WO1998056760A1

WO1998056760A1 - Peroxyacids

Info

Publication number: WO1998056760A1
Application number: PCT/EP1998/003666
Authority: WO
Inventors: John Oakes; David William Thornthwaite
Original assignee: Unilever Plc; Unilever N.V.
Priority date: 1997-06-10
Filing date: 1998-06-05
Publication date: 1998-12-17
Also published as: AU8338098A; EP0988283A2; BR9809977A; TR199902992T2; ZA985027B; CA2292894A1

Abstract

There is provided a cationic organic diperoxyacid having general formula (I) wherein: R1 and R2 are each independently an optionally substituted, linear or branched, C3-C10 alkyl or alkenyl group, or an optionally substituted aryl group; R3 and R4 are each independently a linear or branched C1-C4 alkyl group; p is 0 or 1; z is an integer selected from 0-3; y is an integer selected from 0-5; w is 0 or 1; and X- is a counter anion. The peroxyacid has been found to have good bleaching performance, including in conditions of alkaline pH.

Description

PEROXYACIDS

Field of the invention

The present invention relates to cationic peroxyacids and to compositions including these peroxyacids as bleaches, in particular detergent compositions used for washing fabrics.

Background of the invention

It is well known that organic peroxyacids can be used as bleacnmg agents m detergent compositions. Many different types of organic peroxyacids have oeen proposed such as peroxyoenzoic acid, peroxyphthalic acid, peroxyalkanoic acid and dιperoxyalκanedιoιc acids, described m US patents 4,110,095, 4,170,453, and 4,325,828. Other classes of peroxy acids which have been disclosed include amidoperoxyacids which contain a polar amide linkage part way along a hydrocarbon cnain (US Patents 4,634,551 and 4,686,063) and phthalimido-substituted peroxyalkanoic acids (EP-A-325,288) .

There is now an increasing interest m cationic organic peroxyacids, particularly for use in bleacning and detergent compositions, since, when compared to their non- catiomc counterparts, they (i) are more substantive;

(ii) have a better bleaching performance; and (iii) are pH-robust.

A range of peroxyacids comprising a quaternary ammonium group is described in Japanese patent application JP4-91075 (KAO) . In particular, this document discloses a range of materials of formula R, - (X)_m(Y)_n - N⁺ - R₄ - C-OOH . R₅ (0)_p -S0₃ ^"

R, O

wherein:

Rj_, is an optionally substituted, linear or branched, Ci-Cjo alkyl or alkenyl group or an unsubstituted or Ci-Cj_o alkyl- substituted aryl group; X and Y represent various groups; R₂ is an optionally substituted C^C^ alkyl group; R₃ is an optionally substituted Cj-Cj alkyl group; R₄ is an optionally substituted alkylene group,

-(CH₂)_h -OCH₂- ,

or -CH₂-C-0-(CH₂)₁- ;

II o h and k are integers from 0 to 3 ; 1 is an integer from 1 to 10; R₅ is a C₂-C₂₀ alkyl group, alkenyl group or alkyl - substituted or unsubstituted aryl group; and , n, and p are 0 or 1.

We have now found a group of peroxyacid compounds containing two C0₃H groups. These compounds were surprisingly found to have superior bleach activity, particularly under conditions of alkaline pH.

Definition of the invention The present invention provides a cationic organic diperoxyacid having the general formula (I) U0₂C-R_x- (C0NH)_p- (CH₂)_Z -N⁺- (CH₂) _y- (CONH) _w-R₂-C0₃H . X^" . (I)

R.

wherein:

R_: and R₂ are each independently an optionally substituted, linear or branched, C₃-C₁₀ alkyl or alkenyl group, or an optionally substituted aryl group;

R₃ and R₄ are each independently a linear or branched C₁-C₄ alkyl group; p is 0 or 1; z is an integer selected from 0-3; y is an integer selected from 0-5; w is 0 or 1; and

X^" is a counter anion.

If R_λ and/or R₂ are alkyl or alkenyl groups, preferably they are selected from optionally substituted linear or branched C₃-C₈ alkyl and alkenyl groups, as appropriate.

Suitable example optional substituents for R_x and R₂ include one or more halide groups, C_x-C₄ alkyl groups and Ci-C, alkoxy groups.

In preferred embodiments R₃ and R₄ are each a methyl group.

Preferably w = 0 when p = 1, or p = 0 when w = 1.

In cases where p = 0 and R_λ is an optionally substituted linear or branched alkyl or alkenyl group, preferably -R₁-(CH₂)_Z- provides an alkyl chain of up to about 10 carbon atoms. Typically, when R_x is alkyl or alkenyl and p = 0, then suitably z = 0. Similarly, in cases where w = 0 and R₂ is an optionally substituted linear or branched alkyl or alkenyl group, preferably -(CH₂)_y-R₂- provides an alkyl chain of up to about 10 carbon atoms. Also, when R₂ is alkyl or alkenyl and w = 0, then suitably y = 0.

In cases where p is 0 and R_λ is an optionally substituted aryl group, then z is conveniently at least 1, and possibly 2 or 3. If w is 0 and R₂ is an optionally substituted aryl group, then y is suitably at least 1 and may be 2 , 3, 4 or 5.

In some preferred embodiments z is 0, 1 or 3. z is suitably 3 when p is 1. y is also preferably 0, 1 or 5. y is conveniently 5 when w is 1.

In certain particularly preferred embodiments R is an optionally substituted aryl group, p = 1 and z = 3, y = 0, w = 0 and R₂ is an optionally substituted branched or unbranched alkyl or alkenyl group having from 5 to 10 carbon atoms, preferably from 5 to 7 carbon atoms.

In other preferred embodiments all of p, z, y and w are 0. In such embodiments R_x and R₂ are preferably selected from optionally substituted aryl groups and C₅-C₁₀ alkyl or alkenyl groups. In some embodiments it may be preferred for an aryl group of R_x and/or R₂ to be unsubstituted.

X" may be any suitable counter anion, particularly N0₃ ^", HS0₄", S0₄ ²", CH₃S0₄ ^", and R₅- (O) _q-S0₃ ^" , wherein R₅ is a C₂-C₂₀ alkyl group, alkenyl group, or alkyl substituted or unsubstituted aryl group, and q is 0 or 1. It is particularly advantageous to employ a counter anion selected from sodium dodecyl sulphate (SDS) , sodium fatty acid alpha sulphonate (SFAΞ) and tosylate, especially SDS and tosylate. The invention also provides a bleaching detergent composition, comprising from 3 to 40% by weight of one or more surface-active compounds, from 5 to 80% by weight of one or more detergency builders and an effective amount of a cationic diperoxyacid according to the present invention, as the bleach component.

The term "effective amount", as used herein, means that the cationic diperoxyacid is present in a quantity such that it is operative for its intended purpose, i.e as a bleaching agent, when the detergent composition is combined with water to form an aqueous medium which may be used to wash and clean clothes, fabrics and other articles. Preferably, the cationic diperoxyacids of the present invention, when present as the bleach component, will be present in bleaching detergent compositions in amounts of from 0.5 to 15% by weight, more preferably from 2 to 10% by weight.

According to a third aspect, the present invention provides a bleaching additive composition comprising from 50 to 90% by weight of a cationic diperoxyacid according to the present invention, as the bleach component.

Detailed description of the invention

As mentioned above, the cationic diperoxyacids of the present invention were found to exhibit superior bleach performance, particularly under conditions of alkaline pH. In addition to these advantages, the present cationic diperacids were found to be highly weight-effective (caused by the presence of two peracid groups per molecule) . The present cationic diperacids are expected to be biodegradable to a commercially useful level. Another advantage of the peroxy acids according to the present invention is that the route by which several of the materials are made is simple in that it is capable of utilising available starting materials.

Example preparation techniques and reaction routes are noted in more detail below. In brief, cationic diperoxyacids of the present invention may be prepared by reaction of an amine containing an acid or ester group (as appropriate) with a halide containing an acid or ester group (as appropriate) to form a quaternary ammonium diacid ester salt. This is subsequently peroxidised to form the desired cationic diperoxyacid.

The diperoxyacids of the present invention may find use in a wide range of industrial applications and processes, for example in the field of plastics as polymerisation initiators, or as oxidants for olefin epoxidation, or as bleaching agents in the paper industry.

They are also particularly useful as bleaching or cleaning agents in washing, cleaning and disinfecting compositions, such as laundry bleaches, hard surface cleaners, toilet bowl cleansers, automatic dishwashing compositions, denture cleaners and other sanitizing compositions.

The cationic diperoxyacids of the present invention find particular application in detergent compositions since they show good bleach performance at medium to low washing temperatures, that is 60 to 20° C. This means that detergent compositions containing such peroxyacids may readily be used at the medium to low wash temperatures which are becoming increasingly common.

Surfactants

The bleaching detergent compositions of the invention will contain at least one surface-active compound, which may be anionic, cationic, nonionic or amphoteric in character, present in an amount from about 3 to about 40%, pref-erably from 5 to 35% by weight.

Generally, mixtures of the above surface-active compounds are used. In particular, mixtures of anionic and nonionic surface-active compounds are commonly used. Amounts of amphoteric or zwitterionic surface-active compounds may also be used but this is not generally desired owing to their relatively high cost. If used, they will be present in small amounts.

The surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof. Many suitable actives are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

Synthetic anionic surfactants are well known to those skilled in the art. Examples include alkylbenzene sulphonates, particularly sodium linear alkylbenzene sulphonates having an alkyl chain length of C₈-C₁₅; primary (C₁₂-₁₅) and secondary alkyl sulphates (C₁₄-₁₈) , particularly sodium C₁₂-₁₅ primary alcohol sulphates; olefin sulphonates; alkane sulphonates; dialkyl sulphosuccinates; and fatty acid ester sulphonates.

It may also be desirable to include one or more soaps of fatty acids. These are preferably sodium soaps derived from naturally occurring fatty acids, for example, the fatty acids from coconut oil, beef tallow, sunflower or hardened rapeseed oil . Soaps may be incorporated in the compositions of the invention, preferably at a level, of less than 25% by weight. They are particularly useful at low levels in binary (soap/anionic) or ternary mixtures together with nonionic or mixed synthetic anionic and nonionic compounds . Soaps which may be used are preferably the sodium, or, less desirably, potassium salts of saturated or unsaturated C₁₀-C₂₄ fatty acids or mixtures thereof. Typically such soaps may be present at levels between about 0.5% and about 25% by weight, with lower levels of between about 0.5% to about 5% being generally sufficient for lather control. If the soap is present at a level between about 2% and about 20%, particularly between about 5% and about 10%, this can give beneficial detergency effects. The inclusion of soap is particularly valuable in detergent compositions to be used in hard water since the soap acts as a supplementary builder.

The preferred anionic surfactant is sodium C₁₂.₁₅ primary alcohol sulphate.

Suitable nonionic detergent compounds which may be used include the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example, aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide.

Specific nonionic detergent compounds are alkyl (C₆_₂₂) phenol-ethylene oxide condensates, the condensation products of linear or branched aliphatic ₈-_2o primary or secondary alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine . Other so-called nonionic detergent compounds include long-chain tertiary amine oxides and tertiary phosphine oxides.

Further suitable nonionic surfactants are alkyl polyglycosides of general formula R₄0 (R₅0) _t (G) _y in which R₄ is an organic hydrophobic residue containing 10 to 20 carbon atoms, R₅ contains 2 to 4 carbon atoms, G is a saccharide residue containing 5 to 6 carbon atoms, t is in the range 0 to 25 and y is in the range from 1 to 10. Alkyl polyglycosides of formula R₄0(G)_y, ie . a formula as given above in which t is zero, are available from Horizon Chemical Co.

Other suitable nonionic surfactants include O-alkanoyl glucosides described in International Patent Application WO 88/10147 (Novo Industri A/S) . Further possible hydrophobic nonionic surfactants are monoglyceryl ethers or esters of the respective formulae

0

R_R0CH₉CHCH,0H and R_flCOCH₂CHCH₂OH

OH OH

R₈ is preferably a saturated or unsaturated aliphatic residue .

The monoglyceryl ethers of alkanols are known materials and can be prepared, for example by the condensation of a higher alkanol and glycidol. Glycerol monoesters are of course well known and available from various suppliers including Alkyril Chemicals Inc. Detergency Builders

The bleaching detergent composition of the invention, will generally contain one or more detergency builders, suitably in an amount of from 5 to 80 wt%, preferably from 20 to 80 wt%. This may be any material capable of reducing the level of free calcium ions in the wash liquor and will preferably provide the compositions with other beneficial properties such as the generation of an alkaline pH and the suspension of soil removed from the fabric.

Preferred builders include alkali metal (preferably sodium) aluminosilicates , which may suitably be incorporated in amounts of from 5 to 60% by weight (anhydrous basis) of the composition, and may be either crystalline or amorphous or mixtures thereof.

Examples of phosphorus -containing inorganic detergency builders include the water-soluble salts, especially alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates . Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, orthophosphates and hexametaphosphates . Preferably such inorganic phosphate builders are present at levels of not more than 5 wt% of the composition.

Other builders may also be included in the detergent composition of the invention if necessary or desired: suitable organic or inorganic water-soluble or water-insoluble builders will readily suggest themselves to the skilled detergent formulator. Inorganic builders that may be present include alkali metal (generally sodium) carbonate; while organic builders include polycarboxylate polymers such as polyacrylates , acrylic/maleic copolymers, and acrylic phosphinates ; monomeric polycarboxylates such as citrates, gluconates, oxydisuccinates, glycerol mono-, di- and trisuccinates , carboxyτnethyloxysuccinates , carboxymethyloxymalonates , dipicolinates , hydroxyethyliminodiacetates ; and organic precipitant builders such as alkyl- and alkenylmalonates and succinates, and sulphonated fatty acid salts.

Especially preferred supplementary builders are polycarboxylate polymers, more especially polyacrylates and acrylic/maleic copolymers, suitably used in amounts of from 0.5 to 15 wt% and monomeric polycarboxylates, more especially citric acid and its salts, suitably used in amounts of from 3 to 20 wt%.

Other Ingredients

It is desirable that the compositions according to the invention be approximately neutral or at least slightly alkaline, that is when the composition is dissolved in an amount to give surfactant concentration of 1 g/1 in distilled water at 25°C the pH should desirably be at least 7.5. For solid compositions the pH will usually be greater, such as at least 9. To achieve the required pH, the compositions may include a water-soluble alkaline salt. This salt may be a detergency builder (as described above) or a non-building alkaline material.

Apart from the components already mentioned, the detergent compositions of the invention may contain any of the conventional additives in amounts in which such materials are normally employed in fabric washing detergent compositions. Examples of these components include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants such as alkyl phosphonates and silicones, anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted alkyl cellulose ethers; heavy metal sequestrants such as ethylene diamine tetraacetic acid and the phosphonic acid derivatives (ie Dequest^R types) , fabric softening agents such as fatty amines, fabric softening clay materials; inorganic salts such as sodium and magnesium sulphate; and, usually present in very small amounts, fluorescent agents, perfumes, enzymes such as cellulases, lipases, amylases and oxidases, germicides, colourants or coloured speckles and pigments .

Other optional, but highly desirable components ingredients which may be employed in the detergent composition of the invention include polymers containing carboxylic or sulphonic acid groups in acid form or wholly or partially neutralised to sodium or potassium salts, the sodium salts being preferred.

Preferably the polymeric material is present at a level of from 0.1 to about 3% by weight and has a molecular weight of from 1000 to 2000000 and may be a homo- or co -polymer of acrylic acid, maleic acid or salt or anhydride thereof, vinyl pyrrolidone, methyl or ethyl -vinyl ethers and other poly erisable vinyl monomers. Especially preferred materials are polyacrylic acid or polyacrylate, polymaleic acid/acrylic acid coplymer; 70:30 acrylic acid/hydroxyethyl maleate copolymer, 1:1 styrene/maleic acid coplymer; isobutylene/maleic acid and diisobutylene/maleic acid copolymers; methyl- and ethyl- -vinylether/maleic acid copolymers; ethylene/maleic acid copolymer; polyvinyl pyrrolidone; and vinyl pyrrolidone/maleic acid copolymer. Other polymers which are especially preferred for use in liquid detergent compositions are deflocculating polymers such as for example disclosed in EP 346995.

It may also be desirable to include in the detergent composition of the invention an amount of an alkali metal silicate, particularly sodium ortho-, meta- or preferably neutral or alkaline silicate, at a level of, for example, of 0.1 to 10 wt%

The cationic diperoxyacids of the present invention may be used in a variety of product forms including powders, on sheets or other substrates, in pouches, in tablets or in non-aqueous liquids, such as liquid nonionic detergent compositions .

When incorporated in a bleach and or detergent bleach composition the cationic diperoxyacids will preferably be in the form of particulate bodies comprising said cationic diperoxyacid and a binder or agglomerating agent. In such a form the cationic diperoxycid is more stable and easier to handle.

Many diverse methods for preparing such particulates have been described in various patents and patent applications such as, for example, GB 1,561,333; US 4,087,369; EP-A-0,240,057; EP-A- 0 , 241 , 962 ; EP-A-0 , 101 , 634 and EP-A-0, 062, 523, all of which are incorporated herein by reference. Any one of the methods described therein may be selected and used for preparing particulates comprising the cationic diperoxyacids of the invention.

When used in a detergent bleach composition, particulates incorporating the cationic peroxyacids of the invention are normally added to the base detergent powder in a dry-mixing process. However, it will be appreciated, the detergent base powder composition to which the peroxyacid part_.icles are added may itself be made by any one of a variety of methods, such as spray-drying, high energy mixing/granulation, dry-mixing, agglomeration, extrusion, flaking etc. Such methods are well known to those skilled in the art and do not form part of the present invention.

The cationic diperoxyacids of the present invention may also be incorporated in detergent additive products. Such additive products are intended to supplement or boost the performance of conventional detergent compositions and may contain any of the components of such compositions, although they will not comprise all of the components present in a fully formulated detergent composition. Such additive products containing, for example, up to 90% by weight of the cationic diperoxyacid and a surface active material maybe particularly useful in hygiene applications eg hard surface cleaners.

Additive products in accordance with this aspect of the invention may comprise the cationic diperoxyacid alone or in combination with a carrier, such as a compatible particulate substrate, a flexible non-particulate substrate or a container (e.g. pouch or sachet) .

Examples of compatible particulate substrates include inert materials, such as clays and other aluminosilicates, including zeolites both of natural and synthetic of origin. Other compatible particulate carrier substrates include hydratable inorganic salts, such as phosphates, carbonates and sulphates. Additive products enclosed in bags or containers can be manufactured such that the bags/containers prevent egress of their contents when dry but are adapted to release their contents on immersion in an aqueous solution.

The invention is further illustrated by way of the following non- limiting examples in which parts and percentages are by weight unless indicated otherwise.

Preparation Examples

Example 1

This concerns the preparation of 4 -Peroxycarboxybenzyl-6 ' - dimethyl ammonium - perhexanoic acid tosylate.

1.1 6-Bromo ethylhexanoate

6-Bromohexanoic acid (44g; 0.226mole) was dissolved in ethanol (150ml), p-toluene sulphonic acid (0.5g) was added and the solution refluxed for 7 hours. The reaction being followed by FT-IR. The solution was concentrated under reduced pressure to yield a brown oil (50g; yield=100%) . The oil was then dissolved in diethyl ether (200ml) and washed successively with saturated sodium bicarbonate solution (3 x 100ml) ; water (100ml) and brine (100ml) . The ethereal solution was dried over anhydrous sodium sulphate, filtered, washed with ether (100ml) and concentrated under reduced pressure to yield a clear yellow oil (45g; yield=89.5%) . Relevant FT-IR bands: 6-bromohexanoic- carbonyl band at 1710 cm"¹; 6-bromoethylhexanoate- carbonyl band at 1735 cm"¹. The product has a carbonyl at 1735 cm^"1. Purity by GLC=98.3%. ^:Hnmr (δ CDC1₃) 4.14, q, 2H, CH₂CH₃ ; 3.4, t, 2H, BrCH₂; 2.3, t, 2H, CH₂CO; 1.9, p, 2H, CH₂CH₂CO; 1.68, p, 2H, BrCH₂CH₂; 1.5, p, 2H, BrCH₂CH₂CH₂; 1.25, t, 3H, CH₂CH₃ ppm.

1.2 6-Dimethylamino ethylhexanoate

6-Bromoethylhexanoate (44g; 0.197mole) was dissolved in 33% dimethylamine/ethanol solution (150ml, large xs) and then refluxed for 7 hours. The brown solution was concentrated under reduced pressure to yield a brown oil . The ό^~il was dissolved in a sodium hydroxide solution (7.88g; 0.197mole) in water (50ml) then extracted with ether (3 x 100ml) . The ethereal fractions were combined washed with water (2 x 50ml) , brine (50ml) , dried over anhydrous sodium sulphate, filtered, washed and concentrated under reduced pressure to yield a clear brown oil (34.76g; yield=94%) . ^xHnmr (δ CDC1₃) 4.13, q, 2H, CH₂CH₃ ; 3.4, t ; 2.4, t, 2H, CH₂C0; 2.34, s, 6H, N(CH₃)₂; 2.3, t, 2H, CH₂N; 1.65, p, 2H, CH₂CH₂CO; 1.6, p, 2H, NCH₂CH₂; 1.38, p, 2H, NCH₂CH₂CH₂; 1.25, t, 3H, CH₂CH₃ ppm.

1.3 4-Carboxybenzyl-6 ' -dimethylammonium hexanoic acid tosylate

p-Chloro-4-toluic acid (8.35g; 0.05mole) was dissolved in propan-2-ol (50ml) with warming and this was added to a solution of sodium hydroxide (2g; 0.05mole in 50ml water). This mixture was then heated to 50°C and 6-dimethylamino ethyl hexanoate from 1.2 above (9.35g; 0.05mole) dissolved in propan-2-ol (20ml) was added over 15 minutes with stirring. On complete addition the solution was heated at 80°C for 2 hours. The solution was then filtered to remove any insoluble material and the filtrate concentrated under reduced pressure to yield an orange oil. The oil was then triturated with diethyl ether (3 x 100ml) decanted off and azeotrope with propan-2-ol to yield a sticky white solid. The solid was dissolved in water (100ml) and to this was added a solution of p-toluene sulphonic acid (13g; 0.07mole; 100ml water) giving an immediate white precipitate. The solid was filtered, transferred to a rotary flask and partially dried (2g removed for analysis) . The remaining solid was then added to a 3% solution of sulphuric acid (50ml) and refluxed for 14 hours. The yellow solution was then concentrated under reduced pressure to yield a viscous yellow oil. The oil was then boiled with acetonitrile until a white solid formed, cooled, filtered, washed with a little ether and dried in vacuo over phosphorous pentoxide (10.5g; yield=50%) . ^xHnmr (δ D₂0/DMSO) 8.13, d, 2H, C0Ar-H_; 7.68, d, 2H,

CH₂Ar-H; 7.64, d, 2H, CH₃Ar-H; 7.22, d, 2H, CH₃Ar-H; 4.55, s, 2H, CH₂Ar; 3.28, m, 2H, CH₂-N+; 3.0, s, 6H, N+Me₂ ; 2.4, t, 2H, H0₂C-CH₂; 2.4, s, 3H, CH₃Ar ; 1.9, m, 2H, H0₂CCH₂CH; 1.67, p, 2H, CH₂CH₂N; 1.4, p, 2H, CH₂CH₂CH₂N, ppm. 'Hnmr Assay (δD₂0/DMS0; trioxan) =98% based on tosylate anion. Material contains mixed anions : Tosylate and sulphate. Nmr ref : OR1021 LBN 9959/87.

1.4 4-Percarboxybenzyl-6 ' -dimethylammonium perhexanoic acid tosylate

4-Carboxybenzyl-6 ' -dimethylammonium hexanoic acid tosylate (3g, 0.0064m) was dissolved in distilled methane sulphonic acid (12g) and hydrogen peroxide 80% (2.31g, 0.065m) was added dropwise over 2mins with stirring, the maximum temperature recorded was 7°C. The mixture was allowed to come to room temperature and stirred for a further 5h. Ether (400ml) was added and an oily precipitate formed and the ether was decanted off and triturated with more ether (2x 100ml) . An aqueous solution of sodium tosylate (llg in 30ml) and a solution of toluene sulphonic acid (1.47g in water (50ml)) was added and a precipitate formed which was separated byh filtration, washed with water and dried in vacuo over P₂0₅ to give a solid (2.72g, 85% yield) . Peracid by titration = (96.8; 98.8%).

Ηnmr (δD₂0/DMSO) 8.1, d, 2H, COAr-H; 7.66, d, 2H, CH₂Ar-H; 7.64, d, 2H, CH₃Ar-H; 7.3, d, 2H, CH₃Ar-H; 4.5, s, 2H, CH₂-Ar; 3.25, m, 2H, CH₂-N+; 3.0, s, 6H, N+Me₂; 2.36, t, 2H, H0₃C-CH₂; 2.33, s, 3H, CH₃Ar; 1.85, m, 2H, H0₃CCH₂CH; 1.63, p, 2H, CH₂CH₂N; 1.35, p, 2H, CH₂CH₂CH₂N, ppm.^{" x}Hnmr Assay (δD₂0/DMS0; trioxan) = 98% based on tosylate anion.

Example 2

This concerns the preparation of 4 -Peroxycarboxy- terephthalamido propyl-3 ' -dimethylammonium- 6 ' ' -perhexanoic acid tosylate.

2.1 3-N,N-Dimethylamino-propyl terephthalamide methyl ester

mono-Methyl terephthalate (25.2g; 0.14mole) was added to thionyl chloride (100ml) . This mixture was then heated to reflux for 7 hours. The solution was concentrated under reduced pressure to yield a brown oil that solidified on cooling at room temperature. The solid was triturated with ether (3 x 200ml) , the ether decanted and the solid evaporated to dryness to yield a white solid (27g; yield=97%) . 3-Dimethylamino propylamine (13.9g; 0.146mole) was dissolved in acetonitrile (100ml) and cooled to 0°C. The acid chloride (27g; 0.136mole) was dissolved in acetonitrile (50ml) then added slowly dropwise to the cooled amine. The temperature was kept below 15°C during the addition by use of an ice bath. On complete addition the ice bath was removed and white suspension stirred at room temperature (21°C) for 4 hours. The suspension was concentrated under reduced pressure to yield a white solid (41g; yield=100%) . The solid was dissolved in 2N sodium hydroxide solution (68ml; 0.136mole) and then extracted with ethyl acetate (4 x 200ml) , dried over anhydrous sodium sulphate, filtered and evaporated to dryness to yield a buff solid (33.9g; yield=94.4%) . Ηnmr (δCDCl₃) 8.7, s, H, NH; 8.1, d, 2H, Ar-H, 7.8,^" d, 2H, Ar-H; 3.94, s, 3H, CH₃; 3.6, q, 2H, CH₂NH; 2.54, t, 2H, CH₂NMe₂; 2.3, s, 6H, Me₂ ; 1.8, p, 2H, CH₂CH₂N ppm.

2.2 4-Methylterephthalamidopropyl-3 ' -dimethylammonium-3 ' ' - ethylhexanoate tosylate

3-N,N-Dimethylamino-propyl terephthalamide methyl ester (15.84g; O.Oδmole) and 6-Bromo ethylhexanoate (13.38g; 0.06mole) were dissolved in acetonitrile (150ml) and then refluxed for 7 hours. The solution was concentrated under reduced pressure to yield a brown oil . The oil was triturated with ether (3 x 150ml) , the ether was decanted from the solid and the solid dried in vacua to yield a white solid (26.8g; yield=91.7%) . 4- Methylterephthalamidopropyl -3 ' -dimethylammonium-3 ' ' - ethylhexanoate bromide (10g; 0.021mole) was dissolved in water (50ml). p-Toluene sulphonic acid sodium salt (8.96g; 0.041mole) was dissolved in water (20ml) and then the two solutions mixed together. Water (30ml) was added to the cloudy solution and then left for 30 minutes at room temperature. The product did not precipitate as hoped, therefore the cloudy solution was extracted with dichloromethane (2 x 200ml) . The dichloromethane fractions were combined washed with water (50ml) , dried over anhydrous sodium sulphate, filtered and evaporated to dryness to yield a white solid (13g) . The solid was. triturated with ether (4 x 70ml) , decanted off and the solid evaporated to dryness to yield a white solid (10.77g; yield=91%) .

Ηnmr (δD₂0) 8.13, d, 2H, COAr-H; 7.89, d, 2H, COAr-H; 7.7, d, 2H, CH₃Ar-H; 7.37, d, 2H, CH₃Ar-H; 4.13, q, 2H, CH₂CH₃; 4.0, s, 3H, Me-O; 3.54, t, 2H, CONHCH₂ ; 3.4, m, 2H, CONHCH₂CH₂CH₂ ; 3.3, m, 2H, N+CH₂ (CH₂) ₄ ; 3.1, s, 6H, Me₂; 2.4, s, 3H, Me-Ar; 2.3, t, 2H, CH₂COOH; 2.13^", m, 2H, CONHCH₂CH₂; 1.7, m, 2H, CH₂CH₂COOH; 1.5, p, 2H, N+CH₂CH₂ (CH₂) ₃; 1.34, p, 2H, N+CH₂CH₂CH₂CH₂CH₂ ; 1.25, t, 3H, CH₂CH₃ ppm.

2.3 4-Terephthalamidopropyl-3 ' -dimethylammonium-3 ' ' - hexanoic acid tosylate

4-Methylterephthalamidopropyl -3 ' -dimethylammonium-3 ' ' - ethylhexanoate tosylate (10.77g; 0.0185mole) was added to 2N sodium hydroxide solution (18.5ml; 0.037mole) and water (25ml) . The solution was stirred at 40°C for 48 hours, p- toluene sulphonic acid (7.03g; 0.037mole) in water (20ml) was added resulting in a cloudy solution (pH=2-3) . The cloudy solution was concentrated to low bulk until a white solid was observed, cooled, filtered and dried in vacuo over P₂0₅ to yield a white solid (7.55g; yield=76%) . ^xHnmr (δD₂0) 8.10, d, 2H, COAr-H; 7.88, d, 2H, COAr-H; 7.6, d, 2H, CH₃Ar-H; 7.3, d, 2H, CH₃Ar-H; 3.5, t, 2H, C0NHCH₂; 3.35, m, 2H, CONHCH₂CH₂CH₂ ; 3.25, m, 2H, N+CH₂(CH₂)₄; 3.04, s, 6H, Me₂ ; 2.37, Ξ, 3H, Me-Ar; 2.3, t, 2H, CH₂COOH; 2.07, m, 2H, CONHCH₂CH₂ ; 1.7, m, 2H, CH₂CH₂COOH; 1.5, p, 2H, N+CH₂CH₂ (CH₂) ₃ ; 1.3, p, 2H, N+CH₂CH₂CH₂CH₂CH₂ ppm. FT-IR carboxylic carbonyl bands at 1710 cm^"1 and 1734 cm^"1. 2.4 4-Peroxycarboxy-terephthalamidopropyl-3 ' - dimethylammonium-6 ' ' -perhexanoic acid tosylate

4-terephthalamidopropyl-3 ' -dimethylammonium- 6 ' ' -hexanoic acid tosylate (3g, 0.0055m) was dissolved in distilled methane sulphonic acid (lOg) and hydrogen peroxide (1.9g, 0.056m) was added dropwise over 2mins with stirring, the maximum temperature recorded was 5°C. The mixture was allowed to come to room temperature and stirred for a further 5h. Ether (400ml) was added and an oily precipitate formed and the ether was decanted off and triturated with more ether (2 x 100ml) . An aqueous solution of sodium tosylate (5g in 20ml) and a solution of toluene sulphonic acid (1.55g in water (50ml)) were added and a precipitate formed which was separated by filtration and dried in vacuo over P₂0₅ to give a solid (2.2g, 70% yield) . Peracid by titration = (49%) . ^lR nmr Assay (D₂0/trioxan) =46% ; 24.8% CH₃S0₃H; 19.9% Sodium tosylate; (δ D₂0) 8.1, d, 2H ArH; 7.8, d, 2H ArH; 7.6, d, 2H ArH; 7.3, d, 2H ArH; 3.45, t, 2H CONHCH₂ ;

3.35, m, 2H CONHCH₂CH₂CH₂N⁺ ; 3.24, m, 2H (CH₂)₄CH₂N⁺; 3.05, s, 6H N⁺Me₂; 2.4, s, 3H ArMe ; 2.25, t, 2H CH₂COOOH; 2.05, m, 2H CONHCH₂CH₂CH₂N⁺; 1.65, m, 2H (CH₂) _SCH₂CH₂N⁺ ; 1.45, m, 2H CH₂CH₂COOOH; 1.3, m, 2H CH₂ (CH₂) CH₂CH₂N⁺ppm.

Example 3

This concerns the preparation of 4-peroxycarboxy- terephthalamidopropyl-3 ' -dimethylammonium-8 ' ' -peroctanoic acid.

3.1 4-Methylterephthalamidopropyl-3 ' -dimethylammonium-3 ' ' - ethyloctanoate tosylate 3-Dimethylamino propylamido methyl terephthalate (17g; 0.064mole) acetonitrile and 8-Bromo ethyloctanoate (16.2g; 0.064mole) were dissolved in acetonitrile (200ml) and then refluxed for 5 hours. The solution was concentrated under reduced pressure to yield an orange oil . The oil was triturated with ether (3 x 150ml) , the ether was decanted and the solid evaporated to dryness to yield a yellow solid. The solid was dissolved in water (100ml) and p- toluene sulphonic acid sodium salt (25g; 0.129mole) in water (50ml) was added. The solution was then extracted with dichloromethane (3 x 200ml) , dried over anhydrous sodium sulphate, filtered and dried in vacuo to yield a white solid (35g; yield=89.7%) . ^λU nmr (δD₂0) 8.10, d, 2H, COAr-H; 7.85, d, 2H, COAr-H; 7.6, d, 2H, CH₃Ar-H; 7.3, d, 2H, CH₃Ar-H; 4.1, q, 2H, CH₂CH₃; 3.9, s, 3H, Me-0; 3.4, t, 2H, CONHCH₂ ; 3.3, m, 2H, CONHCH₂CH₂CH₂ ; 3.2, m, 2H, N+CH₂(CH₂)₅; 3.0, s, 6H, Me₂; 2.3, s, 3H, Me-Ar; 2.2, t, 2H, CH₂COOH; 2.0, m, 2H, C0NHCH₂CH₂; 1.6, m, 2H, CH₂CH₂COOH; 1.4, m, 2H, N+CH₂CH₂(CH₂)₅; 1.2, p, 6H, N+CH₂CH₂ (CH₂) ₃CH₂CH₂ ; 1.2, t, 3H, CH₂CH₃ ppm.

3.2 4-Terephthalamidopropyl-3 ' -dimethylammonium-3 ' ' - octanoic acid tosylate

4-Methylterephthalamidopropyl-3 ' -dimethylammonium-3 ' ' - ethyloctanoate tosylate (10.3g; 0.017mole) was dissolved in sodium hydroxide solution [2.72g; 0.068mole; water (50ml)] and stirred at room temperature for 20 hours. p- Toluene sulphonic acid (12.92g; 0.068mole) in water (50ml) was added to give a cloudy solution. The solution was evaporated to dryness and dried in vacuo over P₂0₅ to yield a yellow solid (23.6g; contains xs p-toluene sulphonic acid sodium salt) . The solid was added to water (50ml) to give a slightly cloudy solution, cooled in an ice bath until crystallisation occurred. The solid was then filtered and washed with cold water (10ml) , dried in vacuo over P₂0₅ to yield a white solid (5.85g; yield=61%) . ^XH nmr (δD₂0) 8.10, d, 2H, COAr-H; 7.85, d, 2H, COAr-H; 7.6, d, 2H, CH₃Ar-H; 7.3, d, 2H, CH₃Ar-H; 3.5, t, 2H, CONHCH₂; 3.35, m, 2H, CONHCH₂CH₂CH₂ ; 3.28, m, 2H, N+CH₂(CH₂)₅; 3.05, s, 6H, Me₂ ; 2.4, s, 3H, Me-Ar; 2.3, t, 2H, CH₂COOH; 2.1, m, 2H, CONHCH₂CH₂ ; 1.7, m, 2H, CH₂CH₂COOH; 1.5, , 2H, N+CH₂CH₂ (CH₂) ₅ ; 1.2, p, 6H, ^" N+CH₂CH₂(CH₂)₃CH₂CH₂ ppm.

3.3 4 -Peroxycarboxy-terephthalamidopropyl-3 ' - dimethylammonium- 8 ' ' -peroctanoic acid tosylate

4-terephthalamidopropyl-3 ' -dimethylammonium- 8 ' ' -octanoic acid tosylate (3g, 0.0053m) was dissolved in distilled methane sulphonic acid (12g) and hydrogen peroxide 80% (1.8g, 0.0532m) was added dropwise over 2mins with stirring, the maximum temperature recorded was 5°C. The mixture was allowed to come to room temperature and stirred for a further 5h. Ether (400ml) was added and an oily precipitate formed and the ether was decanted off and triturated with more ether (2 x 100ml) . An aqueous solution of sodium tosylate (5g in 20ml) and a solution of toluene sulphonic acid (1.55g in water (50ml)) was added and a precipitate formed which was separated by filtration and dried in vacuo over P₂0₅ to give a solid (2.35g, 75% yield). Peracid by titration = (90; 89.4%). ^XH nmr Assay (D₂0/trioxan) =99% ; (δD₂0) 8.1, d, 2H ArH;

7.8, d, 2H ArH; 7.6, d, 2H ArH; 7.3, d, 2H ArH; 3.45, t, 2H CONHCH₂; 3.35, m, 2H CONHCH₂CH₂CH₂N⁺ ; 3.24, m, 2H (CH₂)₆CH₂N⁺; 3.05, s, 6H N⁺Me₂ ; 2.4, s, 3H ArMe; 2.25, t, 2H CH₂COOOH; 2.05, m, 2H CONHCH₂CH₂CH₂N* ; 1.65, m, 2H (CH₂ ) ₅CH₂CH₂2N⁺ ; 1 . 45 , , 2H CH₂CH₂COOOH ; 1 . 3 , m, 6H CH₂ ( CH₂ ) ₃CH₂CH₂N⁺ ppm .

Example 4

This concerns the preparation of 11-N, N-dimethyl ammonium- diperoxyundecanoic acid tosylate.

4.1 11-Bromo methylundecanoate

11-Bromoundecanoic acid (23g; O.lmole) was dissolved in methanol (150ml), p-toluene sulphonic acid (0.5g) was added and the solution refluxed for 7 hours. The reaction being followed by FT-IR. The solution was concentrated under reduced pressure to yield an oil (24g; yield=100%) . The oil was then dissolved in diethyl ether (200ml) and washed successively with saturated sodium bicarbonate solution (3 x 100ml) ; water (100ml) and brine (100ml) . The ethereal solution was dried over anhydrous sodium sulphate, filtered, washed with ether (100ml) and concentrated under reduced pressure to yield a clear oil (22g; yield=91%) . Relevant FT-IR bands: 6-bromohexanoic- carbonyl band at 1710 cm"¹,- 6-bromoethylhexanoate- carbonyl band at 1735 cm^"1. The product has a carbonyl at 1735 cm^"1. Purity by GLC=98.3%.

Ηnmr (δ CDC1₃) 4.4, s, 3H, COOCH₃ ; 3.4, t, 2H, BrCH₂ ; 2.3, t, 2H, CH₂CO; 1.9, p, 2H, CH₂CH₂CO; 1.68, p, 2H, BrCH₂CH₂; 1.5, p, 12H, BrCH₂CH₂ (CH₂) ₆. ppm.

4.2 11-Dimethylamino methylundecanoate

11-Bromomethylundecanoate (13.85g; 0.05mole) was dissolved in a 33% dimethylamine/ethanol solution (150ml, large xs) and then refluxed for 7 hours. The brown solution was concentrated under reduced pressure to yield a straw coloured oil . The oil was dissolved in a sodium hydroxide solution (7.88g; 0.197mole) in water (50ml) then extracted with ether (3 x 100ml) . The ethereal fractions were combined washed with water (2 x 50ml) , brine (50ml) , dried over anhydrous sodium sulphate, filtered, washed and concentrated under reduced pressure to yield a clear oil (12g; yield=96%) . G.C, 2 peaks rt 10.7 and 11.9 mins m/e 243 and 256 respectively corresponding to Methyl and Ethyl esters ratio 50:50. ^xHnmr (δ CDC1₃) 4.13, q, 2H, COOCH₂CH₃; 4.4, s, 3H COOCH₃; 3.4, t; 2.4, t, 2H, CH₂CO; 2.34, s, 6H, N(CH₃)₂; 2.3, t, 2H, CH₂N; 1.65, p, 2H, CH₂CH₂CO; 1.6, p, 2H, NCH₂CH₂; 1.38, p, 12H, NCH₂CH₂ (CH₂) ₆; 1.25, t, 3H, CH₂CH₃ ppm.

4.3 11-N.N-Dimethylammonium-di peroxy undecanoanoic acid tosylate

11-Bromomethylundecanoate (7.2g; 0.026mole) was dissolved in acetonitrile (30ml) and 11-N, N-dimethylamino methylundecanoate (6.5g, 0.026mole) was added and the mixture was refluxed for 7 hours. The solution was cooled and a solid material crystallised out of solution, this solid was separated by filtration and dried in vacuo (13.4g, 97% yield). Ηnmr Assay (δ CDCl₃/trioxan) =97% ;

4.4, s, 6H 2 x COOCH₃; 3.55, t, 4H, 2 x CH₂N⁺ ; 3.4, s, 6H, N⁺(CH₃)₂; 2.4, t, 4H, 2 X CH₂CO; 1.75, p, 4H, 2x N^*CH₂CH₂ ; 1.38, bs, 28H, 2x N⁺CH₂CH₂ (CH₂) ₇. ppm.

This solid (5.22g, O.Olmole) was dissolved in water (100ml) with methanol (20ml) and p-toluene sulphonic acid (lOg) was added. The solution was heated at 100°C for 12h after removal of the metanol a solid crystallised out of solution, this was removed by filtration and dried in vacuo (5.1g, 87% yield) IR 1722cm^"1 identified as the diacid. This diacid (2.94g, 0.005mole) was dissolved in distilled methane sulphonic acid (12g) and hydrogen peroxide 80% (6.0ml, 5x xs) was added dropwise over 2mins with stirring, the maximum temperature recorded was 5°C. The mixture was allowed to come to room temperature and stirred for a further 5h. This solution was poured into ice cold water (100ml) containing p-toluene sulphonic acid (lOg) . A precipitate formed which was separated by filtration and dried in vacuo (2.63g, 85% yield) . % peracid by titration = 98, 97.5; Ηnmr Assay (δ DMSODδ/trioxan) = 97%; ^"7.6 d, 2H ArH; 6.95, d, 2H ArH; 3.15, t, 4H, 2x CH₂N⁺ ; 3.0, s, 6H, N⁺(CH₃)₂; 2.2, s, 3H ArCH₃; 2.1, t, 4H, 2 CH₂COOOH; 1.75, p, 4H, 2x N⁺CH₂CH₂; 1.5, bs , 8H, 2x N⁺CH₂CH₂CH₂+ 2x CH₂CH₂COOOH; 1.15, bs, 20H 2xNCH₂CH₂CH₂ (CH₂) _s .ppm.

Bleaching Experiments

The bleaching efficacy of the diperoxyacid 4- peroxycarboxybenzyl-6 ' -dimethylammonium perhexanoic acid tosylate was investigated. This is the diperacid prepared in Example 1 above and has the formula

Me

H0₃C- oo CH₂- N⁺- (CH₂)₅C0₃H. OTS^"

Me

The bleaching experiments were carried out in a temperature- controlled glass vessel, equipped with a magnetic stirrer, thermocouple and a pH-electrode, at a constant temperature of 40°C.

The diperoxyacid prepared according to Example 1 (0.5 x 10^"3 M) was added to 100ml demineralised water in the glass vessel. Thereafter tea-stained (BC-1) test cloths were immersed in the solution for 30 minutes. The liquor to cloth ratio was greater than 20:1. After rinsing with water, the cloths were dried in a tumble drier.

For reasons of comparison, two peracids of the prior art, i.e. trimethylammoniumpropenyl imidoperoxymellitic acid methane sulphate (cationic BIPTA) , and phthaloylamino peroxycaproic acid (PAP) were tested, using this method. In all cases the total peracid concentration was 1 x 10^"3M.

All these tests were carried out and repeated at several pH-values of the solution in the glass vessel, i.e. a pH of 6, 7, 8, 9, and 10.

The bleaching performance of all peroxyacids tested was determined, using an Instrumental Colour Systems Micromatch to measure the reflectance, at 460 nm, of the BC-1 test cloths both before and after treatment.

The difference (deltaR₄₆₀.) in the values gives a measure of the effectiveness of the treatment. The results in terms of this reflectance difference, are given below for the indicated pH-values :

Experiment Peroxyacid pH- -value

6 7 8 9 10

A diperoxyacid (of 34 33.5 30.5 23.5 15

Example 1)

B cationic BIPTA 25 21 20 11 6 C PAP 13 12.5 10 5 2

It can be seen that the tested cationic diperoxyacid compound of the invention gives a superior bleaching performance as compared to the peroxyacid compounds of comparative Examples B and C, especially under conditions of alkaline pH. This is especially useful for commercial applications. It is desirable for bleaching detergent compositions to provide effective bleaching in wash liquors of about pH 9 or 10. This experiment shows that a cationic diperoxyacid of the present invention shows greatly improved bleaching activity in this pH range. It is at this pH level that the prior art peroxyacid compounds were particularly ineffective.

The above conclusions are further supported by the results of a bleaching experiment involving DPDA (diperoxydodecaneoic acid) . As before the experiment involved bleaching BC-1 test cloths for 30 minutes at 40°C. In this case, the peracid concentration was increased to 1.2 x 10"³M. The results are as follows:

Experiment Peroxyacid pH value D DPDA 7 8 9 reflectance 11.5 12.5 8.5 difference

Thus, the cationic diperoxyacid of the present invention also shows greatly improved bleaching activity over another diperacid, DPDA.

Thermal Stability Experiments

The thermal stability of three of the diperoxyacids exemplified above was investigated. The compounds used were as follows: i) 4-peroxycarboxybenzyl-6 ' -dimethylammoniumperhexanoic acid tosylate prepared according to Example 1 above and having the formula

Compound ( I )

ii) 4-peroxycarboxyterephthalamidopropyl-3 ' - dimethylammonium-8 ' ' -peroctanoic acid tosylate prepared according to Example 3 above and having the formula

Compound (II]

iii) ll-N,N-dimethyl ammonium diperoxyundecanoic acid tosylate prepared according to Example 4 above and having the formula

Compound ( I I I )

These molecules were subjected to thermal stability tests where they were heated at 40°C for a period of six days. The peracid activity was determined before and after the period of heating and the results were compared to known compounds having the following structures:

Compound (IV)

This compound is disclosed in JP-A-64 -56797 (Kao) as compound I -c .

v)

Compound (V)

1, 12-diperoxydodecanoic acid (DPDA) i)

Compound (VI)

peroxyadipylphthalimide (also known as phthalaylaminoperoxycaproic acid - PAP)

The results are given below for the % peracid before and after heating at 40°C for a period of six days.

Compound %peracid before %peracid after %loss after %avai heating heat ing heating oxyge

I 92.5; 93 93; 93 0 6.4 II 90; 89 88; 88.5 0.75 5.36

III 92 ; 93 88; 88.5 4.25 5.0

IV not tested not tested not tested 11.6

V 90; 89 76; 75.5 13.75 12

VI 91; 91.3 89; 88.5 2.4 5.77

Compound IV could not be tested due to its extremely unstable nature. It is predicted that there would be a total loss of activity after being heated at 40°C for six days .

It can be seen that the tested cationic diperoxyacid compounds of the invention give superior thermal stability results compared to the known peroxyacid compounds. Dye Damage Experiments

Compounds I, II and III were used in dye fading experiments to investigate the "local" dye damage caused by them.

For comparative purposes, trimethylammoniumperoxy toluic acid methane sulphonate having the following formula was used:

Compound (VII)

Compound (VII) is expected to have similar solubility to compound (IV) but with less available oxygen (5.2 vs 11.6% respectively) . This means that compound (VII) would be expected to cause less dye damage than compound (IV) .

The test was carried out by adding lOmg of each solid peracid to the centre of a cotton test cloth (10cm²) which had been dyed with sulphur green (immedial green) dye. Five drops of pH 10 buffer solution was added to the peracid on the test cloth and the cloths were left for 30 seconds to allow damage. The cloth was then thoroughly rinsed in demineralised water and air dried before being evaluated. The evaluation was carried out using a "Texican Spectroflash 500" spectrometer and the cloths were read against a white background using an average of 8 readings around the test area (or "spot") . The data is expressed as a difference in reflectance at 640 and 510nm. The results are presented below:

Reflectance Difference at 640 and 510nm of "immedial green" dyed cotton

Compound Delt.a R @ 640nm Delta R @ 510nm

I 17.4 1.0 II 14.7 8.8

III 4.2 13.2

VII 28.7 23

It can be seen that the tested cationic diperoxyacid compounds of the invention give much reduced "local" dye damage than known peroxyacid compounds. It is expected that the "local" dye damage of Compound (IV) would exceed that of Compound (VII) .

Claims

1. Cationic organic diperoxyacid having the general formula (I)

HO^-R^ (C0NH)_p- (CH₂)_Z -N 7⁺-' (CH₂) _y- (CONH) _w-R₂-C0₃H . X^" (I)

wherein:

R_x and R₂ are each independently an optionally substituted, linear or branched, C₃-C₁₀ alkyl or alkenyl group, or an optionally substituted aryl group;

X^' is a counter anion.

2. A diperoxyacid according to claim 1 wherein R_x is an unsubstituted aryl group.

3. A diperoxyacid according to claim 1 or 2 wherein at least one of R₃ and R₂ is an unsubstituted linear C₅-C₁₀ alkyl group.

4. A diperoxyacid according to any preceding claim, wherein y and w are 0.

5. A diperoxyacid according to any preceding claim wherein p and z are 0.

6. A diperoxyacid according to any one of claims 1 to 4 wherein p is 1 and z is 3.

7. A diperoxyacid according to any of the preceding claims, wherein X^" is selected from the group consisting of N0₃-, HS0₄ ^", S0₄ ^2", CH₃S0₄', and R₅- (0) _q-S0₃ ^" , wherein R_s is a C₂-C₂₀ alkyl group, alkenyl group, or alkyl substituted or unsubstituted aryl group, and q is 0 or 1.

8. A diperoxyacid according to claim 7, wherein X^" is selected from sodium dodecyl sulphate (SDS) , sodium fatty acid alpha sulphonate (SFAS) and tosylate.

9. Bleaching detergent composition, comprising from 3 to 40% by weight of one or more surface-active compounds, from 5 to 80% by weight of one or more detergency builders and an effective amount (as defined herein) of a cationic diperoxyacid according to any of claims 1-8, as the bleach component .

10. Composition according to claim 9, wherein the cationic diperoxyacid is present at a concentration of from 0.5 to 15% by weight.

11. Bleaching additive composition, comprising from 50 to 90% by weight of a cationic diperoxyacid according to any of claims 1-8, as the bleach component.