IE56906B1 - Detergent ingredients,and their use in cleaning compositions and washing processes - Google Patents

Description

This invention relates to the field of oxidisable stain removal, especially but not solely to the removal of oxidisable stains from fabrics and is particularly concerned with the removal of these stains using peroxygen bleaches at temperatures £60*C such as are encountered in domestic washing and laundering operations.

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

Recently , as described in European Published Application No. 0068547, it has been fotxid that selection of the chainlength of the aliphatic moiety of the peroxy acid permits the peroxy acid to be concentrated in the area there stain removal is required. Thus for removal of fugitive dyestuffs in bulk solution, a 'hydrophilic' bleach species is satisfactory, whereas for stains cn 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 No. 4412934 issued to Stanley Y Chung & Gianfranco L Spadini, on November 1st 1983 entitled Bleaching Ooepositions, and Fahertfc No. entitled Detergent Additive Product compositions are disclosed which incorporate a acyloxy conpound capable of forming a aliphatic peroxy acid on reaction with alkaline hydrogen peroxide, the acyl group being linear in nature.

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

It has naw been found that certain non-linear aliphatic peroxy acid precursors, when added to aqueous liquors containing a source of alkaline hydrogen peroxide, provide effective bleaching of oxidisable stains, particularly at temperatures at or below GO °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 complete inorganic peroxy bleach-containing detergent cospasition or as part of a laundry additive product added to an -aqueous solution of an inorganic peroxy bleach-containing detergent composition. Such conpositlons and additive products are described and claimed in Patent Specification No.

According to the invention therefore there is provided a non linear aliphatic peroacycarbaxylic acid precursor adapted to for· a non linear aliphatic peroxy acid in aqueous alkaline hydrogen peroxide solution wherein the precursor has the general fornula: r1- c- A-l i111 wherein the group: R11 r1- ei111 is an aliphatic hydrocarbyl organic moiety of non linear structural configuration, at least one of R11 and R111 being hydrogen, the other of R11 and R1X1 being independently selected fram hydrogen and alkyl groups, the group: RX10 R1- o- AAxxx containing at least five carbon atoms in a linear chain 15 extending from and including the carboryl carbon and being the acyl moiety of a oarboacylic acid having a logPoct of from 1.9 to 4.1, wherein PQct is the partition coefficient of the carboxylic acid between n-octanol and water at 21 *C, and L ia a leaving group having the formula lb wherein R? is an alkyl group containing from 1 to 4 carbon atone; x is 0 or an integer fron 1 to 4 and Y is selected frcms - SOgM -osoy* - CJOjM - N+(R2)3Q - N( R^-JO wherein M is H, alkali metal, alkaline earth metal >anmoniun or substituted ammxiium; and Q is halide or methosulphate, the conjugate add of said leaving group L having a pKa in the range from 6 to 13.

These leaving groups have a pKa more preferably in the range from 7 to 11, nost preferably fnsn S tc 10.

Preferred leaving grtxpe are those of formula a) above in wiiidh x is O and Y is selected frun -SO^M and -OO^ «herein M is an alkali netal preferably sodium.

Preferably the groqpt R11 R1- Cia a alkyl groqp and preferred compounds are alkali metal, anoniua or substituted aemonium 2-etlyl hexanoyl oxybenzene sulphonates and 3,5,5-trimethyl hexanoyl oxybenzene sulphonates, with sodlun being the preferred cation.

The coapounde found to be useful es organic peroxyacid bleach precursors have tha formula wherein the groqpt if i111 is an aliphatic hydrocarbyl organic moiety of non linear* structural configuration, at least one of R11 and R111 being hydrogen, the other of R11 and R111 being independently selected from hydrogen and C_-C i 4 alkyl groupe, the grovp: O v o* Pu containing at least five oarhon atoms in a linear chain extending from and including the carbonyl carbon and being ths acyl moiety of a carboxylic acid having a logP^ of from 1.9 to 4.1, wherein P^.L ls the partition coefficient of the carboxylic acid between n-octanol and water at 21 *C, and L ii a leaving grap the conjugate acid of which has a pKa in the range fron 6 to 13.

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

The effects of structure on the hydrophobicity of organic coapounds as represented ty 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 Lo^Pggp (there Fg^p is the partition coefficient between n-octanol and water) associated with the incorporation of various substituents into a range of structures. This permits a value for ^OCT to be predicted for any structure.

All of the conpounds display surface activity but this property is not very marked for coapounds in which the group R -C(R «XXA)- contains less than 8 carbon atone ani only those coapounds in which R^-CtR^R1·11)- contains more than 10 carbon atoms display detergent characteristics. Hydrocarbyl group branching confers increased solubility relative to linear compounds of the same number of carbon atoms and this increased solubility is associated with a decrease in surface activity relative to the corre^anding linear conpound. This effect also holds true for the aliphatic peroxy acids produced on perhydrolysis of the compounds. However, it has now surprisingly been found that aqueous liquors containing non linear aliphatic peroxy carboxylic acicfe in which non linearity preferably occurs on the 2arxl/or 3-carbon atoms with respect to the carhonyl carbon have a less intense odour of noire aesthetically acceptable character than those containing the corresponding linear aliphatic peroxyacids. 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 atoms further removed from the carbonyl carbon than the 3-carbon atom position is less.

ID beneficial for nee-cyclic aliphatic moieties where little or no odour benefit is seen for non linearity cosmencing at 5- or higher carbon atom positions relative to the carbonyl carbon. Accordingly, branching an 5- and hicher carbon atoms where the group r1- C(RURnl)X is a non-cyclic aliphatic acyl group is not believed to be crtt- jcXl· to the odour forming capability of the conpound. The reason for this difference in behaviour between branched and linear aliphatic peroxy acids is not wall understood and does not appear to be predictable.

The introduction of non linearity into the organic gxtxp R^R11*111)- also affects the rate of perhydrolysis of the precursor in alkaline hydrogen peroxide solutions.

Substitution and, in particular, di substitution of an adLkyl. grotp on the 2-carbon causes a lowering in the rate of perhydrolysis of the precursor because it hinders the approach of perbydroxyl ion and is believed to reduce the effectiveness of the percarboxylic acid as a bleach. Conpounds in accordance with the invention should therefore have at least one hydrogen atom on the 2-carbon atom. Non linearity on the 2-carbon is less preferred than on the 3-carbon where e-g. di alkyl substitution has much less effect on the perhydrolysis of the conpound whilst still providing an aliphatic peroxy acid of inproved odour.

One preferred forn of the group: R11 R1- Cwherein R1X and R111 are as previously defined, is thus the group: R1V R11 I I R — C — C — wherein RV A111 R1V and RV are each independently selected fron hydrogen and alkyl groups and the group: R — C- C — Rv A111 is a Cc-C1£ alkyl group in which at least one of 11 in 6iv6 v R R R and R are C^-C^ alkyl» there being a linear chain of five or nore carbon atoms extending frcm and including the carbonyl carbon· Preferably R1X and RXXX are each a hydrogen atom.

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

A preferred number of carbon atoms in the alkyl group: R1V R11 I ι R—C-C — AV RU1 is from 7 to 9 carbon atoms with a linear chain of from 5 to 10 8 caxbon atoms and with R1V and/or Ry conprising a side chain i.e. in the 3-carbon position with reepect to the carbonyl carbon atom.

The most preferred R groip 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 moiety.

Structures in accordance with the invention for the group where is aliphatic include: CH, 0 I 3 » CH,— C — CH- - CH — CH- - C — 3,5,5-trimethyl hexanoyl J , | CH3 ch3 I CH,(CH,),- CH - C - 2-ethyl hexanoyl3 2 3 , CH« I 2 CH c - (ch2)3 I c5-methyl hexanoylH 0 1 I CH3 - C - (CH2)4 c 6-methyl heptanoyΙοί the above,the 3,5,5-trimethyl hexanoyl structure is the most preferred for odour and rate of perhydrolysis with the -methyl hexanoyl and 6-methylheptanoyl structures being less preferred for odour and the 2-ethyl hexanoyl being less preferred for the rate of perhydrolysis· An example of a structure in accordance with the invention for the group R v- ill! κ— 1θ where incorporates a cyclo aliphatic or aromatic functionality is (0¾)^ cyclohexyl butyroyl “5 The leaving groip L must be capable of displacement from the bleach precursor eus a consequence of the nucleophilic attack on the bleach precursor by perhydroxyl anion generated fcy alkaline hydrogen peroxide. This, the perhydrolysis reaction, results in the formation of the percarboxylic acid. Generally, for a grop to be a suitable leaving group it must exert an electron withdrawing effect within the precursor molecule as this facilitates the nucleophilic displacement by the perhydroxyl anion.

Suitable leaving groups for this purpose have conjugate acid forms, the pKa of which should lie within the range from to 13. pKa values above 13 make the electron withdrawal effect so small as to be ineffective in promoting nucleophilic attack fcy perhydroxide anion, an exanple of such a leaving group being - OO^. pKa values below 6 reflect such a large electron withdrawal effect as 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 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 groups such as sulphonamide grcxps, having conjugate acid forms of the appropriate pKa, do not provide sufficient aqueous solubility to the precursor molecule and therefore do not give a sufficient rate of perhydrolysis to be practicable in a laundry detergent liquor.

The leaving grotpe L found to he useful in conpounds of the present invention are those having the formula a) or b) «»2>χΥ u N - C - R2 ch2 wherein R2 is an alkyl group containing fron 1 to 4 carbon atoms; x is 0 or an integer from 1 to 4 and Y is selected from: - so3M - OSO-M - «tyf» wherein M is H, alkali metal, alkaline earth metal amoniim or substituted aranoniiv; and Q is halide or methosulphate.

The preferred leaving group L has the formula a) in which x is 0, and Y is a sulphonate or earbaoylate.

The position of the solubilising group Y on the benzene ring in formula a) is not critical in that o -, m - and p-positians provide operable species. Nevertheless polar and steric factors make the o-substi tuted material most difficult to synthesise and of least value in that steric hindrance impedes the approach of perhydroxyl ion. In the preferred enfcodiment of leaving grocp L, there 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 oospounds of the invention can he illustrated generally by a sequence of reactions in which a α7~°17 acid θ1· chloride is formed in which the acyl group has the required branched structure and the subsequent reaction of this with a compound of formula a) above «herein the free bond is satisfied by a hydrogen atom.

The C7-CI7 acid cr 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 CRD syntheses can be used in *hich alpha-olefins are reacted with carbon monoxide and water in the presence of cobalt catalysts to form a mixture of acids of which 60-65% have either 2-methyl or 2-ethyl 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 temperature and pressure. The dimerisation of isobutene or the oodimerisation 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 by aldol condensation of the aldehyde followed by hydrogenation of the aldol condensation product and final oxidation. ttonufacture of the acid reactant used in the preparation of sodiun 3,5,5- tr imethyl hexanoyl axybcnzene sulphonate, a preferred compound in accordance with the invention, involves the condensation of two moles of butene to form diisobutene followed by carbonylation to produce the aldehyde and subsequent oxidation to form the isononanoic acid. This is then converted into the acid chloride in known nanner. The acid chloride is refluxed with sodium phenol sulphonate in a nitrogen current at 100-150*C for 10-20 hours to form the scdiun 3,5,5-trimetlyl hexanoyl benzene sulphonate.

Alternatively, the isononanoic acid can be transesterif ied, refluxing at 160-180*C with sodium phenol sulphonate and acetic anhydride in the presence of a small amount of sodium acetate catalyst, thereafter volatilising the by-product acetic acid and precipitating the sulphonate salt product from an organic solvent. A similar reaction procedure starting with n-ncnanoic acid is disclosed and claimed in Patent Specification No.

Similar procedures to the above are also enplcyed in the synthesis of sodiun 2-ethyl hexanoyl axybensene sulphonate.

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

Sodium 3,5,5-trimethyl hexanoyl oocybensoate and sodium 2-etlyl hexanoyl oocybenzoate are preferred menters of this class of oonpounds. Although the above compounds are described in terms of their sodium salts, other alkali metal and alkali earth metal cations and ammonium and substituted quaternary ammonium salts such as tri ^^3 anmoniun salts oan also be enplcyed.

This aspect of the invention is illustrated in the following description of the preparation of two oonpomds useful as organic peroxyacid bleach precursors. 1) Synthesis of sodiun 3,5,5-trimethyl hexanoyloxybenzene sulphonate Isononanoyl chloride of purity 95.8% and molecular weight 176.5 (supplied ty Akzo BV, Queens Road Hersham, Surrey, England) and sodium phenol sulphonate of purity £99.5% and MWt 196 (sipplied ty BEH Chemicals Ltd, Poole, Dorset, England) were used as the starting materials in the reaction. 19.62 gms of finely powdered, anhydrous eodium phenol sulphonate (l/lOth mole) and 22.06 gms of Akzo isononanoyl chloride (weight 1/lOth mole + 25% excess) were waited into a 500 ml conical flask containing 250 mis of chlorobenzene. The flask was fitted with a magnetic stirrer, a 2-way head carrying a N2 9s8 inlet (leading to the base of the flask) and a reflux condenser (+ CaCJLg ttfce) and was surrounded ty an oil-bath. The flask was heated with stirring to 120*C and with gas passing through the flask, was maintained at that tenperature overnight (20 hours). The heating was then turned off and the flask contents allowed to cool to room tenperature. The contents were then washed with 3x1 litre diethyl ether, filtering between each wash (a Silveraon stirrer was used for agitation). The resulting white solid was dried in a vacuus oven (no heat) after tAiich the product was ground into a fine powder and dried again in the vacuum oven. yields 27,40 gms (81.5% yield) nmr analysis showed 81.4% required conpound. 2) Synthesis of sodium 2-ethyl hexanoyl oxybenzene sulphonate 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 under nitrogen and heated to 160’C under reflux; vigorous boiling occurred and was maintained for 4.5 hours.

At this point the nitrogen lead was transferred from the IO 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 teeperature wee gradually increased to 260°C during 1.5 hours; the still-head temperature rose to 131*C. The contents of the reaction pot were then allowed to cod overnight to anbient teeperature before being washed with 3 x 1.5 litres diettyl ether, filtering between washes, and then being dried.

The yield of sodium 2-etfyl hexanoyl oxybenzene sulfbonate was 88.3g, 91.3% of theory.

Purity (fay cat. SO^ determination) - 93.4%.

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

A wide range of surfactants can be used in the present laundry oespositions. A typical listing of the classes and 30 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 polyethaocy ether sulphates, paraffin sulphonates, alpha-defin sulphonates, alpha-sulpho-carboxylates and their esters, alkyl glyceryl ether sulphonates, fatty acid monoglyceride sulphates and sulphonates, alkyl phenol polyethaocy ether sulphates, 2-acyloary alkane-l-sulphonates, and beta-alkylaxy alkane sulphonates. 18 A particularly suitable class of anionic surfactants includes Miter-soluble salts, particularly the alkali metal, ammoniian and alkanolammoniro salts of organic sulphuric reaction products having in their molecular structure an alkyl or alkaryl grotp 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 alkyl portion of acyl grope). Exanples of this group of synthetic detergents which form part of the detergent IO aonpositicns of the present invention are the sodium and potassium alkyl sulphates, especially those obtained by sulphating the higher aliphatic alcohols (£3-^3) produced by reducing the glycerides of tallow or coconut oil and sodlun and potassium alkyl benzene sulphonates, in which the alkyl grop contains from 9 to 15, especially 11 to 13, carbon atoms, in straight chain or branched chain configuration, e.g· those of the type described in U.S.P. 2,220,099 and U.S.P. 2,477,383 and those prepared from alkylbenzenes obtained by alkylation with straight chain chloroparaffins (using aluminium trichloride catalysis) or straight chain olefins (using hydrogen fluoride catalysis). Especially valuable are linear straight chain alkyl benzene sulphonates in which the average of the alkyl group is 11.8 carbon atoms, abbreviated as θ IAS, and £^2^15 methyl branched alkyl sulphates.

Other anionic detergent conpounds herein include the sodium c^q_jq alkyl glyceryl ether sulphonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulphonates and sulphates; and sodium cr potassium salts of alkyl phenol ethylene oxide ether sulphate containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl grope contain 8 to 12 carbon atone.

Other useful anionic detergent conpounds 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 group; water-soluble salts of 2-acyloxy-alkane-l-sulphonic acids containing fron 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulphates containing from 10 to 18, especially 12 to 16, carbon atoms in the alkyl group and from 1 to 12, especially 1 to 6, more especially 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 made fay reaction with sulphur trioocide followed ty neutralization under conditions such that any sultones present are hydrolysed to the corresponding hydroxy alkane sulphonates; water-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 be derived from natural sources such as coconut oil or tallow, or can be made synthetically as for exasple using the Ziegler or Oxo processes. Water solubility can be achieved ty using alkali metal, anmoniian or alkanolammonium cations; sodiisn is preferred. Suitable fatty acid soaps can be selected from the ordinary alkali metal (sodium, potassium), annonium, and alkylolasmonium salts of higher fatty acids containing from 3 to 24, preferably from 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, for instance, from soybean oil, castor oil, tallow, whale and fish oils, grease, lard and mixtures thereof. The fatty acids also can be synthetically prepared (e.g., ty the oxidation of petroleum, or ty hydrogenation of carbon monoxide ty the Fischer-Tropech process). Resin acids are suitable such as rosin and those resin acids in tall oil. Naphthenic acids are also suitable. Sodiian and potassiw soaps can be made ty direct saponification of the fats and oils or ty the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodiian 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 fron 5x1 to 1:5, preferably fro· 5:1 to 1:2, more preferably fron 3:1 to 2:3· Especially preferred is a 1:1 mixture of an alkyl benzene sulphonate having from 9 to 15, especially 11 to 13 carbon atone in the alkyl radical, the cation being an alkali metal, preferably sodium; and either an alkyl sulphate having fron 12 to 18, preferably 14 to 16 carbon atcsn in the alkyl radical or an alkyl ethoxy sulphate having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6, having an alkali metal cation, preferably sodium.

The nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) 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 or aromatic in nature and the length of the polyoxyethylene groqp tfrich is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble conpound having the desired degree of balance between hydrophilic and hydrophobic elements.

Examples of suitable nonionic surfactants include: 1. The polyethylene ocxide condensates of alkyl phenol, e.g. the condensation products of alkyl phenols having an alkyl group containing from 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 3 to 30, preferably 5 to 14 moles of ethylene oxide per mole of alkyl phenol. The alkyl substituent in such conpounds may be derived, for example, fron polymerised propylene, di-isobutylene, octene and nonene. Other exanples include dodecylphenol condensed with 9 moles of ethylene oxide per mole of phenol; dinanylphenol condensed with 11 moles of ethylene oxide per mole of phenol; nanylphenol and di-isooctylphenol condensed with 13 noise of ethylene oxide. 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 conprises between 9 and 18 carbon atoms and is ethoxylated with between 2 and 9, desirably between 3 and 8 moles of etlylene oxide per mole of aliphatic alcohol. The preferred surfactants are prepared from primary alcohols which are either linear (such as those derived from natural fate or, prepared hy the Ziegler process from ethylene, e.g. myristyl, cetyl, stearyl alcohols), or partly branched such as the Lutensols, Dobanols and Neodols which have about 25% 2-methyl branching (Lutensol being a Trade Name of BASF, Dobanol *and Neodol being Trade Names of Shell), car Synperonics, 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 exanples 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, Syrperonic 6, Synperonic 14, the condensation products of coconut alcohol writh 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 writh an average of between 7 and 12 molee of ethylene oxide per mole of alcohol, the tallow portion conprising essentially between 16 and 22 carbon atoms. Secondary linear alkyl ethoxylates are also suitable in the present conpositions, 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.

* Trade Mark Useful nonionic surfactants also include those in which ethylene oxide is condensed with a hydrophobic base fanned fay 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 Pluronic ^supplied hy Wyandotte Chemicals Corporation.

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

Cationic surfactants suitable for use herein include quaternary amnonium surfactants and surfactants of a semi-polar nature, for exanple amine oxides. Suitable quaternary ammonium surfactants are selected from mono Cg-C^, preferably C^-C^ N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted hy methyl, hydroxyethyl or hydroxyprapyl groups. Suitable amine oxides are selected from mono Cg-C^Q* preferably N-aUqrl or alkenyl amine oxides and propylene-1,3-diamine dioxides therein the remaining H positions are again substituted hy methyl, hydroxyethyl or lydroxypropyl groups.

The detergent oonpositions can comprise from l%-70% hy weight of surfactant, but usually the surfactant is present in an amount of from 1% to 20%, more preferably from 5-15% ly weight. Mixtures of surfactant types are preferred, particularly anionic-cationic mixtures. Particularly preferred mixtures are described in British Patent No. 2040967 and Patent Specification No. wj13 .

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

Suitable inorganic peroxygen bleaches include sodium perborate mono and tetra hydrate, sodiun percarbonate, sodium persilicate and the clathrate 4Na2S04 : 2¾¾ : * Trade Mark lNaCl. 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 amomt of from 1% to 40%, more preferably from 5% to 35% fcy weight of the composition and will most frequently be present in an amount of from 10% to 30% fcy 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 fcy the source to precursor compound is greater than 1.5:1, normally at least 2.0. under the usage conditions enoomtered in domestic European laundry practice, this molar ratio is generally greater than 5.0:1 and meet preferably is greater than 10:1.

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

Suds suppressors useful in the detergent conpositicn aspect of the invention, particularly cospoeitions used in laundering fabrics, are represented hy materials of the silicone, wax, vegetable and hydrocarbon oil and phosphate ester varieties. Suitable silicone suds 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 am /s (cSt), and mixtures of siloxanes and hydrophobic silanated (preferably trimethylsilanated) silica having a particle size in the range from 10 millimicroineters to 2 millimicroineters 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 77*C by ASTM-D1321, and also paraffin waxes, synthetic waxes and natural waxes. Suitable phosphate esters include mono- and/or di-C^-C^ alkyl or alkenyl phosphate esters, and the corresponding mono- and/or di alkyl or alkenyl ether phosphates containing vp to 6 ethoxy groups per molecule· Suds sippressors are normally included at levels of from 0.01% to 5% by weight of the coepoeition, dependent on the type of suds suppressor used, more conmonly 0.1% to 2% by weight.

A highly preferred component of detergent oonpoeitions in accordance with the invention is one or more detergent builder salts vdiich may comprise vp to 90% of the composition, more typically from 10% to 70% by weight thereof. Suitable detergent builder salts useful herein can be of the polyvalent inorganic and polyvalent organic types, or mixtures thereof. Non-limiting exanples of suitable water-soluble, inorganic alkaline detergent builder salts include the alkali metal carbonates, borates, phosphates, pyrophosphates, tripolyphoephates and bicarbonates.

Exanples of suitable organic alkaline detergency builder salts are water-soluble polycarboxylates auc£i as the salts of nitrilotriacetic acid, lactic acid, glycollic acid and ether derivatives thereof as disclosed in EE -A- 821,368, 821,369 and 821,370; succinic acid, malonic acid, (ethylenedioxy)diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic acid and funaric acid; citric acid, aconltlc acid, citraccrdc acid, carbasymethyloKysuccinic acid, lactaxysuccinic acid, and 2-cay-l,l»3-prcpane tricarboxylic acid; oxydisuccinic acid, 1,1,2,2-ethane tetracarboxylic acid, 1,1,3,3-prcpane tetracarboxylic acid and 1,1,2,3-propane tetracarboxylic acid; cyclopentane cis, cis,cis-tetraoarboxylic acid, cyclcpentadiene pentacarboxylic acid, 2,3,4,5-tetrahydrofuran-cis, cis, cia-tetraoarboxylic acid, 2,5-tetrahydrofuran-cis-dicarboxylic acid, 1,2,3,4,5,6-hexane-hexacarboxylic acid, mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in GB -A- 1,425,343.

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

A further class of builder salts is the insoluble alumino silicate type vhich 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£(A102)z(SiO2)^.adl2O 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. Compositions incorporating builder salts of this type form the subject of GBrA-1,429,143 pihlished Iferch 24, 1976, EE-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 oan also be present. The alkali metal silicate is preferably from 3% to 15%. Suitable silicate solids have a molar ratio of SiO^alkali meta^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, nitrilotriacetic and ethylene diamine tetra acetic acids and their salts, organic phosphorate derivatives such as those disclosed in Diehl US Patent No. 3,213,030 issued 19 October, 1965; Roy US Patent No. 3,433,021 issued 14 January, 1968; Gedge US Patent No. 3,292,121 issued 9 January, 1968; and Bersworth US tetent Nb. 2,599,807 issued 10 June, 1952, and carboxylic acid builder salts such as those disclosed in Diehl US Patent No. 3,308,067 issued 7 March, 1967.

Preferred chelating agents include nitrilotriacetic add (ΝΈΑ), nitrilotrimethylene phosphonie acid (N1MP), ethylene diamine tetra methylene phosphonie acid (STOP) and diethylene triamine penta methylene phosphonie acid (ΕΕΓΡΜΡ), and these are incorporated in amounts of from 0.1% to 3%, more preferably 0.2% to 2% ly weight of the composition. 2β Antiredeposition and eoil suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and tydroxyethyloellulose, and homoor co-polymeric poiyoarboxylic acids or their salts in which the poiyoarboxylic acid comprises at least two carboxyl radicals separated from each other ty not mace than two carbon atone. Polymers of this type are disclosed in GB-A-1,596,756. Preferred polymers include copolymers or salts thereof of maleic anhydride writh ethylene, methylvinyl ether, acrylic acid or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer.

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

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. Photoactivators are discussed in EF-A-57088, highly preferred materials being zinc phthalocyanine tri- and tetra-sulphonates.

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

Anionic fluorescent brightening agents are well-known materials, exanples of which are disodiun 4,4 ,-bis-(2-diethanolamino~4~anilino-s-triazin-6--ylainino) stilbene-2:2'disulphcnate, disodiun 4,4*-bis-(2-morpholino-4anilino-e-triazin-6-ylamino ) stilbene-2:2 '-disulphcnate, disodiun 4,4' -bis- (2,4-dianilino-s-triazin~6-ylamino) stilbene-2:2'-di-sulphcnate, disodiun 4,4'-bis-(2anilino-4-(N-methyl-»-2-hydroxyethylaniino)-s-triazin-6-ylamino) stilbene-2,2'-di-sulphcnate, disodium 4,4*-bis-(4-phenyl —2,1,3-triazol-2-yl)-stilbene-2,2 '-disulphcnate, disodiun ΙΟ 4,4 * -his ( 2' -ani lino-4-( 1-methyl-2-hydrotxyetlylainino) -s-triazin6-ylamino) stilbene-2,2'disulphonate, sodium 2(stilbyl-4H(naptho-1' ,2* :4,5)-1,2,3-triazole-2M-sulphonate and di-sodium 4,4*-bis(2-sulphonato styryl)biphenyl.

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

A preferred fluorescer is the anionic material available frcm Ciba Geigy S.A. under the trade name Tinopal (BS (Trade Mark) and mixtures thereof with materials available under the trade names Tinopal EMS and Blarikophor MBBN* (Trade Mark), the latter being sold by Farbenfabrlken Bayer AG.

The non-linear aliphatic peroxy acid precursors of the present invention are normally eaployed at levels of from 1% to 15% by weight more preferably at from 1% to io% 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, meet 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 be formed into particulates by spray cooling, prilling, marumerising, agglomeration or granulation, either alone or together with a carrier material which may be organic or inorganic in type. Suitable inorganic materials include clays and other natural and synthetic aluminosilicates, as well as hydratable salts such as phosphates, carbonates and sulphates. Suitable organic materials include ethoxylated C^-C^g ai-oohola ar>d a^kyl phenols, polyethylene glycols of MWT 4,000-10,000, ^12^18 fatty and esters thereof with monohydric and polyhydric alcohols· In cne preferred method of manufacturing the precursor, disclosed in ’ Specif tc^/joo No. , the liquid reaction product containing the precursor is blended with the carrier material under an inert gas atmosphere before being processed further to form the particulate material to be added to the detergent. This technique is particularly suitable when the carrier is a waxy organic solid such as an ethoxylated alcohol or ester and a highly preferred exanple, eaploying a glyceryl mono C^q-C^ fatty acid ester carrier is disclosed in the Applicants* Published European Application No. 0 123 423.

Patent In another method of manufacturing the preferred alkali metal branched chain acyl oxybenzene sulphonate phenol sulphonate precursors, one of the reaction components e.g. alkali metal phenol sulphonate or fatty acid is enployed in a greater excess than is necessary to achieve the desired completeness of reaction. The excess reactant is used as a binder material for the reaction product which is taken from the reactor and, without separate crystallisation or solvent extraction steps, is compacted to form particulates thich can IO 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' Patent Specification No. and Published European Application No. 0 106 634.

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

The peroxy add precursors of the present invention can also be incorporated into detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent tions and may contain any of the conponents of such conpositions, although they will not conprise all of the conponents present in a fully formulated detergent oanpoeiticn. 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. sa Additive products in accordance with this aspect of the present invention may oosprise the coxpound alone in combination with a carrier such as a compatible particulate substrate, a flexible non particulate substrate or a container. Exanples of cospatible 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 bags or containers are manufactured such that the containers prevent egress of their contents then dry but are adapted to releaee their contents cn immersion in an aqueous solution.

A convenient execution of this form of the additive product cooprises a particulate solid compound as hereinbefore defined enclosed in a container. Usually the container will be flexible, such aa a bag cr pouch. The bag may be of fibrous construction coated with a water ixpermeable protective material so as to retain the contents, such as is disclosed in European published Patent Application No. 0018678. Alternatively it nay be formed of a water insoluble synthetic polymeric material provided with an edge seal or closure designed to npture in aqueous media, as disclosed in European published Patent Application Nos. 0011500, 0011501, 0011502, and 0011968. A convenient form of water frangible closure coeprises a water soluble adhesive disposed along and sealing one edge of a pouch formed of a water iapermeable polymeric film such as polyethylene or polypropylene.

An alternative form of the additive product aosprises a ccnpound as hereinbefore defined in water releasable combination with a non particulate flexible substrate in a weight ratio of 1:10 to 30sl. Additive products of this type are disclosed in Specif ication Να .

British Published Patent Application No. 2,125,453.

The substrate may itself be water soluble or water insoluble and in the latter case it should possess sufficient structural integrity 0 under the conditions of the wash to he 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 less satisfactory for the purposes of the present invention.

Water soluble materials include certain cellulose ethers, alginates, polyvinyl alcohol and water soluble polyvinyl pyrrolidone polymers, which oan 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, qronges and films.

The substrate may have any one of a number of physical forms such as sheets, blocks, rings, balls, rods or tubes. Such forms should be amenable to unit usage ty 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 unit lengths of rods or tubes. Certain of these substrate types oan also be 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 ccnprises a sponge material releasably enclosing enough organic peroxy compound precursor to provide bleaching action during several washing cycles. This multi-use article oan 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 can be used to treat several loads of fabrics in conventional washing machines, and has the adrontage that it can remain in the washer after use.

A highly preferred execution of this type of additive product utilises a flexible sheet eo as to mate it compatible with the movement of the fabrics ih the washing machine and to facilitate its handling during manufacture of the product. Preferably the sheet is water pervious,,!.e. water can pass from ons 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 ootnt/unit length, such as is used far surgical dressings, ar of the type known as cheese cloth. Loading limitations on sheet type substrates limit the amount of precursor conpound that can be applied to the sheet and, in practice, .the weight ratio of precursor conpoundxsheet substrate normally lies within the range from 1x2 to 10x1.

Variations on the above sheet substrate product forms are also contemplated for the purposes of the present invention. For exanple, laminated sheet products can be employed in which a central layer is iapregnated and/or coated with a oonposition incorporating the bleach precursor and then cne 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 on contact with water to facilitate the release of the coated or iapregnated material.

An alternative laminate form oanprises one layer embossed or deformed to provide a series of pouch-like containers into each of which the bleach precursor and optionally other detergent components are deposited in measured amounts, with a second layer overlying the first layer and sealed thereto in those areas between the pouch-like containers where the two layers are in contact. The bleach precursor and any acconpanying components 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. The layers may separate or may remain attached together on contact with water, the only requirement being that the structure should permit rapid release of the contents of the pouch-like containers into solution. The nunfcer 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.

Aa stated above, suitable nmterials Which can be used ae 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 ccsprises an absorbent foam like material in the form of a sheet. The term 'absorbent foam-like material' is intended to enconpass three dimensional absorptive materials such as 'gas blown foams', natural sponges and composite fibrous based structures such as are disclosed in US Patent Nos. 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 preferred exanple of this foam type comprises a hydrophilic polyurethane foam of density 0. 036 g/cra^ with a cell count of between 8 and 40 cells per cm, preferably from 24 to 32 per cm available from the Scott Paper Cdnpany, Eddystone, Pennsylvania USA., under the Registered Trade Mark Hydrofoem. Preferred sheets of this type of material have thicknesses in the range from 3 to 5 mm.

Preferred sheet substrates for use in this type of additive product are apertured and non apertured non woven fabrics whidi can 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 oonprising 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 ccnpletely haphazard distributional orientation) or substantially aligned. Tbe fibres or filaments can 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 cloths can provide substrates possessing a variety of desirable traits. FOr exanple, the absorbent capacity of the doth can be increased, decreased, or regulated by respectively using a hydrophilic binder-resin, a Tydrophobic binder-resin or a mixture thereof in the fibre bonding step. Moreover, the hydrophobic binder-resin, when used singly or as the predominant conpound of a hydrophobic-hydrophilic mixture, provides non-woven cloths which are especially useful as substrates when the precursor-substrate conbinaticns disclosed herein are used in an automatic washer.

When the substrate herein is a banded nan-woven cloth made from fibres, deposited haphazardly or in random array an the screen, the coepositians 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 made from cellulosic fibres, particularly from regenerated cellulose or rayon, which are lubricated with standard textile lubricant. Preferably the fibres are from 4 to 50 ran in length and are from 0.15 to 0.55 Tex (1.5 to 5 denier) (Denier is an internationally recognised unit in yam measure, corresponding to the weight in grains of a 9,000 meter length of yarn). Preferably the fibres are at least partially orientated haphazardly, particularly substantially haphazardly, and are adhesively banded together with hydrophobic or sihstantially hydrophobic binder-resin, particularly with a nonionic self-crosslinking acrylic polymer or polymers. Conveniently, the cloth comprises 70% fibre and 30% binder-resin polymer by weight and has a basis 2 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. Exenplary apertured non-woven substrates are disclosed in US Patent Nos. 3,741,724, 3,930,086 aid 3,750,237.

A suitable diamond patterned apertured substrate is obtainable from Chicopee Manufacturing Co., Milltown, New Jersey, USA under the Code No. SK 650 WX 577 and conprising a polyester-wood pulp mixture having a basis weight of 50 g/m and approximately 13 apertures per square an.

Another preferred example of an apertured non-woven substrate, also available from Chicopee Manufacturing Go., under the Code No. AK 30 ML 1379 conprises a regenerated cellulose sheet of 3.0 denier fibres banded with Rhoplex BA 8 binder (fibrexbinder ratio 70:30) having a basis weight of 40 2 g/m aixi 17 apertures/cm . A highly preferred square patterned «pertured substrate of similar oonposition but 2 fibrexbinder ratio of 80:20 and basis weight 35 g/m is also available from Chioopee BV Holland.

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

The size and shape of the substrate sheet is a matter of choice and is determined principally hy factors associated with the convenience of its use. Thus the sheet should not be so small as to become trapped in the crevices of the machine or the clothes being washed or so large as to he 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 2 2 cm to 780 cm · Additive products in particulate substrate form oan ccnprlse powders, flakes, chips, tablets or noodles which may be used as-is or may themselves be enclosed in containers for ^addition to an aqueous liquor.

More usually, additive products in accordance with the invention contain other detergent ingredients in addition to the hereinbefore defined coepounds. 3S 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, or a carrier, ty the loading limitations of the substrate. This 5 inposes a maxinun weight ratio of optional ingredients to substrate of about 10:1, and in the case of coated sheet sihstrates of about 8:1. As described in more detail hereinafter, materials that are capahle of reaction with the precursor oan be incorporated in additive products of the present invention but it is essential that the precursor is epatially separate therefrom, i.e. is diqxssed 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 or waxy and of high or low melting or softening point.

Highly desirable optional conponents are solid, water 20 soluble or water dispersible organic processing aids of a waxy nature having a Mpt in the range 30-80*C. The most preferred processing aids have a softening point greater than. 40C 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-hygroscopic 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 primary and secondary alcohols and ^^^20 ^att^ acids and ethoxylates thereof containing from 15 to 80 ethylene oxide groups per mole of alcohol, sorbitan esters of fatty acids and polyethylene glycols of Mwt 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 cf Wt 4,000-8,000, are particularly effective when used in amounts such that the weight ratio of ccxpoundssprocessing aid lies in the range 20:1 to 1:2 particularly 4:1 to 1:1.

In addition to the foregoing optional components that are of primary value in incorporating the precursor onto, and releasing it from, the substrate, conventional detergent ingredients can be incorporated into the conpositicn provided that they are not reactive towards conpounds as hereinbefore defined. Thus, surfactants, suds modifiers, chelating agents, anti-redepositicn and soil suapending agents, optical brighteners, bactericides, anti-tarnish agents, enzymatic materials, fabric softeners, antistatic agents, perfuses and bleacdi 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 comprise a peroxy bleach precursor oospound, as hereinbefore definedi disposed an a substrate of either particulate or non particulate form, the substrate is preferably absorbent and the coeposition 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 150*C, one form 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 media.

Preferred oppositions axe ·· substantially anhydrous and , thus incorporation on the substrate is best acoonplished by utilisation of a non aqueous liquid medium.

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

Where the substrate emprises a non-sheet like reticulated foam article, direct inpregnaticn of the article by a liquid mediun incorporating the dispersed precursor, either alone or with other conpanents of the formulation can be used, enploying methods known in the art and described in more detail hereinafter· Where the substrate oosprises a non-woven material or a foam article of sheet-like form, it is preferred to mix the bleach precursor with a compatible non-hygroscopic 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 antVor ae a dispersed phase. The melting point range and waxy nature of polyethylene glycols of molecular weight >4000 make them useful for this purpose.

Where nonionic surfactants form conponents of the conposition, their physical properties nay permit their use as, or as part of, a liquid medium in which the precursor and other solid conponents are incorporated.

As previously indicated, materials reactive towards the peroxy bleach precursor conpounds 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 bleaches vhieh either contain water or hydrogen peroxide in tydrogen bonded form, such as sodium perborate monohydrate and tetrahydrate, sodium percarbonate, sodium persilicate or sodium perpyrophoephate, 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 ty applying the melt or suspension to separate webs of substrate which are subsequently joined longitudinally. Preferably the bleach is applied as a dispersion of solid particles in a molten processing aid (as hereinbefore described) at a teaperature in the range 40* to 60*C. Using this technique, bleachssubetrate weight ratios of ip 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 bleach:substrate weight ratios of no more than 8:1· Furthermore, loading limitations inposed by the substrate surface area required for the incorporation of the precursor may limit the amount of bleach to less than than this and bleachssubstrate weight ratios in the range 5:1 to 1:2 are normally enployed. Provision must also be made for the separation of the bands or areas of bleach and the corresponding bands or areas of precursor during transport and/cac storage. This is achieved 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 forms of detergent additive product is by applying a spray of the conpositicn as a solution,dispersion,or molten suspension, on to a moving bed of particulate substrate in a rotating drum or pan fluidised bed, or a rotating blade mixer of the Schugi or Patterson-Kelly type.

In a preferred netted of making sheet substrate additive products in accordance with the invention, the precursor(s), dissolved or dispersed in a molten processing aid, are held In a trough formed by the nip of two horizontal rolls arranged side by side and rotating in opposite directions such that 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 those speed is the same as that of the roll and which contacts the roll over a limited length of its periphery. The inpregnated substrate is then contacted by a smoothing and spreading roll having a direction of rotation such that its contact surface is moving in the opposite direction to that gf the substrate. The rolls enployed in this technique are fabricated in metal and are heated to maintain the impregnating mixture in the liquid phase.

Bleaching compositions can also be formulated oonprising a precursor conpound as hereinbefore defined in combination with a source of hydrogen peroxide in the form of an alkali netal inorganic pexray salt or a hydrogen peroxide clathrate . or oonposed of the perosy ΙΟ 3» acid derived from the precursor oospcund in combination with a stabilising agent.

In the embodiment conprising a mixture of the precursor and a source of alkaline hydrogen peroxide it is very desirable that the two oonponents be isolated from each other in order that a reaction does not occur prior to use. Although a reaction can be prevented ty making an arhydrous 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 s^arate the oonponents physically, ly coating one or both with inert materials that dissolve or disperse in aqueous media, ty incorporating each in separate or ocBpartmsntal packaging, or by fixing each component 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 ccnpositions of this type contain from 30% to 95% by weight of the hydrogen peroxide source and 70% to 5% ty weight of the precursor conpound as hereinbefore defined; more generally from 50% to 90% of hydrogen peroxide source and from 50% to 10% of precursor compound, most preferably from 75% to 90% pf hydrogen peroxide source and from 25% to 10% of precursor compound.

Where the peroxy acid derived from the precursor canpound is enplcyed in the bleaching conposition, 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 salt. Stabilising agents of thia type are disclosed in Sprout USP 2,838,459, Sennewald et al USP 3,442,937, and Gann USP 3,192,255. A preferred system eaplcys a mixture of 8-hydroxy quinoline and an acid pyrophosphate salt in a ratio of from 1:1 to 5:1. The stabilising agents are incorporated at a level of from 0.005% to 1.0% ty weight of the conposition.

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

The present invention also finds utility in the fonration of aqueous bleaching liquors by 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 Pqqj. from 1.9 to 4.1 particularly with the C^-C^g branched alkyl grocp-containing precursor compounds specifically described above, or by means of the addition of the above-described detergent or bleaching oonpositicns to an aqueous medium.

Aqueous bleaching liquors in accordance with this aspect of the invention develop low intensity or bland odours which are caspatihle with,and/or are capable of being masked by, the perfume ccnpoeitions 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 pungent odour which is aesthetically undesirable.

In addition to the non linear precursor conpounds of the present invention, products and ccnpoeitions 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 CQ-C1Q acyl oxybenzene sulphonate or oarbaxylate with peracetic acid precursors are preferred, examples of such peracetic acid precursors including tetra acetyl ethylene diamine, tetra acetyl methylene diamine, tetra acetyl glycouril, sodium p-nacetaxybenzene sulphonate, penta acetyl glucose, and octa acetyl lactose. However, the invention also contemplates blends of branched C^-C10 carbon chain-containing precursors with e.g. pexoxybenzoic and peroxyphthalic acid precursors where different combinations of bleaching properties are required.

In blends of the preferred branched Cq-C^q acyl axybenzene sulphonate precursors with other peroxyacid precursors it has been found that the acyl oocybenzene 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 wadi liquor, in order that the benefit of the Cg-C^Q Ρβ*01^ can be realised. Generally the weight ratio of the acyl oocybenzene sulphonate precursor to the other peroxy acid (e.g. peracetic acid) precursor ehould be such as to provide a C8^10 aliphatic peroxy acidzperacetic 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 “V1 oocybenzene sulphonate delivers frcm 5 to 15 ppn available oxygen in the wash liquor are preferred.

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

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 compound percuraor assuming quantitative conversion.

Various aspects of the invention are illustrated in the following Examples in which all parts and percentages are by weight unless otherwise specified.

EXftMPUS 1 Preparation of aoditm 3,5,5 trimethyl hexanoyl oocytaenzene 100 gms of dehydrated sodium phenol sulphonate and 117 gms (30% molar excess) of isononancyl chloride* (ex Akzo BV, M*t 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 hy Aldrich Chemical 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 was continued with nitrogen passing, for 19.5 hours.

The reaction mixture was then cooled to room tenperature, poured into 3 litres of diethyl ether and well washed using a Silverscn stirrer. The solid material was filtered off fay Buchner filtration and the resulting solid was washed with 2x2 litres of ether, filtering off after each wash. The resulting solid was dried over p2°5 a vacuum desiccator, was powdered in a coffee grinder and re-dried in a vacuum desiccator over P2°5* >Ι^Ίβ 108 140 9°8 and tWR analysis showed the solid to conprise 92% sodium 3,5,5 trimethyl hexanoyl oxybenzene sulphonate and 8% sodium phenol sulphonate.

♦This is the ccnmon teem used in the trade to describe 3,5,5 trimethyl hexanoyl chloride.

EXmE 2 Preparation of sodium 3,5,5 trimethyl hexanoyl oxybenzoic acid The ««we apparatus was used as in Exanple 1. 74.5 g of p-hydraxybenzoic acid was mixed with lOOg of 3,5,5-trimethyl hexanoyl chloride (5% molar excess) and 3.7 g of tetrabutyl annonium bromide catalyst. The mixture was stirred and heated to 100*C in a current of nitrogen for 2 hours. The resultant white, porous, solid mass was cooled, broken ip under petroleum ether (tp 40-60’C), filtered, washed and dried. The product, 126 g (84%) wae found ty NMR analysis to be 95% 3,5,5-trimethyl hexanoyl oxybenaoic acid and 5% p-hydroxy bensoic acid.

Claims (14)

1. 4«

1. A non linear aliphatic peroxycarboxylic acid precursor adapted to form a non linear aliphatic peroxy acid in aqueous alkaline hydrogen peroxide solution , the percursor haviixj the r R 1 —C— lli! o II C-L wherein the group: is an aliphatic hydrocartyl organic moiety of non linear structural configuration, at least one of R 11 and R 11 ' 1 being hydrogen, the other of R 11 and R 111 being independently selected from hydrogen and C^-C^ alkyl groups, the group: containing at least five carbon atoms in a linear chain extending fron and including the carbonyl carbon and being the acyl moiety of a carboxylic acid having a logP Qct of from 1.9 to 4.1, wherein Ρθ^ is the partition coefficient of the carboxylic acid between n-octanol and water at 21*C, and L is a leaving group selected from: a) and O II b) - N - C - Fj Y wherein 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: - Nd^y^o wherein M is H, alkali metal, alkaline earth metal anmonium or substituted ammonium and Q is a halide or methosulphate, the conjugate add of said leaving group 1« having a pKa in the range fron 6 to 13.

2. A non linear aliphatic peroxyoarbaxylic acid precursor according to claim 1, wherein R 1 ocnprlses the group: .IV R' therein R^ V and R V are each independently selected from hydrogen and alkyl grotps, and the group : R 1V R U I 1 ft- C - CA v ά 111 is a Cg-C. 6 alkyl . group in which, at least one of R 11 , R 111 , R 1V ^awd R V are Cj-C 4 alkyl, there being a linear alkyl chain of five or more carbon atoms extending from and including the carbonyl carbon.

3. A non linear aliphatic peroxycarboxyl ic acid precursor according to eitlicr of claims L or 2, wherein: R 11 rf- C— R 1U i:> a group wherein R*’® ;md 1 are cuih a hydnxjen atom.

4. A non linear aliphatic peroxycarboxyl ic acid precursor according to claim 3, wherein: R 11 R 1 -^A U1 is a Cy-Cg group.

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

6. * A conpound according to Claim 5, wherein the pKa is in the range from 8 to 10.

7. A conpound according to claim 5 or 6, wherein L has the formula a) given in Claim 1 in vhieh x is 0 and Y is -βΟ^Μ or GD ^ 4 * wherein M is as defined in Claim 1.

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

9. An alkali metal ammonium or tri ^3*^3 alkanolaranonium 3,5,5-tr ime thyl hexanoyl oxybenzene sulphonate.

10. 2-Ethyl hexanoyl oxybenzoic acid or an alkali metal, alkaline earth metal, ammonium or tri Cj-C^ alkanolamnonium salt thereof. U. 3,5,5-TrlmetlTyl hexanoyl oxybenzoic acid or alkali metal, alkaline earth metal, ammoniun or tri Cj-Cj alkanol ammonium salt, tliereof.

11. 12. A non-linear aliphatic peroxycarboxylic acid 5 precursor according to claim 1, substantially as hereinbefore described with particular reference to the accompanying Exanples.

12. 13. A process for preparing a non-linear aliphatic peroxycarboxylic acid precursor according to claim 1, l 0 substantially as hereinbefore described with particular reference to the accompanying Examples.

13.

14. A non-linear aliphatic peroxycarboxylic acid precursor according to claim 1, whenever prepared by a process claimed in claim 13.