that tesperature overnight (20 hours). The heating wo* than turned off and the flask contents allowed to cool to room teaperature. The contents were then washed with 3x1 litre diethyl ether, filtering betwaen each wash (a 15 Silver son stirrer was used for agitation). Hie 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.

Yieldt 27.40 gms (81.5% yield) NMR analysis showed 81.4% required oonpcxxid. 18 2) Synthesis of sodif 2-ethyl hexanoyl axybenzene sulphonate Anhydrous sodium phenol sulphonate (58.85g; 0.3 sole) Mas added to a stirred Mixture of acetic anhydride (36.75g; 0.36 mole), 2-ethylhexanoic acid (129.8g; 0.9 vole) and 5 sodiun acetate (3g). the resultant Mhite suspension w stirred inter 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 fron the 10 condenser top to a spare inlet an the flanged-top of the reaction vessel and the condenser was set up in a distillation node. The pot tenperature was gradually increased to 260°C during 1.5 hours; the still-head teiperature rose to 131*C. The contents of the reaction 15 pot Here then allowed to oool overnight to aiibi ent tenperature before being washed with 3 x 1.5 litres diethyl ether, filtering between Mashes, and then being dried. the yield of sodium 2-ethyl hexanoyl axybenzene 20 sulphonate was 88.3g, 91.3% of theocy.

Purity (by oat. SOj determination) » 93.4%.

A aocond aspect of the invention relates to detergent compositions incorporating the conpounds, as defined above, primarily as peroxyacid blearii precursors, (the so-called low 25 tenperature bleach activators). Such detergent canpositians conprise an organic surfactant, a conpowd 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 30 laundry compositions. A typical listing of the classes and species of these surfactants is given in U.S.P. 3,663,961 issued to Morris on May 23, 1972.

Suitable synthetic anionic surfactants are water-soluble salts of alkyl benzene sulphonates, alkyl sulphates, alkyl 35 polyethoxy ether sulphates, paraffin sulphonates, alpha-olefin sulphonates, alpha-sulpho-carbaxylates and their esters, alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkyl phenol polyethoxy ether sulphates, 2-acylaxy alkane-l-eulphanateB, 4q and beta-alkylaxy alkane sulphonates. 19 A particularly suitable class of anionic surfactants includes Mater-soluble salts, particularly the alkali netal, ansonius and aUcanolamoniuB salts of organic sulphuric reaction "products having in their molecular structure an 5 alkyl or alkaryl groip containing fron 8 to 22, especially fron about 10 to about 20 carbon atoms and a sulphonic acid or sulphuric acid ester groif>. (Included in the tern "alkyl" is the alkyl portion of acyl grope). Examples of this grotp of synthetic detergents Mhidi form part of the detergent K> compositions of the present invention are the sodius 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 sodium and potassium alkyl benzene sulphonates, in Mhidi 15 the alkyl group contains fron 9 to 15, especially 11 to 13, carbon atoms, in straight chain or branched chain configuration, e.g. those of the type described in D.S.P. 2,220,099 and U.S.P. 2,477,383 and those prepared from alkylbenzenes obtained by alkylaticn with straight chain 20 chlarcparaf£ ins (using aluminiimi trichloride catalysis) or straight chain olefins (using hydrogen fluoride catalysis). Especially valuable are linear straight chain alkyl benzene sulphonates in wtiidi the average of the alkyl group is 11.8 25 carbon a tons, abbreviated as g LAS, and ci2~Cl5 methyl broncxrai alkyl sulphates.

Other anionic detergent compounds herein include the sodium ciQ_i8 alkyl glyceryl ether sulphonates, especially those ethers of higher alcohols derived from tallow and 30 coconut ail; sodium coconut oil fatty acid monoglyceride 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 cartoon atoms.

Other useful anionic detergent compounds herein include the water-soluble salts or 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 groip; water-soluble salts of 2-acyloxy-alkane-l-sulphanic acids containing from 2 to 9 carbon atoas in the acyl group and fron 9 to 23 carbon atoas in the alkane noiety; alkyl ether sulphates containing feat 10 to 18, especially 12 to 16, carfign atoms in the alkyl groqp and fron 1 to 12, especially 5 1 to 6, mere especially 1 to 4 moles of ethylene oxide; water-soluble salts of olefin sulphonates containing fron 12 to 24, preferably 14 to 16, carbon atoms, especially those nade by reaction with sulphur trioocide followed by neutralization under conditions such that any sultones 10 present are hydrolysed to the corresponding hydroxy alkane sulphonates; water-soluble salts of paraffin sulphonates containing frcn 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 IS in the alkane moiety.

Hie alkane diains of the foregoing non-soap anionic surfactants can be derived from natural sources audi as coconut oil or tallow, or can be nude synthetically as far sample using the Ziegler or Oxo processes. Vfeter solubility 20 can be achieved by using alkali metal, ammonium or alkanolaamoniuii cations; sodium is preferred. Suitable fatty acid seeps can be selected from the ordinary alkali metal (sodium, potassium), araonium, and alkylolaanonium salts of higher fatty acids containing from 8 to 24, preferably from 25 10 to 22 and especially from 16 to 22 carbon atoms in the alkyl chain. Suitable fatty acids can be obtained from natural sources such as, far instance, from 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., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tzopedi 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 imde by direct 35 saponification of the fats and oils ae by the neutralisation of the free fatty acids which 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. 31 Mixtures of anionic surfactants are particularly suitable herein, especially nixtures of sulphonate and sulphate surfactants in a weight ratio of fron 5il to li5, preferably fron 5tl to 1)2, mace preferably fron 3il to 2i3. Especially 5 preferred is a ltl mixture of an alkyl benzene sulphonate having fron 9 to 15, especially 11 to 13 carbon atoas in the alkyl radical, the cation being an alkali natal, preferably sodiun; and either an alkyl sulphate having fron 12 to IS, preferably 14 to 16 carbon atoas in the alkyl radical or an alkyl 10 ethoxy sulphate having fron 10 to 20, preferably 10 to 16 carbon atone in the alkyl radical and an average degree of ethoxy lation of 1 to 6, having an alkali nstal cation, preferably aodiun.

The nonicnic surfactants useful in the present invention 15 are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range fron 8 to 17, preferably fron 9.5 to 13.5, more preferably fron 10 to 12.5. The hydrophobic noiety nay be aliphatic or aromatic in 20 nature and the length of the polyoxyothylene group which is condensed with any particular hydrophobic groip can be readily adjusted to yield a water-solttole ocapound having the desired degree of balance between hydrophilic and hydrophobic Exanples 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 fron 6 to 12 carbon atoas in either a straight chain or branched chain configuration, 30 with ethylene oxide, the said ethylene oxide being present in anounts equal to 3 to 30, preferably 5 to 14 moles of ethylene aside per anle of alkyl phenol. The alkyl subetituent in audi ccnpounds may ba derived, for example, fron polymerised propylene, di-isobutyiene, 35 octene and nonene. Other Temples include dodecylphenol condensed with 9 anles of ethylene oxide per mole of phenol; dinonylphenol condensed with 11 moles of ethylene oxide per mole of phenol; nonylphenol and 22 di-ieooctylphenol condensed with 13 males of ethylene oxide. 2. The oondenaation product of primary or secondary aliphatic alcohols having fron 8 to 24 carbon a toots, in 5 either straight chain or branched chain configuration, with fron 2 to 40 noles, preferably 2 to 9 noles of ethylene oxide per mole of alcohol. Preferably, the aliphatic alcohol emprises 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 mole of aliphatic alcohol. The preferred surfactants are prepared fron primary alcohols which are either linear (audi as those derived fron natural fats or, prepared ky the Ziegler process fron ethylene, e.g. myristyl, cstyl, IS atearyl alcohols), or partly branched such as the Lutensols, Dobanols and Neodols which have about 25% 2-nethyl brandling (Lutensol being a Trade Name of BASF, Dcbanol and Neodol being Trade Names of Shell), or Syiperonics, Which are understood to have about 50% 20 2-methyl brandling (Synperonic is a Trade Kune of I.C.I.) or the primary alcohols having more than 50% branched chain structure sold under the Trade Name Lial by Liquichimica. Specific exaaples of nonionic surfactants useful Cor the purposes of the invention include Dobanol 25 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 alodial with an average of between 5 and 12 moles of ethylene oxide per mole of alcohol, the 30 coconut alkyl portion having frcn 10 to 14 carbon atons, and the oondenaation 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 ethoxy lates are also suitable in the present oonpoeitions, especially those ethoxy latea of the Tergitol series having from 9 to 15 aarban atoms in the alkyl group and up to 11, especially from 3 to 9, ethoxy residues per molecule. 33 Useful ncnianle surfactants also include those in Which ethylene oxide is condensed with a hydrophobic 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. sudi synthetic nonionic detergents are available an the market under the Trade Name of "Plutonic" sqpplied by Wyandotte Chemicals Corporation.

Especially preferred nonionic surfactants for use herein are the C^-C^ primary alcohol ethoocylates containing 3-8 moles of ethylene oxide per nole of alcohol, particularly the C12~C15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol.

Cationic surfactants suitable for use herein include quaternary anmcnium surfactants and surfactants of a semi-polar nature, for exaqale amine cocides. Suitable quaternary anmonitmi surfactants are selected from mono Cg-C^g, preferably C^-C^ N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, ftydroxyetfyl or hydraxypropyl groups. Suitable amine oxides are selected from mono Cg-C^g, preferably C^^ N-alkyl or alkenyl amine oxides and prqpylene-1,3-diamine dioxides Wherein the remaining W positions are again substituted by methyl, hydroxysthyl or hydroxyprqpyl grcxpe.

The detergent aoapositions can ccmprise from U-70% by weight of surfactant, but usually the surfactant is present in an amount of fron 1% to 20ft, more preferably from 5-15% by weight. Mixtures of surfactant typos are preferred, particularly anionic-oationic mixtures. Particularly preferred mixtures are described in British Patent No. 2040987 and EP-A-0 OB7 914.

A source of hydrogen peroxide can be provided by any of the commercially available inorganic peroxygen bleaciies and also by certain hydrogen peroxide adducts.

Suitable inorganic peroxygen bleaches include sodium perborate mono and tetra hydrate, soditaa per carbonate, sodium persilioate and the clathrate 4Na2SO^ i 2i^0^ : 34 INaCl. A separate source of alkalinity is required for clathrate Materials and for stability reasons this should preferably be kept 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 anoint of from 1% to 40%, note preferably frcn 5t to 35% by weight of the coBpoeition and will most frequently be present in an amount of from 10ft to 308 by weight.

In preferred embodiments of this aspect of the invention the levels of hydrogen peroxide source and precursor coopound are arranged so that the molar ratio of hydrogen peroxide yielded by the source to precursor coapound is greater than 1.5il, normally at least 2.0. Under the usage conditions 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 ccnpositicns, in accordance with the invention, will include those coaponents canncnly included in heavy duty laundry detergents sudi as suds suppressing agents, detergent builders, chelating agents, sail suspending and anti redcposition agents, optical brightening agents, enzymes, colours and perftmes..

Suds suppressors useful in the detergent cosposition aspect of the invention, particularly expositions used in laundering fabrics, an represented by materials of the silicone, wax, vegetable and hydrocarbon oil and phosphate ester varieties. Suitable silicone suds controlling agents include polydimethylsilaxanee having a molecular weight in the range from 200 to 200,000 and a kinematic viscosity in tha range from 20 to 2,000,000 mn2/s (cSt), preferably from 3000 to 30,000 m2/s (cSt), and mixtures of siloxanes and hydrophobic silanated (preferably trlmethylsilanated) silica having a particle size in the range frcn 10 millimlcrcmeters to 2 nillimicrcmeters and a specific surface area above 50 m /g. Suitable waxes include microcrystalline vexes having a melting point in the range fron 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 77*C by ASXM-D1321, and also paraffin Maxes, synthetic Maxes and natural Maxes. Suitable phosphate esters include Bono- and/or di-C^g-C^ alkyl or alkenyl phosphate esters, and the corresponding mono- and/or 5 di alkyl or alkenyl ether phosphates containing ip to 6 ethoocy groqps per Molecule.

Suds suppressors are normally included at levels of frca 0.01% to 5% by Msight of the composition, dependant on the type of suds suppressor used, wore oannonly 0.1% to 2% by 10 Height.

A highly preferred cospcnent of detergent aonpositians in accordance with the invention is one or sore detergent builder salts Which nay oaaprise up to 90% af the composition, rare typically fztai 10% to 70% by weight IS thereof. Suitable detergent builder salts useful herein can be of the polyvalent inorganic and palyrolent organic types, or Mixtures thereof. Nan-Uniting exaiples of suitable viater-soluhle, inorganic alkaline detergent builder salts include the alkali metal carbonates, borates, phosphates, 20 pyrophosphates, tripolyphoephates and bioarbonates.

Exaiples of suitable organic alkaline detergency builder salts are Mater-soluble polyoarbosylates such as the salts of nitrilotriacetic acid, lactic acid, glycollic acid and ether dsri'Atives thereof n disclosed in BE -A- 821,368, 821,369 25 and 821,370; succinic acid, anionic acid, (ethylenedioxy)diaoetic acid, aaleic acid, diglyoollic acid, tartaric acid, tartronic acid and fuaaric acid; citric acid, aconitic acid, dtraocnic acid, aarboocynathyloxysuccinic acid, lactoKysuocinic acid, and 2-axy-l,1,3-prcpana 30 tricarboxylic acid; axydisuccinic acid, 1,1,2,2-ethane tetraoartoxylic acid, 1,1,3,3-prcpane tetracarbaocylic acid and 1,1,2,3-prcpane tetracarbaxylic acid; cyclcpentane cis, cis,cis-tetracarboocylic acid, cyclopentadiene pentacarboxylic acid, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetraoarbaxylic 35 acid, 2,5-tetrahydrofuran-cis-dicarboxylic acid, 1,2,3,4,5,6-hexane-hexacarbaxylic acid, nsllitic acid, pyrcmellitic acid and the phthalic acid derivatives disclosed in GB -ft- 1,425,343. 26 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 tripolyphoophate, trisodiimi nitrilotriacetate, and trisodium 5 ethane-l-hydroxy-1,1-diphoqphonate.

A further class of builder salts is the insoluble alumino silicate type which functions by cation exchange to wow polyvalent mineral hazdnass and heavy metal ions from solution. A preferred builder of this type has the lO formulation Na^AlOj) ^(SiOjJy.jdSjO 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 from 15 to 264. Ccspositions incorporating builder salts o£ this type farm the subject of Pajfcent' Spte£e*<kion A)o. -• IS DE-A-2,433,485 published February 6, 1975 and EB-A-2,525,778 published January 2, 1976.

An alkali metal, or alkaline earth metal, silicate can also be prunrnt, preferably in an anount of fron 3% to 15%. Suitable silicate solids have a molar ratio 20 of SiOj/alkali metal^O in the range from 1.0 to 3.3, more preferably from 1.5 to 2.0.

Chelating agents that can be incorporated include citric acid, nitri lotriacetic and ethylene diamine tetra acetic acids and their salts, organic phoaphonate derivatives such 25 as those disclosed in Diehl US Patent Ho. 3,213,030 issued 19 October, 1965; Soy US Patent No. 3,433,021 issued 14 January, 1968; Gedge OS Patent No. 3,292,121 issued 9 January, 1968; and Bersworth OS Patent No. 2,599,807 issued 10 June, 1952, and carbaxylic acid builder salts such as thoss disclosed in 30 Diehl US Patent No. 3,308,067 issued 7 March, 1967.

Preferred chelating agents include nitrilotriacetic add (NEA), nitrilotrimethylene phoephonic acid (NIMP), ethylene diamine tetra methylene phosphonic acid (BTOff) and diethylene triamine penta methylene phoqphonic acid (DETPMP), 35 fund these are incorporated in amounts of from 0.1% to 3%, more preferably 0.2% to 2% ty Height of the ccqposition. 87 Antiredeposlti.cn and soil suspension agants suitable herein include cellulose derivatives such as msthylcellulose, □arboxymethylcellulose and lydxaoiyethylaellulose, and twno-or co-polyneric polycarboxylic acids or their salts in Which 5 the polycarboxylic add comprises at least two aarbaocyl radiaals separated fron each other fcy not mora than two aarbon a teas. Polymers of this type are disclosed in GB-A-1,596,756. Preferred polyaers include copolymers or salts thereof of maleic anhydride with ethylene, methylvinyl 10 ether, acrylic acid or nethacrylic add, the maleic anhydride constituting at least 20 mole percent of the copolymer.

These polymers are valuable for improving Whiteness maintenance, fabric ash deposition, and cleaning performance an clay, proteinaceous 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 McCarty and McCarty et al issued July 7, 1970 and January 5, 1971, respectively. Riotoactivators are discussed in EP-A-57088, 20 highly preferred materials being zinc phthalocyanine tri- and tetrar-sulphonates.

Anionic or nonionic optical brlghteners are also preferred ingredients of detergent compositions in accordance with th> invention, being nomally peasant at levels af from 25 0.01% to 1% fcy weight, more preferably at levels of from 0.02% to 0.5% fcy wei£tt.

Anionic fluorescent brightening agents are well-known materials, examples of Which are disodium 4,4* -bia-( 2-diethanolamino-4-anilino-s-tr iaxin-6-ylaaino) 30 stilbene-2:2'disulphanate, disodiw 4,4,-bis-(2-norpholint>-4-anilino-s-tr iazin-6-ylasino) stilbene-2:2' -disulphcnate, disodium 4,4' -bis- ( 2,4-dianilino-s-triazin-6-ylaiiino) stilbene-2:2'-di-sulphcnate, disodiun 4,4'-bis-(2-anilino-4- (N-nethyl-»-2-hydraxyethyla»ino)-8-triazin-6-ylamino) 35 stilbene-2,2'-di-suljphonate, disodiun 4,4'-bis-(4~phenyl -2,1,3-triazol-2-yl)-stilbene-2,2'-di sulphonate, disodiun 28 4,4'-bis( 2'-anilino-4-( l-nethyl-2-hydroxyethylamino)-s-triazin-6-ylaraino)stilbene-2,2'disulfho(nate, sodium 2(stilbyl-4n-(naptho-11,2":4,5)-l,2,3-triaajle-2"--sulphcnate and di-sodiimi 4,4'-bis(2-sulphcnato styryl)biphenyl.

Other fluorescers to which the invention can be applied include the 1,3-diaryl pyrazolines and 7-alkylaminocouiiarin&.

A preferred fluareecer is the anionic material available fron Ciba Geigy S.A. under the trade name Tinopal CBS and mixtures thereof with materials available under the trade 10 names Tinopal EMS and Blarikophor ICEN, the latter being sold ty Farbenfabriksn Bayer AG.

The nan-linear aliphatic peraxy acid precursors useful in the present invention are normally employed at levels of from 1% to 15% by weight more preferably at from 15 1% to 10% and most frequently at from 2% to % fcy weight of a detergent composition. They can be incorporated into a detergent composition in a nunfaer of ways, most if not all of which are intended to minimise any reaction between the precursor and other components during 20 storage prior to use.

Thus the precursor may be formed into particulates by spray cooling, prilling, aarunsrising, agglomeration or granulation, either alone or together with a carrier material whicii may be organic or inorganic in type. Suitable 25 inorganic materials include clays and other natural and synthetic aluminosilicates, as well as hydratable salts such as phosphates, carbonates and sulphates. Suitable organic materials include ethoxylated C^-C^g alcohols and alkyl phenols, polyethylene glycols of MWT 4,000-10,000, 30 C12~C1B £atty *cids an& esters thereof with monohydric and polyhydric alcohols. In one preferred method of manufacturing the precursor, disclosed in Patent Specification No. $bOif-S1 • the liquid reaction product containing the precursor is blended 35 with the carrier material under an inert gas atmosphere before being processed further to form the particulate material to be added to the detergent. Hiis technique is particularly suitable when the carrier is a waxy organic solid such as an' ethoxy lated alcohol or ester and a highly 40 preferred example, employing a glyceryl mono Cjq-C14 fatty acid ester carrier is disclosed in BP-A-0 123 423. 29 In another method of manufacturing the preferred alkali netal C^-C^ branded chain acyl axybenzene sulphonate phenol sulphonate precursors, one of the reaction components e.g. alkali netal phenol sulptanate or fatty acid is employed 5 in a greater excess than is necessary to adiieve the desired ccnpleteness of reaction. Die excess reactant is used as a binder material far the reaction product which is taken fron the reactor and, without sqxurate crystallisation or solvent extraction steps, is compacted to form particulates Mhidi can 10 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' EP-A-O 106 624 and Patent Specification No. *3?3L <o • 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 2o detergent composition to tftiidi the precursor particulates ara added may itself be mode in a variety of ways sud> as dry™siting, agglcseratioii 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 peraxy acid precursors whose carbaxylic acid analogues have a logPg^j, of from 1.9 to 4.1. Sudi additive products are intended to sqpplement or boost the performance of conventional detergent 30 compositions and may contain any of the components of such compositions, although they will not comprise all of the cooponents 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 35 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 comprise the compound alone in combination with a carrier such as a compatible particulate substrate, a flexible ran particulate substrate or a container. Exaiples of ccnpatible 5 particulate substrates include inert materials such as clays and other aluminosilicates 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 or containers are manufactured such that the'containers prevent egress of their contents when dry but are adapted to release their contents on immersion in an aqueous solution.

A convenient execution of this form of the additive product IS comprises 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 coated with a water itperaoable protective material go as to retain the contents, such as is disclosed in European published Patent 20 Application No. 0018678. Alternatively it may be formed of a water insoluble synthetic polymeric material provided with an edge seal or closure designed to nature in aqueous media as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure 25 comprises a water soluble adhesive disposed along and sealing one edge of a pouch farmed of a water impermeable polymeric fila such as polyethylene or polypropylene.

An alternative fOra of the additive product comprises a compound as hereinbefore defined in water releasable combination with a nan 30 particulate flexible substrate in a weight ratio of lilO to 30<1. Additive products of this type.are disclosed in Patent Specification No . tfOrStf- andft2040983B and 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 structured integrity under the conditions of the Mash to be recovered fron the machine at the end of the .laundxy cycle. Structures Which are water disintagratahle, i.e. that break down in aqueous media to insoluble individual fibres or particles, are considered less satisfactory for the purposes of the present invention.

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

The substrate any have any one of a number of physical forms such as sheets, blades, rings, balls, rods or tubes. Such forms should be amenable to unit usage by the consumer, i.e. they should be capable of addition to the washing liquor in measured amounts, such as individual sheets, blocks or balls and wit lengths of rods or tubes. Certain of these substrate types can also be adapted far single or multiple uses, and can be provided with loadings of organic peraxy acid precursor to a precursor: substrate ratio of 30:1 by weight.

One sudi article comprises a aponga material rieleasably enclosing enough organic peraxy compound precursor to provide bleaching action during several washing cycles. This multi-use article con un m'm by iipregnating a sponge ball or block with about 20 grans of the precursor and ary adjuncts therewith. In use, the precursor leaches out through the pores of the qaonge into the wash liquor and reacts with the inorganic peraxy bleach. Such a filled sponge aan be used to treat several loads of fabrics in conventional washing machines, and has the adwntage 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 mate 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 apposite 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 32 count/unit length, such as is used for surgical dressings, or of the type known as cheese doth. loading limitations ion sheet type substrates limit the amount of precursor ooapound that can be applied to the sheet and, in practice, the weight S ratio of precursor ocnpound:sheet substrate nornally lies within the range from 1:2 to lOtl.

Variations on the above sheet substrate product forms are also aonteaplated for the purposes of the present invention. For exanple, laminated sheet products can be 10 employed in which a central layer is impregnated and/or coated with a oonposition incorporating the bleach precursor and then one or more outer layers are applied to produce a fabric-like aesthetic effect. The layers nay be sealed together as as to remain attadwd during use or may separate IS on contact with water to facilitate the release of the coated or impregnated material.

An alternative laminate form aoaprises one layer wnbonwd or deformed to provide a series of pouch-like containers into each of which the bleach precursor and optionally other 20 detergent coeponents are deposited in maasursd amounts, with a second layer overlying the first layer and sealed thereto in those areas between the poud»-lika containers where the two layers are in contact. The bleach precursor and any anrmmaiying components may be deposited in particulate, 25 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. The layers may separate or nay remain attached together on contact with water, the only requirement being that the structure should permit rapid 30 release of the contents of the pouch-like containers into solution. The ranter 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 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 5 present invention ccnqprises an absorbent foam like Material in the fin of a sheet. The term 'absorbent foam-like material' is intended to enccupass three dimensional absorptive materials such as 'gas blown foams', natural sponges and composite fibrous based structures audi as axe 10 disclosed in US Patent Kb. 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 exaqale of this foam type comprises a hydrophilic polyurethane foam of density 0.036 y/an3 with a cell count of between 8 and 40 cells per cm, preferably fran 24 to 32 per cm available from the Scott Paper Ooqpaiy, Eddysbone, Pennsylvania USA., tnder the Registered Trade Hark 20 "Hydrofoam". Preferred sheets of this type of material have thicknesses in the range from 3 to 5 ma.

Preferred sheet substrates for use in this type of additive product are apartured and ncn apertured nan woven fabrics whidi can generally be defined as adhesively banded 25 fibrous or filamentous products, having a web or carded fibre structure (where the fibre strength is suitable to allow carding) or comprising fibrous nats, 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 -30 orientation of the fibres is frequently present as well as a completely haphazard distributional orientation) or substantially aligned. The fibres or filaments can be 34 natural (e.g. wool, silk, mood pulp, jute, heap, cotton, linen, sisal, or raaie), synthetic (e.g. rayon, cellulose, ester, polyvinyl derivatives, polyolefins, polyamides, or polyesters) or mixtures of any of the above. 5 The choice of binder-resins used in the manufacture of non-woven cloths can provide substrates possessing a variety Of desirable traits. For exaxple, the absorbent capacity of the cloth can be increased, decreased, or regulated by respectively using a hydrqphilic binder-resin, a lydrcphbbic 1° binder-resin or a mixture thereof in the fibre bonding step. Macecwar, the hydrophobic binder-resin, (ten used singly or as the predominant compound of a hydrdixiiic-hydrophilic mixture, provides non-woven cloths tAiicb are especially useful as substrates When the precursor-substrate 15 confeinaticna disclosed herein are used in an autonatic washer.

When the substrate herein is a banded nan-woven cloth made fron fibres, deposited haphazardly or in randan array on the screen, the compositions exhibit excellent strength in all directions and are not prone to tear or separate when 20 used in the Masher.

Preferably, the non-woven cloth is Hater-laid or air-laid and is cade fro cellulosic fibres, particularly fron regenerated celluloee or rayon, which are lubricated with standard textile lubricant. Preferably the fibres are fron 4 25 to 50 nn in length and are fron 1.5 to 5 denier (Denier is an internationally recognised unit in yarn measure, corresponding to the weight in grans of a 9,000 neter length of yarn). Preferably the fibres are at least partially orientated haphazardly, particularly substantially 30 haphazardly, and are adhesively banded together with hydrophobic or substantially hydrophobic binder-resin, particularly with a nonionic self-crosslinking acrylic polyner or polymers. Conveniently, the cloth conprises 70% fibre and 30% binder-resin polyner by weight and has a basis 35 weight of frcn 10 to 100, preferably fron 24 to 72 g/m2.

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

A suitable diamond patterned apertured substrate is obtainable free Chloopoe Manufacturing Co., Mllltown, Haw Jersey, USA under the Code No. SC 650 WX 577 and conprising a polyester-wood pulp- mixture having a basis weight of 50 2 g/m and approximately 13 apertures per square an. 10 Another preferred emple of an apertured non-woven substrate, also available frcm Chicopee Manufacturing Co., under the Code No. AK 30 (C. 1379 oooprises a regenerated rnllnlnnn sheet of 0.33 Tex fibres banded with Etaoplex RA 8 binder (fibreibinder ratio 70i30) having a basis weight of 40 2 2 g/m and 17 apertures/cm . A highly preferred square patterned apertured substrate of similar composition but fibreibinder ratio of 80i20 and basis waic^it 35 g/m2 is also available from Chiccpee BV Holland.

In general, apertured fabrics for the purposes of the 2 invention have from 10 to 20 apertures/an , preferably 12-18 2 apertures/cm • The sin and shape of the siiastrate sheet is a matter of choice and is determined principally fcy factor* associated with the convenience of its use. Thus the sheet should not 25 be so small as to taaooma trapped in the crevices of the machine or the clothes being washed or so 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 on to 1300 cm are acceptable, the preferred area lying in the rang* of from 520 an2 to 780 cm2.

Additive products in particulate substrate form can ccsprise powders, flakes, chips, tablets or noodles which may be used aa-is or may themselves be encloeed in oontainers for addition to an aqueous liquor.

More usually, additive products in accordance with the invention contain other detergent ingredients in addition to the hereinbefore defined ocmpounds. 36 The type and level of audi optional materials is ocnstrained 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. This 5 inposes a maxima 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 spatially 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 ^ 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.

Highly desirable optional components are solid, water 30 soluble or water dispersible organic processing aids of a waxy nature having a tf>t 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 sifcstrate and ideally are non-hygrosccpic solids that are nixed with the precursors and melted to provide mixtures having a viscosity of ip to 30,000 centipoises at 30 50*C.

Typical solids are Cy-Cjj primary and secondary alcohols and fatty acids and ethoxylates thereof containing from 15 to 80 ethylene oxide groips per mole of alcohol, sorbitan esters of C^-Cjq fatty acids and 35 polyethylene glycols of Mbt 4,000-10,000. As stated hereinbefore, preferred materials are those of low hygroscapicity particularly the C^-C^g saturated fatty acids.

The Cj£~Cjg fatty acids and polyethylene glycols of 40 MWt 4,000-8,000, are particularly effective when used in amounts sucil that the weight ratio of conpounds:pcocessing aid lies in the range 20:1 to 1:2 particularly 4:1 to 1:1. 37 In addition to the foregoing optional components that are of prinary value in incorporating the precursor onto, euid rele&sing it fron, 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, delating agents, anti-redeposition and soil suspending agents, optical brightoners, bactericides, anti-tarnish agents, enzymatic materials, fabric softeners, antistatic agents, perfumes and 10 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 compositions IS oaqarise a peraxy bleach precursor compound as hereinbefore defined disposed on a substrate of either particulate or non particulate form, the substrate is preferably absorbent and the composition is inpregnated 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 acyloocybemzene sulphonate or oarboocylate precursors are solid at temperatures in excess of 150*C, one form of application is by solution in organic solvents which are volatilised after implication, whilst another enplcys a 25 slurry or suspension of the finely divided solid in water or other liquid media.

Preferred compositions in accordance with the invention are substantially anhydrous and thus incorporation on the substrate is best accomplished by utilisation of a non 30 aqueous liquid meditat.

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

Where the substrate comprises a rxxi-sheet like reticulated foam article, direct impregnation of the article fcy a liquid medium incorporating the dispersed precursor, either alone or with other components of the formulation can 3H be used, employing methods known in the art and described in gore detail hereinafter. Where the substrate comprises a non-woven material or a foam article of sheet-like form, it is preferred to mix the bleach precursor with a compatible 5 non-taygrosoapic material of melting point <;80*C, such 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 10 molecular weight >4000 make them useful for this purpose.

Where nonionic surfactants font components of the composition, their physical properties nay peimit their use as, or as part of, a liquid medium in vhich the precursor and other solid components are incorporated. 15 As previously indicated, materials reactive towards the penalty 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 form, such as sodium perborate monohydrate and tetrahydrate, aadiua percarbonate, sodiun persilicate or sodium perpyrcphoqphate, 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 on 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 vtoich 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 temperature in the range 40* to 60*C. Using this technique, bleach:substrate weight ratios of up to 15:1 can be obtained. TOiis level of loading is attainable with »9 cellular substrates but substrates of fibrous character tend to be United in practice to bleach:substrate weight ratios of no more than 8sl. Furthermore, loading limitations i«T»3Bed by the substrate surface area required for the 5 incorporation of the precursor may limit the amount of bleach to less than than this and bleadi:substrate weight ratios in the range 5:1 to 1:2 are normally employed. Provision must also be made far the separation of the bands or areas of bleadi and the corresponding bands or areas of precursor 10 during transport and/or storage. This is adiieved by 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 IS forms of detergent additive product is ty applying a spray of the composition as a solution, dispersion, or molten suspension, en 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 precursar(s), dissolved or dispersed in a molten processing aid, are held in a trough farmed ty the nip of two horizontal rolls arranged side by side and rotating in apposite 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 same as that of the roll and whidi contacts the roll over a limited length of its 30 periphery. The impregnated substrate is then contacted by a smoothing and spreading roll having a direction of rotation such that its contact surface is moving in the apposite direction to that of the substrate. The rolls employed in this tedmique are fabricated in metal and are heated to 35 maintain the inpnegnating mixture in the liquid phase.

A further aspect of the present invention comprises a bleaching composition composed of a precursor compound as hereinbefore defined in combination with a source of hydrogen peroxide in the form of an alkali metal inorganic peraxy salt 40 or a hydrogen peroxide clathrate or oospoeed of the peraxy 40 acid derived from the precursor compound in combination with a stabilising agent.

In the embodiment comprising a mixture of the precursor and a source of alkaline hydrogen peroxide it is very 5 desirable that the two components be isolated fron each other in order that a reaction does not occur prior to use.

Although a reaction oan be prevented fcy making an artydxous mixture of the two components, the maintenance of such a mixture in the anhydrous state is very difficult wder normal 1° storage conditions. A preferable technique is to separate the components physically, ty coating one or both with inert materials that dissolve or disperse in aqueous media, by incorporating each in separate or coapartnental packaging, or fcy fixing each ccnponent to separate locations an a non 15 particulate substrate. 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 from 30% to 95% fcy weight of the hydrogen peroxide source aid 70% to 5% 20 fcy weight of the precursor compound as hereinbefore defined; rare generally fron 50% to 90% of hydrogen peroxide source and fron 50% to 10% of precursor coopound, most preferably fron 75% to 90% of hydrogen peroxide source and fron 25% to 10% of precursor compound.

Where the peroxy acid derived fron the precursor compound is eeplcyed 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, Sennewold et al USP 3,442,937, and Cann USP 3,192,255. A preferred system enploys a mixture of 8-hydroxy quinoline and an acid pyrophosphate salt in a ratio of fron 1:1 to 5:1. The stabilising agents are incorporated 35 at a level of fron 0.005% to 1.0% ty weight of the composition.

In addition, exothezm control agents are also preferred components of solid bleaching compositions incorporating 41 organic peraxy acids, preferred examples of such agents including boric acid as disclosed in Hutdiins et al USP 4,1100,095, or hydrated inorganic salts as disclosed in Nielsen USP 3,770,816.

The present invention also embraces the formation of aqueous bleaching liquors fcy means of the reaction of a source of alkaline hydrogen peroxide with additive products containing precursors of an aliphatic peraxy acid whose oarboxylic acid analogue has a log of fron 1.9 to 4.1 10 particularly with the C^-C^g branched alkyl grcup-containing precursor compounds specifically described above, or by Beans of the addition of the above-described detergent or bleaciiing compositions to an aqueous medium. Aqueous bleaching liquors in accordance with this aspect of 15 the invention develop low intensity or bland odours which are oompatihle with, and/or are capable of being masked by, the perftsse compositions conventionally used in detergent 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 puigent odour which is aesthetically undesirable.

In addition to the non linear precursor ccspcunds of the present invention, products and compositions made in 25 accordance with the invention may optionally contain any of the organic peraxy 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 c^-c^ acyl 30 oxybenzene sulphonate or carboxylate with peracetic acid precursors are preferred, exaiples of such peracetic acid precursors including tetra acetyl ethylene diamine, tetra acetyl methylene dianine, tetra acetyl glycouril, 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 peraxyphthalic acid precursors where different combinations of bleaching properties are required. 42 In blends of the preferred branched acl'1 ootybenzene sulphonate precursors with other peroxyacid precursors it has been found that the Cg-C^ acyl axybenzene sulphonate should preferably be pruauiiL in an 5 amount to provide a level of at least 2 ppm and preferably at least 5 ppn available oxygen in the wash liquor, in order that the benefit of the Cg-C^0 peraxy acid can be realised. Generally the weight ratio of the Cg-C^ acyl cxxybenzene sulphonate precursor to the other peraxy acid 10 (e.g. peracetic acid) precursor should be such as to provide a Cg-Cyj aliphatic peraxy acid :peracetic 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. tinder European washing conditions, blends in which the Cg-C^ acyl axybenzene 15 sulphonate delivers fron 5 to 15 ppm available oxygen in the wash liquor are preferred.

The level of usage of the precursor will naturally be dependent cn a muter of factors e.g. the size of the fabric load in the madiine, the level of bleaching performance 20 desired, the amnt of perhydraxyl ion in the wash solution, the bleaching efficacy of the organic peraxy species derived from the precursor and the efficiency of conversion of the precursor into that peraxy species, it is conventional with inorganic peraxy bleaches to provide a level of available 25 oxygen in solution fron 50 ppm to 350 ppa by weight for heavy duty laundry purposes. However, When using organic peroxy bleaches a level of available oxygen provided ty the organic peraxy aoqpound may lie in the range from 1 ppa to 50 ppet, levels of from 1.5 pgn to 16 ppm being appropriate under 30 conventional US washing conditions while levels of from 20 ppa to 50 ppm are more ccsnonly 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 exqslqyed. 35 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 peraxy canpound percursar assuming quantitative conversion.

Various aspects of the invention are illustrated in the 40 following Exaiples in which all parts and percentages are by weight unless otherwise specified. 43 IS 40 Cj2 LAS : Sodiisa linear C12 alkyl benzene sulphonate C13 IAS Sodiimi linear Cjj alkyl benzene sulphonate ASC Disodiun salt of ot -sulphonated stearic acid TAS : Sodim tallow alcohol sulphate c14/15 : Sodium C14-CJ5 alkyl sulphate C12/14 AS : Sodium C12-C14 alkyl sulphate TAE,, : Tallow alcohol ethoxy lated with n moles of ethylene oxide per mole of alcohol C141M\B : C14 alkyl trinethyl anaonium bromide C14 TOWS : C14 alkyl trinethyl ammoniun methyl sulphate Cx2fRAB C12 alkyl trinethyl anmonium bromide A 45E7 : A ci4_i5 primary alcohol condensed with 7 moles of ethylene oxide.

A 23 B6.5 : A C12-C13 primary alcohol condensed with 6.5 moles of ethylene oxide.

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

FES : Polyethylene glycol (Mft normally follows) TAED : Tetraacetyl ethylene diamine PAS : Penta acetyl glucose ACBS Sodium p-acetoxy benzene sulphonate ISONOBS : Sodium 3,5,5 trimethyl hexanoyl oxybenzene sulphonate ISONOBA : Sodium 3,5,5 trimethyl hexanoyl oxytoenzoic acid EHOBS Sodium 2-ethyl hexanoyl oxybenzene sulphonate Silicate : Sodium silicate having an Si02:Na20 ratio of 1.6 Sulphate : Anhydrous sodium sulphate OTP Sodium tripolyphosphate Zeolite A Sodium aluminosilioate of formula Bai2(AXi02.SiO2)i227H2O. 44 Carbonate : CMC Silicone Ccspound: Silicone Prill : Nft/AA MVQA Perborate : Perborate t monohydrate Enzyme EDEA i OTA t Bricpitener 1 : Brightener 2 : DBITW EXOMP : 40 HjP2 I Clathrate Mixed Suds : Suppressor Anhydrous sodium carbonate Sodim cartaxyrathyl cellulose 85% polydimethyl silcxane 15% silica Coqprising 0.14 parts by weight of an 85115 by weight mixture of silanated silica and silicone, granulated with 1.3 parts of sodium 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 weicflit about 80,000. tfaleic arhydride/vinyl methyl ether copolymer, believed to have an average molecular weight of 240,000. This notarial, was prehydrolysed with MaCB before addition.

Sodium perborate tetrahydrate of nominal formula NaBO2.3H2O.H2Q2 Anhydrous sodium perborate bleach of empirical formula NaB02-H2O2 Mixed proteolytic and and amylolytic enzyme sold fcy Now Industrie AS.

Sodium ethylene diamine tetra acetate Sbdium nitrilotriacetate.

Diaodium 4,4'-bis(2-morpholino-4~ anilino-s-txia2in-6-ylanino) stilbene-212 '-disuljciionate.

Disodiun 4,4,-bis(2-sulphonato styryl) bipheryl Di ethylene triaaine penta (methylene phosphoric acid), marketed by Monsanto under the Trade name Dequest 2060 Ethylenadiamine tetra (methylene phosphorite acid), marketed by Monsanto, under the Trade name Dequest 2041 A clathrate of 4Na2®-*4 1 2H2O2 : INaCI % paraffin wax f$3t 5CPC, 17% hydrophobic silica, 58% paraffin oil. exam>iz i 45 Preparation of sodium 3,5,5 trimethyl hexanoyl oxybenzene sulphonate 100 gms of ddwdrated sodiun phenol sulfonate and 117 5 gms (30% niar excess) of iaanonanoyl chloride* (ex Akao BV, H*t 176.5) were weighed into a 2 litre conical flask. Hie flask was fitted with Magnetic stirrer are! 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 10 were added and the resulting suspension was stirred. 5 gns of tetrabutylamncniun bromide (supplied by Aldrich Chesical Co. Inc., Milwaukee, Wisconsin 53233, USA) were added as catalyst and the resulting suspension was 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 temperature, poured into 3 litres of diethyl ether and well washed using a Silverson stirrer. The solid material was filtered off by Budmer filtration and the resulting solid was washed with 20 2x2 litres of ether, filtering off after eadi wash. The resulting solid was dried over P^Og in a vacuum desiccator, was powdered in a coffee grinder and re-dried in a vacuum desiccator over PjO^. The yield was 140 gas and NMR analysis showed the solid to comprise 92% sodium 3,5,5 25 trinethyl hexanoyl oxybenzene sulphonate and 8% sodium phenol sulphonate.

*This is the canton tern used in the trade to describe 3,5,5-trimethyl hexanoyl chloride.

EXAMPLE 2 Preparation of sodium 3,5,5 trinethyl hexanoyl oxybenzolc acid The same apparatus was used as in Exanple 1. 74.5 g of p-hydroxybenzoic acid was nixed with lOOg of 3,5,5-trimethyl 46 hexanoyl dvLoride (5% molar excess) and 3.7 g of tetrabutyl ansoniua bromide catalyst. The nixture was stirred and heated tb 100*C in a current of nitrogen far 2 hours. Hie resultant white, porous, solid mass was cooled, broken vp 5 under petroleum ether (tp 40-60*C), filtered. Hashed and dried. The product, 126 g (84t) Mas found ty NMR analysis to be 95% 3,5,5-trinethyl hexanoyl axybenzoic acid and 5% p-hydraxy benzoic acid. examples 3-8 Detergent compositions incorporating a oonpound in aocordanoe with Exanple 1 have the following percentage formulations: 3 4 6 7 8 cu las - 6.0 4.7 - - 6.0 c^ias 4.0 - - 9.0 8.0 - c14/15 m 8.0 6.0 7.0 3.0 - 6.0 a45e7 - 2.0 2.1 2.5 - 2.0 c14u«b 2.0 2.0 2.1 - 1.5 2.0 1hab - - - 1.5 - - sip 24.0 24.0 18.0 32.0 24.0 12.0 ta/aa 1.5 1.7 - - 1.5 3.0 muqsv - - 1.0 0.5 0.5 - Silicate .0 .0 7.5 .0 7.5 .0 Carbonate .0 .0 .0 - 2.5 .0 BMP 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 Peraxy acid precursor 3.0 3.0 .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 .0 12.0 6.4 .35 15.0 Moisture + Misc.

To 100— Typically a spray dried base powder is made ocntaining the anionic and cationic surfactants, STP, inorganic salts, brightener, copolymer and EDTMP and then the remaining ingredients are incorporated ty spray on to the base powder of 47 nonionic, dry mixing (perborate) or via prill addition (peraxy acid precursor, silicone and enzyme).

An additional comparative formulation 4A was made lp in accordance with Exanple 4 except that the peraxy acid precursor had the structural formula Formulations 4 and 4A Mere eatfi mode tp 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 minutes. However, Whilst formulation 4A had a Strang 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 odcxir to the solution of formulation 4. bowles 9-14 The following formulations represent exaiiples of the detergent coaposition aspect of the invention. 48 9 10 U 12 13 14 US 4 8 8 - 7 5 C14/15AS 4 - - 9 - 3 TPS - " - 4 3 C12/14AS - - - - 2 - cu tmab -22-2- Dobanol 45-E-7 4 6 5 6 5 10 TREU 0.5 - - 2 TMS 0.5 - 6 lO Silicate 5 6 3 7 4 10 Mixed Suds Suppressor 2 - - 2 - 2 Silicone Prill 2 3 - 0.5 MVQft - - 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 cenw 0.3 - - - - 0.2 ECdMP - - 0.4 - - - Sodium Perborate 12 15 16 18 10 15 Enzyme 0.6 1 0.8 Sodium Tripolyphosptiate 30 28 25 32 28 30 Magnesium Sulphate - 0.5 - 0.5 ISCNQBS 2.5 4 - - 3 EH3BS - - 2 - 5 ISGtKXft 1.5 6 Sodium Sulphate, Moisture To 100 ■ and Miscellaneous EXBMmiS 15-20 Laundry additive products incorporating precursor compounds in water releanahle conbination with a sheet 30 substrate are prepared having the oaqpositions shown below in parts by weight: 49 16 17 18 19 ISCNOBS 7.6 .2 .5 8.4 4.2 .2 aa - - - 2.5 4.0 - TAB) - 3.6 - - - - AQBS - - - - - 3.0 A4SE7 .0 .0 .0 .0 .0 .0 FEB 8000 .0 7.0 8.0 8.0 6.0 6.0 C14TMB - 2.0 - - 2.0 - c14owo - - ~ 2.0 - 2.0 EDflMP 0.5 0.5 0.5 0.5 0.5 0.5 MVBA 0.3 0.3 0.3 0.3 0.3 0.3 Silicone OsyxiMd 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 each instance is a square patterned apertured non-woven sheet, of size 23 x 35 as and basis weight 2.8 g, formed of 100% unhleac&ed crimed rayon fibees (801 fibre, 201 polyacrylate binder). In the oase of and 17 the products are made ty forming a melt of tha PEG and A 45E7 at approximately 80*C, dispersing tha other cxMponents (except tha perfume) therein and applying the resultant slurry to the substrata frca an agplicatcr roll with Whic3i the substrate is brought into contact. Additional rolls are used to spread the slurry before it is cooled to ambient temperature to solidify the composition. Perfume is then sprayed an to the impregnated substrate to produce the final product.

Exaiples 16 and 18-20 use 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 M5E7 and 2.0 parts of PEG 8000 from the formulation to be applied as a separate stripe. example 21 SO A bleaching ccepositicn in the fan of the aliphatic peroxy acid derivative of the cxxqpomd of Exanple 1 ooapriaes: 3,5,5-tri methyl peroxyhexanoic acid 18.2% S Boric acid 67.8% 8-hydroxyquinoline 0.05% Disodiun dihydrogen pyrophosphate 0.05% Minors, including 10% sodium sulphate 13.9% 100.00 EXAMPUBS 22-26 The following fonulaticns are further detergent ocnpoaitions in accordance with one aspect of the invention. 22 23 24 26 LAS 4 8 C14/15 M 4 - - - - TAS 2 - ASC - - - Soap Dobanol 45-E-7 4 6 TAED 1 1 Silicate 3 7 4 Mixed Suds Suppressor 2 - - - .2 Silicone Prill - 2 3 - 0.5 MVHA - 0.8 1.5 - 1 UFA - 2.5 - 2.5 Brightener 1 0.3 0.4 0.3 0.2 0.2 bebw - - - - 0.2 EDIWP 1 - Sodium Pertorate 12 16 18 Enzyme 0.6 - - - 0.8 Zeolite A - - Carbonate - Sodium citrate - - - ISCNOBS 3 4 BOBS - - - - ISCNQBA - - Sodium Sulphate, Moisture To 100 and Miscellaneous

Claims (4)

1. CLAIMS 1.
2. An aqueous laundry bleaching liquor having a bland odour ccnprisirtg 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 per-axycarbaxylic acid precursor in an smcunt to give fron 1 to 50 ppn of the peroxycarbcoylic acid upcn reaction with said alkaline hydrogen per oxide source, said precursorhavlng the general fantula: R11 O wherein the gtoipi is an organic moiety of non-linear structural configuration, at least one of RU and R1^ being hydrogen, the other R11 and R111 being independently selected from hydrogen and Cj-C^ alkyl groups, the group: 52 being the acyl moiety of a oarboxylic acid having a logP^^ of fro* 1.9 to 4.1, wherein P is the partition coefficient of the carboxylic acid between n-octanol and water at 21"C, and L is a leaving group selected from:;- O )XY and b) - N - C -;f;Y;uharein Rj is an alkyl groqo containing fron 1 to 4 carbon a tons, x is 0 or an integer from 1 to 4 and Y is selected front;-ay;- CSOjM;- COjH;" N+(Rj)^Q~;-;wherein M is H, alkali natal, alkaline earth metal, arancnj.ua or substituted ameniun and Q is a halide or methosulphate,;the conjugate acid of said leaving group L having a pKa in the range from 6 to 13.;An aqueous laundry bleaching liquor according to claim 1 wherein the group R in the peroxycarboxylic acid precursor is a hydrooarbyl moiety.;93;
3. 3. An aqueous laundry bleaching liquor according to either one of claims 1 and 2 wherein ccnprises the groif>:;r1v i;R- C-;wherein R1V and RV are eadi independently selected from hydrogen and C^-C^ alkyl groifje, and the geixp s;R1V R11 i i R- C - C-;R111;* comprises a C.-C^6 alkyl groq? in whidi at least one of r U. R111. R and RV are C^-C^ alkyl, there being a linear alkyl chain of five or noce carbon atoms 10 extending fron and including the carbonyl carbon.
4. 4. An aqueous laundry liquor according to any one of claims 1-3 wherein the group: RU R^-C- 15 is a cg~cx2 ?ctx^3 wherein R1^" and R1U are hydrogen atoas. 54 5. An aqueous laundry liquor according to claim 4 wherein: R11 RX-C- k111 is a cyCg gratis. 6. An aqueous laundry liquor according to any one of claims 1-5 5 wherein the conjugate acid of leaving group L has a pKa in the range from 7 to 11. 7. An aqueous laundry liquor according to claim 6 wherein L has the formula a) in which Z is H, x is 0 and Y is -SO^M or -CO^H. 8. An aqueous laundry liquor according to claim 7 in which the group RU 0 • H lo Rj- C - C- RU1 is either 2-ethyl hexanoyl or 3,5,5 trimethyl hexanoyl. 9. A solid laundry bleaching canposition adapted to form an aqueous laundry bleaching liquor having a bland odour comprising a non-linear aliphatic, aryl aliphatic or alkanyl aliphatic peroxyacid precursor having a general formula as recited in any one of claims 1-6 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. 2Q 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 composition according to either one of claims 10 and II 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 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, 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 oaoprising a canposition incorporating a non linear aliphatic, aryl aliphatic or alkanyl aliphatic peroxycartooxylic acid precursor having a general foniula as recited in any one 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 inpernaable and is provided with a water uoflgitus 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 and 16 wherein the water frangible closure comprises a water soluble adhesive. 56 18. A laundry additive product adapted for addition to an aqueous laundry liquor containing a source of alkaline hydrogen peroxide, said product comprising a composition incorporating a non-linear aliphatic, aryl aliphatic or alkanyl aliphatic peroxyacid pre- 5 cursor having a general formula as recited in any one of claims 1-0, in water releasable ccrnbinaticri 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 0 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. 5 21. A laundry additive product according to any one of claims 14-20 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 to 1:5. A laundry additive product according to any one of claims 14-21 wherein the composition 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 comprising the step of adding a product in accordance with any one of claims 14-22 to an aqueous liquor containing a source 25 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. 22. 20 57 25. A laundry detergent bleaching coaposition adapted to Corn an aqueous laundry bleaching liquor according to claim 10 substantially as described with reference to Exaiples 3-14 and 22-26. 26. A laundry additive product according to claim 14 adapted Cor addition to aqueous laundry liquor containing a source oC alkaline hydrogen peroxide substantially as described with reference to Examples 15-20. Dated this the 9th day of November, 1988. BY: EXECUTIVE 27 Clyde Road, Ballsbridge, Dublin 4. AGENTS FOR THE APPLICANTS.