AU666922B2 - Structured liquids containing amido and imido peroxyacids - Google Patents

Description

1 C6167 (C) STRUCTURED LIQUIDS CONTAINING AMIDO AND IMIDO PEROXYACIDS The invention concerns a detergent composition which is a structured liquid comprising amido and imido peroxy acid bleaches.

It is well-known in the art that stable suspensions of organic peroxyacids in aqueous liquids can be formed.

One of the earliest reports is in U.S. Patent 3,996,152 (Edwards et al) which discloses a suspension of diperoxyacids through non-starch thickening agents such as Carbopol 940 in an aqueous media at low pH. Suitable 15 actives were diperazelaic, diperbrassylic, dipersebacic and diperisophthalic acids. U.S. Patent 4,017,412 (Bradley) reports similar systems except that starch-based thickening agents were employed. From later investigations it became evident that the thickener types mentioned in the foregoing patents formed gel-like matrices which exhibited instability upon storage at elevated temperatures. At high concentrations they caused difficulties by uncontrollably raising viscosity to levels which were too high.

2 C6167 (C) U.S. Patent 4,642,198 (Humphreys et al) describes a variety of water-insoluble organic peroxyacids intended for suspension in an aqueous, low pH liquid. This patent discloses the use of surfactants, both anionic and nonionic, as suspending agents for the peroxyacid particles. The preferred peroxy material was 1,12diperoxydodecanedioic acid (DPDA).

EP 176 124 (de Jong) discloses a pourable bleach composition containing peroxycarboxylic acid in an aqueous suspension with 0.5 to 15% alkylbenzene sulphonic acid and low levels of sulphate salt.

The aforementioned patents have all emphasized optimizing 15 the suspending or thickening chemical components of the liquid bleach to improve physical stability. None of the above patents, however, suggests a system which will allow the compositions to be used as effective heavy-duty liquid detergents in the main wash.

A possible approach to this problem was recently disclosed in U.S. Patent 4,,,992,194 (Liberati et al). Therein it was reported that water-insoluble organic peroxyacids such as N-phthaloyl aminoperoxycaprioc acid, referred to in the industry as "PAP", could be suspended in a surfactant provided a pH-adjusting jump system and a deflocculating polymer were also present. A combination of polyol and borate were utilised for the pH-adjusting jump system.

The deflocculating polymer was in the form of a copolymer of hydrophilic and hydrophobic monomers. While the system of Liberti et al represented a significant step forward towards achieving a commercially acceptable, fullyformulated heavy-duty laundry detergent, there remains considerable room for improvement.

3 C6167 (C) The present invention seeks to provide a fully formulated, aqueous-based heavy-duty liquid laundry detergent composition containing a stably suspended peroxy bleach which has a viscosity and bleaching and cleaning properties which are acceptable to the consumer.

It has been found that certain amido or imido peroxyacids can be successfully suspended, i.e. they do not decompose or undergo phase separation, for extended periods of time in an aqueous surfactant structured liquid. These peroxyacids are characterised by having a particular water solubility.

Accordingly, the invention provides a cleaning composition 15 comprising: i) an amido or imido organic peroxyacid having a water solubility of less than 1 x 10 4 M, present in effective amount for bleaching; ii) a surfactant present in an effective amount for suspending the peroxyacid; and iii) a pH-adjusting system present in an effective amount for maintaining pH from 3.5 to 8.5 during storage and, upon dilution with a wash water, causing pH to rise by at least 0.5 pH units.

It is believed, the pH-adjusting system assists in the stabilisation of the peroxyacids.

Preferably, the amido or imido organic peroxyacid has a water solubility of less than 5 x 10 5

M.

The compositions of the invention find particular application as heavy duty laundry detergent liquids.

4 C6167 (C) Peroxyacids of the present invention are preferably selected from mono- or di- percarboxylic amido or imido acids. Mono-percarboxylic acids are of the general formula: 0 R (RN) nC (NR 2 m-R -COOM wherein: R is selected from the group consisting of Ci-C 1 6 alkyl, Ci-C,6 cycloalkyl and C 6

-C

1 2 aryl radicals;

R

1 is selected from the group consisting of hydrogen, Ci-C16 alkyl, Ci-C 1 6 cycloalkyl and C 6

-C,

2 aryl radicals; S 15 R 2 is selected from the group consisting of hydrogen, Ci-C, 6 alkyl, Cl-C,1 cycloalkyl and C 6

-C

1 2 aryl radicals and a carbonyl radical that can form a ring together with R when

R

3 is arylene;

R

3 is selected from the group consisting of Cl-C16 alkylene, Cs-C 12 cycloalkylene and C6-C, 1 arylene radicals; n and m are integers whose sum is 1; and 25 M is selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, ammonium and alkanolammonium cations and radicals.

Di-percarboxylic acids of the present invention may be of the general formula: 0 0 0 II 11 611 MOOCR C (NR) (NR'),R'COOM 5 C6167 (C) wherein:

R

4 is selected from the group consisting of CI-C, alkylene, Cs-C, 2 cycloalkylene, C 6

-C,

1 arylene and radical combinations thereof;

R

5 is selected from the group consisting of hydrogen, Cl-C16 alkyl and C 6 aryl radicals and a carbonyl radical that can form a ring together with R 3

R

6 is selected from the group consisting of hydrogen, Cl-C16 alkyl and C6-C, 2 aryl radicals and a radical that can form a C 3

-C

12 ring together with R 3 V S 15 R 3 is selected from the group consisting of Ci-C 12 alkylene, Cs-C 1 2 cycloalkylene and C 6 arylene radicals; n' and n" each are an integer chosen such that the sum thereof is 1; m' and m" each are an integer chosen such that the sum thereof is 1; and M is selected from the group consisting of hydrogen, 25 alkali metal, alkaline earth metal, ammonium and alkanolammonium cations and radicals.

Particularly preferred materials are: N,N'-di(4-percarboxybenzoyl)-1,4-butanediamine; N,N'-di(4-percarboxybenzoyl)-1,2-phenylenediamine; N,N'-succinoyl-di(4-percarboxy)aniline; 4-percarboxybenzoyl aniline; N,N-phthaloyl-4-aminoperbenzoic acid; 6 C6167 (C) N,N'-di(4-percarboxybenzoyl)ethylenediamine; N,N'-di(4-percarboxyaniline) terephthalate; N,N,N',N'-1,2,4,5-tetracarboxybenzoyl-di(6aminopercarboxycaproic acid); N,N'-di(4-percarboxybenzoyl)piperazine; N,N'-di(4-percarboxybenzoyl)-1,4-diamine-cyclohexane; N,N'-di(percarboxyadipoyl)phenylenediamine; and N,N'-di(percarboxyadipoyl)ethylenediamine.

N,N'-terephthaloyl-di(6-aminoperoxycaproic acid) is especially preferred.

Another material which may be used in the compositions of the invention is the monononylamide of peroxyadipic acid, the preparation of which is described in US patent 4686063 Amounts of the amido or imido peroxyacids of the present invention may range from about 0.1 to about preferably from about 1 to about 10% by weight.

Another component of the present invention will be that of a surfactant. 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 25 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. The total level of the surface-active material may range up to 70% by weight, preferably being from about 1% to about 50% by weight of the composition, most preferably 4 to Synthetic anionic surface-actives are usually watersoluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 7 C6167 (C) to 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher aryl radicals.

Examples of suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C 8

-C

18 alcohols produced for example from tallow or coconut oil; sodium and ammonium alkyl (C 9

-C

20 benzene sulphonates, particularly sodium linear secondary alkyl (C 10

-C

1 s) benzene sulfonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and ammonium salts of sulfuric acid 15 esters of higher (C 9

-C

18 fatty alcohol-alkylene oxide, particularly ethylene oxide reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and ammonium salts of fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (Cs-C 20 with sodium bisulphite and those derived by reacting paraffins with SO; and C12 and then hydrolysing with a base to produce a random sulphonate; sodium and ammonium C 7

-C

1 2 25 dialkyl sulphosuccinates; and olefinic sulphonates, which term is used to describe the material made by reacting olefins, particularly C10-C 20 alpha-olefins, with SO 3 and then neutralizing and hydrolysing the reaction product.

The preferred anionic detergent compounds are sodium (Cn-

C

15 alkylbenzene sulphonates; sodium (C 16

-C

18 alkyl sulphates and sodium (C 16

-C

18 alkyl ether sulphates.

Examples of suitable nonionic surface-active compounds which may be used preferably together with the anionic surface active compounds, include in particular, the 8 C6167 (C) reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C 6

-C

22 phenols, generally 2-25 EO, i.e.

2-25 units of ethylene oxide per molecule; the condensation products of aliphatic (C 8

-C

18 primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine. Other so-called nonionic surface-actives include alkyl polyglucosides, esters of fatty acids and glucosides, long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulfoxides.

Amounts of amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.

The detergent compositions of the invention will normally also contain a detergency builder. Builder materials may be selected from calcium sequestrant materials, (2) 25 precipitating materials, calcium ion-exchange materials and mixtures thereof.

;Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as Zeolite zeolite C, zeolite X, zeolite Y and also the zeolite P type as described in EP-A-0,384,070.

9 C6167 (C) In particular, the compositions of the invention may contain any one of the organic or inorganic builder materials, such as sodium or potassium tripolyphosphate, sodium or potassium pyrophosphate, sodium or potassium orthophosphate, sodium carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethylmalonate, carboxymethyloxysuccinate, tartrate mono- and di-succinates, oxydisuccinate, crystalline or amorphous aluminosilicates and mixtures thereof.

Polycarboxylic homo- and copolymers may also be included as builders and to function as powder structurants or processing aids. Particularly preferred are polyacrylic acid (available under the trademark Acrysol from the Rohm 15 and Haas Company) and acrylic-maleic acid copolymers (available under the trademark Sokalan from the BASF Corporation) and alkali metal or other salts thereof.

S* These builder materials may be present at a level of, for example, from 1 to 80% by weight, preferably from 3 to by weight.

Upon dispersal in a wash water, the initial amount of peroxyacid should range in amount to yield anywhere from about 0.05 to about 250 ppm active oxygen per litre of water, preferably between about 1 to 50 ppm. Surfactant should be present in the wash water from about 0.05 to :grams per litre, preferably from 0.15 to 2.4 grams per litre. When present, the builder amount will range from about 0.1 to 3.0 grams per litre.

It is well-known that organic peroxyacid bleaches are most stable at a low pH whereas they are most effective as bleaches in moderately alkaline pH solution. To achieve the required pH regimes, a pH jump system is 10 C6167 (C) employed to keep the pH of the product between 3 and for peracid stability during storage, yet allow it to become moderately high (pH 7-9) in a wash water for bleaching and detergency efficacy. Most important is that there is obtained a pH jump of at least 0.5 units, preferably 1.0 units, optimally about 1.5 units. One pH jump system is borax 10H 2 0/polyol. Borate ion and certain cis-l,2-polyols complex when concentrated cause a reduction in pH. Upon dilution, the complex dissociates, liberating free borate to raise the pH. Examples of polyols which exhibit this complexing mechanism with borate include catechol, galactitol, fructose, sorbitol and pinacol. For economic reasons, sorbitol is the preferred polyol. To achieve the desired concentrate pH 15 of less than 7, ratios greater than about 1:1 of polyol to borax are usually required. Therefore, the preferred ratio of polyol to borax should range anywhere from about 1:1 to about 10:1, although the range may be as broad as 1:10 to 10:1. Borate compounds such as boric acid, boric oxide, borax with sodium ortho- or pyroborate may also be suitable as the borate component.

e

S

Preferably, the pH jump system is present in an amount from about 1 to about 40 by weight.

An advantageous optional component in the compositions of Sthe invention is a deflocculating polymer. Copolymers of hydrophilic and hydrophobic monomers usually are employed to form the deflocculating agent. Suitable polymers are obtained by copolymerizing maleic anhydride, acrylic or methacrylic acid or other hydrophilic monomers such as ethylene or styrene sulphonates and the like with similar monomers that have been functionalized with hydrophobic groups. These include the amides, esters, ethers of fatty alcohol or fatty alcohol ethoxylates. In addition to the 11 C6167 (C) fatty alcohols and ethoxylates, other hydrophobic groups, such as olefins or alkylaryl radicals, may be used. What is essential is that the copolymer have acceptable oxidation stability and that the copolymer have hydrophobic groups that interact with the lamellar droplets and hydrophilic groups of the structured liquid to prevent flocculation of these droplets and thereby, prevent physical instability and product separation. In practice a copolymer of acrylic acid and lauryl methacrylate (molecular weight 3800) has been found to be effective at levels of 0.5 to These materials are more fully described in U.S. Patent 4,992,194 (Liberati et al) herein incorporated by reference.

15 Apart from the components already mentioned, the detergent compositions of the invention can contain any of the conventional additives in the amounts in which such materials are normally employed in detergent compositions.

Examples of these additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palmkernel fatty acids and coconut fatty acids, lather depressants such as alkyl phosphates and silicones, antiredeposition agents such as sodium carboxymethylcellulose and alkyl or substituted alkylcellulose ethers, other stabilizers such as ethylene S diamine tetraacetic acid, fabric softening agents, inorganic salts such as sodium sulphate and, usually present in very small amounts, fluorescent whitening agents, perfumes, enzymes such as proteases, cellulases, lipases and amylases, germicides and colorants.

The compositions of the invention may be used to clean a wide of substrates, including hard surfaces, and especially fabrics.

12 C6167 (C) The following non-limiting examples will more fully illustrate the embodiments of this invention. All parts, percentages and proportions referred to herein and in the appended claims are by weight unless otherwise stated.

Example 1 Monomethyl monopotassium terephthalate A solution of 87.5% KOH (143 g, 2.24 moles) in 870 ml of methanol was added to group dimethylterephthalate (434 g, 2.24 moles) in 2,420 ml toluene at room temperature over a period of 45 minutes. The reaction mixture was heated at 65 0 C for three hours with stirring and then allowed to 15 cool to room temperature. The solids were filtered, washed with 3500 ml of warm toluene, and dried to yield S464,08 grams (95% yield) of a white solid. IR (nujol) 1735, 1600, 1550, 1410, 1290, 730 cm-.

S* 20 N,N'-Di(4-Carbomethoxybenzovl) piperazine Monomethyl monopotassium terephthalate (175.8 g, 0.8056 mol) was suspended in toluene (2000 ml) in a 5 litre, 3necked flask equipped with an overhead stirrer, a condenser, and an addition funnel. Thionyl chloride (58.76 ml, 0.8056 mol) was added dropwise to the rapidly stirred suspension and the mixture was heated at 67 0 C for three hours. After stirring overnight at room temperature, the reaction was filtered on a Buchner funnel through a bed of celite and the filtrate containing 4carbomethoxybenzoyl chloride was retained. At this point the acid chloride can be isolated by addition of an equal volume of diethyl ether, filtration of the potassium chloride by-product and removal of the solvent in vacuo.

For most procedures the toluene solution is used directly.

13 C6167 (C) In a 5 litre Morton flask, potassium carbonate (266.2 g, 1.61 mol) and piperazine (34.69 g, 0.4027 mol) were dissolved in 1000 ml of wa;er. The toluene solution of 4carbomethoxybenzoyl chloride was added dropwise while the internal reaction temperature was maintained at 25 0 C. The mixture was stirred overnight, filtered and washed with toluene, water, 1N HC1 and water to provide 127 g of N,N'-di(4-carbomethoxybenzoyl) piperazine as a white solid, mp. 234-237 0 C; IR (nujol) 1730, 1630, 1610, 1510, 1290, 1260, 1010, 730 cm-.

1 H NMR (200MHz, CDC1 3

/CD

3

COCD

3 8 7.48-8.11 (8H, 3.93 (6H, 3.81 (4H, br 3.56 (4H, br 1 C NMR (CDC1 3

/CD

3

COCD

3 5 169.51, 166.05, 139.19, 131.50, 129.89, 15 126.98, 52.31, 43.80, 41.10; IR (nujol) 2920, 2840, 1720, 1620, 1605, 1455, 1430, 1370, 1360, 1275, 1260, 1100, 1000 cm- 1 low res. MS (CI, isobutane) 411 (MHI).

N,N'-Di(4-Percarboxvbenzoyl)piperazine (PCBPIP) 9.

N,N'-Di(4-percarboxybenzoyl) piperazine (4.07 g, 0.0099 mol) was dissolved in methanesulphonic acid (14 ml) and was treated with hydrogen peroxide (3.37 ml of a solution, 0.0891 mol) at 0°C. The mixture was stirred at S 25 room temperature for 5 hours, then poured onto ice-water.

The solids were collected on a Buchner funnel, washed with water until the pH was 5, then allowed to air dry overnight. Yield 3.91 g of a white powder; m.p. 268 (decomposed prior to melting Iodometric tritration indicated 65% peracid. IR (nujol) 3100 (hydroxyl), 1760 (peracid carbonyl) cm 1 14 C6167 (C) Example 2 N,N'-Di(4-Carbomethoxvbenzoyl) ethylenediamine Prepared using the procedure described for N,N'di(carbomethoxybenzoyl) piperazine and substituting ethylenediamine (26.9 ml, 0.4028 mol) for piperazine and using 400 ml of water instead of 1000 ml. Yield 88.6 g mp. 297-2990C; 1 H NMR (200 MHz, DMSO-d) 5 8.82 (2 H, br 8.06-7.94 (8 H, 3.88 (6 H, 3.47 (4 H, IR (nujol) 3300, 1730, 1640, 1550 cm- 1 N,N'-Di(4-Percarboxvbenzoyl) ethylenediamine (PCBED) 15 N,N'-Di(4-carbomethoxybenzoyl) ethylenediamine (5.0 g, 0.0129 mol) was dissolved in 30 ml of methanesulphonic acid and treated with hydrogen peroxide (4.4 ml of a solution) at 0°C. The mixture was allowed to warm to room temperature and was stirred for 5 hours. It was poured 20 onto ice and saturated ammonium sulphate, the solids were filtered and washed with water to a pH of 5. The activity was 78% by iodometric titration.

Example 3 N,.N'-Di (4-Carbomethoxvbenzoyl)-1,4-phenylenediamine 4-Carbomethoxybenzoyl chloride (9.32 g, 0.046 mol) in chloroform (95 ml) was added to 1,4-phenylenediamine (2.59 g, 0.023 mol) in triethylamine (4.81 ml, 0.035 mol) and chloroform (250 ml) at 40C. The reaction was allowed to warm to room temperature overnight. The chloroform was removed in vacuo. The solid was poured onto cold 5% HC1, filtered and washed with dilute HC1. Recrystallization from DMF yielded 6.16 g of a pale yellow powder; mp 15 C6167 (C) >3450C. iH NMR (DMSO-d 6 8 8.06 (8H, 7.74 (4H, s), 3.88 (6H, 1 C NMR (H 2

SO

4

/CD

3

COCD

3 (dec. to aci.d) 8 205, 196, 169.77, 167.10, 132.56, 130.95, 128.16, 127.79, 127.03, 122.85, 119.82, 52.02; IR (nujol) 3330, 2900, 2840, 1720, 1640, 1550, 1455, 1410, 1375, 1280, 1190, 1110 cm- 1 low res. MS(CI, isobutane) 433 271, 257, 223.

N,N'-Di(4-Percarboxvbenzoyl)phenylenediamine (1,4-PCBPD) N,N'-Di(4-carbomethoxybenzoyl)phenylenediamine (3.07 g, 0.0071 mol) was dissolved in methanesulfonic acid (40 ml) and treated with hydrogen peroxide (2.42 ml of a solution, 0.0639 mol) at room temperature. After stirring 15 at room temperature for 6 hours, the reaction was kept at 30C for 12 hours. The mixture was poured onto saturated Sammonium sulphate solution and ice and then isolated as before to yield 1.85 g of an orange powder; mp>315 0 C. Iodometric titration indicated 60% peracid. IR 20 (nujol) 3230 (hydroxyl), 1755 (peracid carbonyl) cm-.

Example 4 N,N'-di(4-Carbomethoxvbenzoyl)-1,4-diaminocyclohexane 4-Carbomethoxybenzoyl chloride (9.057 g, 0.0456 mol) was dissolved in chloroform (180 ml) in a 500 ml 3-necked flask equipped with a mechanical stirrer and an addition funnel. To this solution was added trans-1,4diaminocyclohexane (2.60 g, 0.0228 mol), triethylamine ml, 0.0535 mol) and chloroform (80 ml) at 0°C over a period of 30 minutes. The reaction was stirred for hours and the product filtered from the chloroform. The wet solid was washed with 10% HC1 and saturated aqueous NaCl. The product was dissolved in concentrated sulfuric 16 C6167 (C) acid at 0° and then crashed out from ice water to give a white powder in about 80% yield; m.p. >350 0 C. 1 H NMR (200 MHz, D 2

SO

4 5 8.30-7.94 (8H, 4.27-4.37 (8H, 2.34- 1.80 (8H, br 13C NMR (200 MHz, H 2

SO

4

/CD

3

COCD

3 8 170.92, 132.32, 129.92, 129.25, 127.61, 55.04, 51.83, 24.07; IR (nujol) 3295, 2920, 2850, 1720, 1630, 1530, 1460, 1375, 1285 cm- 1 N,N'-Di(4-Percarboxybenzoyl)-1,4-diaminocyclohexane

(PCBHEX)

N,N'-Di(4-percarboxybenzoyl)-1,4-diaminocyclohexane (1,63 g, 0.0037 .mol) was dissolved in methanesulphonic acid ml) and treated with hydrogen peroxide (1.26 ml of 15 solution, 0.0333 mol) at room temperature. After 7 hours, the reaction was worked-up with ice water and dried in a vacuum oven at 250C to give 1.57 g of a white powder; m.p. >3100C. Iodometric titration indicated 79% peracid. IH NMR (200 MHz, DMSO-d 6 8 8.47-8.44 ester), 8.03-7.91 peracid and ester), 3.88 ester), 3.79 (br s, ester and peracid), 1.94-1.91 ester and peracid), 1.52-1.43 ester and peracid; IR (nujol) 3295 (broad, hydroxyl), 1730 (peracid carbonyl) cm- 1 Example Carboethoxyadipoyl Chloride Adipic acid monoethyl ester (25.63 g, 0.147 mol) was combined with thionyl chloride (34.98 g, 0.293 mol) in a round-bottomed flask equipped with a condenser and heated at 370C for 3 hours. The condenser was replaced by a modified still head and excess thionyl chloride removed at mm Hg. The product (26.84 g, 95%) was distilled as a clear liquid (59 0 C/about 0.1 mm Hg). IR 3550, 3420, 2950, 17 C6167 (C) 2910, 2840, 1785, 1715, 1455, 1360, 1230, 1170, 1140, 1080, 1010, 940 cm-.

N,N'-Di(Carboethoxyadipoyl)-1,4-phenylenediamine Carboethoxyadipoyl chloride (13.74 g, 0.071 mol) in chloroform (40 ml) was added to 1,4-phenylenediamine (3.89 g, 0.036 mol) in chloroform (330 ml) and triethylamine (7.53 ml, 0.054 mol) at 4 0 C. The reaction medium was allowed to warm to room temperature over the course of hours. Recrystallization from ethyl acetate gave 6.30 g of a white fluffy solid; m.p. 156-160 0 C. IH NMR (DMSO-d 6 8 9.81 (2H, s, NH), 7.49 (4H, 4.04 (4H, q), 1.57 (8H, 2.34 (8H, 1.18 (6H, 13C NMR 6 173.65, 15 171.25, 134.38, 120.74, 60.39, 36.90, 33.98, 25.01, 24.42, 14.23; IR (nujol) 3290, 2920, 2840, 1720, 1645, 1540, 1455, 1370, 1370, 1290, 1255, 1170 cm- 1 low res MS(CI, isobutane) 421 0 20 N,N'-Di(Percarboxvadipovl)phenylenediamine

(DPAPD)

N,N'-Di(carboethoxyadipoyl)-1,4-phenylenediamine (6.00 g, 0.0143 mol) was dissolved in methanesulphonic acid (21 ml) and was treated with hydrogen peroxide (4.87 ml of a solution, 0.1287 mol) at room temperature. The product was isolated from ice water after 2 hours to give 4.97 g of a pale orange powder; m.p. 210-212 (dec).

Iodometric titration indicated 87% peracid. IH NMR (200 MHz, DMSO-d 6 8 11.97 (2H, br, 9.83 (2H, s) 7.49 (4H, 4.10 (trace, q, ester), 2.49-2.00 (8H, 1.57 (8H, br 1.17 trace, t, ester); IR (nujol) 3100 (hydroxy), 1750 (peracid carbonyl) cm- 1 18 C6167 (C) Example 6 N,N'Di(4-Carbomethoxvbenzoyl)-1,4-butanediamine 4-Carbomethoxybenzoyl chloride (19.07 g, 0.096 mol) was dissolved in toluene (380 ml) in a 3-necked, 1000 ml round-bottomed flask equipped with mechanical stirrer, thermometer, and addition funnel. A solution of 1,4butanediamine in water (80 ml) was added dropwise over a period of 40 minutes while the temperature of the reaction mixture was maintained at 25 0 C by a water bath. A white solid formed immediately and the reaction mixture stirred for an additional 2 hours. The solid was collected on a frit and washed with toluene, water, 5% HC1, and water.

15 Recrystallization from DMF gave white crystals which were dried in a vacuum oven at 60 0 C; yield 17.91 g m.p.

260-261 0 C. 1H NMR (200 MHz, DMSO-d 6 6 8.70 (2H, 8.05- 7.93 (8H, m) 3.88 (6H, s) 3.34 (4H, 1.58 (4H, IR (nujol) 3300, 1720, 1625, 1530, 1275, 1105, 860, 730 cm-1; 20 low res. MS (CI, isobutane) 413 "C NMR (75 MHz, DMSO-d 6 8 166.9, 165.7, 165.4, 165.2, 138.7, 131.6, 129.0, 127.5, 127.2, 52.3, 26.5.

N,N'-Di(4-Percarboxybenzovl)-1,4-butanediamine

(PCBBD)

N,N'-Di(4-carbomethoxybenzoyl) -1,4-butanediamine (3.00 g, 0.007 mol) dissolved in methanesulfonic acid (25 ml) was treated with hydrogen peroxide (2.50 ml of a 70% solution, 0.066 mol) according to the aforedescribed method. After 5 hours at room temperature and 16 hours at 3 0 C, the peracid was precipitated over ice water, washed with water and dried to give 1.8 g of a white powder; m.p. 180 (dec). Iodometric titration indicated 74% peracid, 5.7% a.o. (theory: 7.7% IR (nujol) 3320-3100 (hydroxyl), 1745 (peracid carbonyl) cm- 1 iH NMR (200 MHz, 19 C6167 (C) DMSO-d 6 8 8.65 (2H, 8.03-7.90 (8H, 3.87 (starting material, 3.29 (4H, 1.58 (4H, s).

Example 7 N,N-Di(4-Carbomethoxybenzoyl)-1,2-phenylenediamine 4-Carbomethoxybenzoyl chloride (18.5 g, 0.093 mol) was dissolved in chloroform (100 ml) under nitrogen and cooled to 0°C. A solution of 1,2-phenylenediamine (5.00 g, 0.046 mol) and triethylamine (12.8 ml, 0.092 mol) in chloroform (350 ml) was added dropwise. After 16 hours at room temperature, triethylammonium chloride was removed by filtration on a frit containing filter paper. The organic S 15 layer was washed with cold 5% HC1 (3 x 200 ml), saturated NaC1 solution (2 x 150 ml), and dried over magnesium sulfate. The product was isolated by removal of chloroform under reduced pressure. Recryallization from ethanol yielded 12.19 g of a white powder; m.p. 211- S 20 216 0 C. 1H NMR (200 MHz, DMSO-d) 8 10.24 (2H, 8.09- 8.07 (8H, 2s), 7.69 (2H, 7.33 (2H, 3.90-3.88 (6H, 2s); "C NMR (50 MHz, DMSO-dG) 8 165.29, 164.37, 138.13, 131.82, 130.94, 128.94, 127.69, 125.79, 125.42, 52.08; IR (nujol) 3380, 3280, 1720, 1645, 1540, 1290, 1275, 1100 cm 1 low res. MS (CI, isobutane) 433 271, 165.

N,N'-Di(4-Percarboxvbenzoyl)-1,2-phenylenediamine (1,2-

PCBPD)

N,N'-Di(4-carbomethoxybenzoyl)-1,2-phenylenediamine (2.75 g, 0.0064 mol) was dissolved in methanesulphonic acid ml) and cooled to 0°C. Hydrogen peroxide (1.57 ml of a solution, 0.058 mol) was added dropwise. After 16 hours at room temperature, the reaction was worked-up as described above.

20 C6167 (C) Idometric titration indicated 70% peracid, 5.2% a.o.

(theory: 7.3% IR (nujol) 3160 (hydroxyl), 1740 (peracid carbonyl) 'H NMR (200 MHz, DMSO-d 6 5 10.20 (2H, 8.09-8.07 (8H 2s), 7.73-7.52 (2H, 7.39-7.22 (2H, 3.89 (ester about "C NMR (50 MHz, DMSO-d 6 8 166.58, 164.76, 137.95, 133.37, 131.19, 129.30, 127.76, 126.01.

Example 8 N,N'-Succinoyl-di(4-carbomethoxy)aniline Succinyl chloride was distilled under reduced pressure prior to use. To a 1000 ml round-bottomed flask under 15 nitrogen, methyl-4-aminobenzoate (20 g, 0.132 mol), pyridine (10.7 ml, 0.133 mol), and chloroform (250 ml) were combined and cooled to 0°C. A chloroform solution of succinoyl chloride (7.5 ml, 0.068 mol) was added dropwise.

A lavender precipitate was observed upon addition. After 2 hours at room temperature, the product was filtered on a frit, washed with 5% HCl (2 x 400 ml) then with water (600 ml) and then allowed to air dry on the frit. The product was recrystallized from DMF and dried in a vacuum oven at 60 0 C to afford 16.09 g of white crystals; m.p. 284- 285 0 C. 'H NMR 200 MHz, DMSO-d 6 8 10.42 (2H, 7.96-7.74 (8H, 3.85 (6H, 2.75 (4H, IR (nujol) 3340, 3320, 1710, 1690, 1675, 1610, 1595, 1530, 1295, 1270, 1175, 1160, 1105, 770 cm-1; low res. MS (CI, isobutane) 385 234, 152; "C NMR (75 MHz, DMSO-d) 5 170.9, 165.7, 143.6, 130.2, 123.6, 118.2, 51.7, 31.0.

N,N'-Succinoyl-di(4-percarboxy)aniline (SDPCA) N,N'-Succinoyl-di(4-carbomethoxy)aniline (5.02 g, 0.013 mol) was dissolved in methanesulfonic acid (30 ml) and 21 C6167 (C) cooled to 0°C. Hydrogen peroxide (4.43 ml of a solution, 0.117 mol) was added dropwise. After 6 hours at room temperature, the product was worked-up as usual to give a light tan powder; m.p. 201 0 C. Iodometric tritration indicated 72% peracid, 6.0% a.o. (theory: 8.2% IR (nujol) 3200 (hydroxyl), 1750 (peracid carbonyl) cm-1; 1 H NMR (200 MHz, DMSO-d 6 8 10.37, 10.34 (2H each, s, one for peracid OH, one for amide 7.92-7.68 (8H, 3.81 ester), 2.72 (4H, s, ester and peracid).

Example 9 N,N'-Di(Carboethoxvadipovl)ethylenediamine 15 Ethylenediamine (1.17 g, 0.0195 mol) in water (5 ml) was added dropwise to a solution of carboethoxyadipoyl chloride (2.5 g, 0.013 mol) in toluene (36 ml) at room temperature. After stirring for an additional 2.5 hours, the white solid was filtered, washed with toluene, water, S 20 0.1 N HC1 and water and dried in a vacuum oven at 63 0

C.

:In an attempt to eliminate an impurity evident in the IR spectrum (3080 cm- 1 the material was taken up in toluene, S!''the insolubles removed by filtration, and the toluene removed in vacuo to yield a white powder (0.31 g, 13%); m.p. 117-1200C (white residue remained after most melted).

H NMR (200 MHz, DMSO-d 6 8 7.83 (2H, br 4.05 (4H, q) 3.37 (H 2 3.07 (5H, br 2.28-2.02 (10H, br 1.49 (9H, br 1.18 (6H, relative to the ethoxy protons, the integration of peaks at 3.07 and 1.49 is high by one proton each, and at 2.28-2.02 by two protons; IR (nujol) 3300, 2920, 2850, 1725, 1640, 1550, 1460, 1375, 1270, 1245, 1180, 730 cm-.

Since the toluene purification did not eliminate the unidentified impurity, the method described for the 22 C6167 (C) preparation of N, N'-(4-carbomethoxybenzoyl) piperazine was used. Carboethoxy-adipoyl chloride (1.0 g, 0.0052 mol) in chloroform (12 ml) was added dropwise to a solution of ethylenediamine (0.16 g, 0.0026 mol), triethylamine (0.54 ml, 0.0039 mol), and chloroform (5 ml) at 4 0 C under nitrogen. The mixture was stirred for hours and worked up as usual to give 0.60 g of a solid. This product was recrystallized from toluene to give 0.20 g of a white powder which still contained the impurity by IR and NMR; m.p. 120-1220C.

Recrystallization from ethyl acetate also did not eliminate the impurity. 1C NMR (200 MHz, CDCl 3

/CD

3

COCD

3 8 207.44, 173.87, 60.38, 40.07, 36.08, 33.90, 25.12, 24.39, 14.33, 14.25; low res. MS(CI, isobutane) 373 N,N'-Di(Percarboxvadipoyl)ethylenediamine N,N'-Di(carboethoxyadipoyl)ethylenediamine (0.023 g, 0.00055 mol) was dissolved in methanesulfonic acid (1.4 20 ml) and treated with hydrogen peroxide (0.19 ml of a solution, 0.00495 mol) at room temperature and stirred for 18 hours. The product, which was difficult to isolate from ice water, was a flaky material (0.0088 g, 46%) which turned black <2200C but did not melt before 350 0

C.

Iodometric titration indicated 55% peracid. 1 H NMR (200 MHz, DMSO-d6, 7.81 (br s, ester and peracid), 4.10 (q, ester), 3.06 2.22 and 2.19 ester and peracid), 1.48 ester and peracid), 1.19 ester). IR (nujol) 3200 (hydroxyl) 1755 (peracid carbonyl) cm 1 23 C6167 (C) Example N-Benzovl-4-aminobenzoic acid Sodium carbonate (26.5 g, 0.25 mol) was dissolved in 200 ml of water in a 500 ml Morton flask equipped with a mechanical stirrer and an additional funnel. 4- Aminobenzoic acid (13.71 g, 0.10 mol) was added portionwise and the mixture was stirred until fully soluble. The mixture was cooled to 0°C and benzoyl chloride (13.92 g, 11.50 ml, 0.099 mol) was added dropwise. A thick, white precipitation soon formed and after stirring for 2 hours at room temperature, the mixture was poured onto cold, dilute HC1. The solid was 15 filtered and washed with dilute HC1 and water.

Recrystallization from ethanol and water yielded 11.69 g of the desired product; mp 284-288 0 C; IR (nujol) 3340, 1680, 1665, 1650, 1515 cm- 1 1 H NMR (200 MHz, DMSO-d 6 12.40 (1H, 10.55 (1H, 8.20-7.45 (9H, m).

N-Benzoyl-4-aminoperoxybenzoic acid (BP-PABA) N-Benzoyl-4-aminobenzoic acid (5.0 g, 0.0207 mol) was dissolved in 20 ml of methanesulfonic acid. The mixture was cooled to 0°C and concentrated hydrogen peroxide (2.40 ml of a 70% solution, 0.0634 mol) was added dropwise. The mixture was allowed to stir for 3 hours at room temperature after which time it was poured onto a large amount of ice water. The precipitate was filtered on a Buchner funnel and washed with water until the pH of the filtrate was 4.5. The activity was 79% 5.22% theory) as indicated by iodometric titration; mp 140 (dc); IR (nujol) 3450 (hydroxy), 3340, 1740, 1655, 1530 cm- 1 1

H

NMR (300 MHz, DMSO) 5 8.05-7.50 (9H, m).

24 C6167 (C) Example 11 4-Carbomethoxybenzov1 aniline 4-Carbomethoxybenzoyl chloride (11 g, 0.055 mol) dissolved in chloroform (200 ml) was stirred under nitrogen by a mechanical stirrer. The flask was cooled to 0 0 C, and a solution of aniline (20.64 g, 0.222 mol) in chloroform ml) was added dropwise. A white precipitate formed during addition. After 2 hours at room temperature, the chloroform was removed by rotary evaporation. The product was washed with 10% HC1, filtered on a frit, washed several times with water, and washed with chloroform.

Recrystallization from toluene gave 5.02 g of a white powder; m.p. 194-195 0 C. 1 H NMR (200 MHz, DMSO-d 6 8 10.45 (1H, 8.09-7.34 (9H, 3.91-3.90 (3H, IR (nujol) 3380, 1720, 1665, 1605, 1540, 1330, 1285, 1170, 1120, 760, 730 cm- 1 13C NMR (50 MHz, CDC1 3

'/D

3

COCD

3 6 166.3, 165.2, 139.2, 138.5, 132.7, 129.6, 128.9, 127.6, 20 124.4, 120.5.

4-Percarboxvbenzovl aniline (PCBA) (4-Carbomethoxybenzoyl)aniline (4.78 g, 0.0187 mol) was dissolved in methanesulfonic acid (25 ml). Hydrogen e* peroxide (2.13 ml of a 70% solution, 0.056 mol) was added dropwise. After 5 hours at room temperature, the reaction was worked-up as usual to give 3.86 g of a pale yellow powder. Iodometric titration indicated 66% peracid, 4.1% a.o. IR (nujol) 3320 (hydroxyl), 1750 (peracid carbonyl) cm- 1 1 H NMR (200 MHz, DMSO-d 6 8 11.90 (1H, br 10,42 (1H, 8.11-7.09 (9H, 3.90 (ester, 25 C6167 (C) Example 12 N,N,N',N'-1,2,4,5-tetracarboxybenzovl-di(6-aminocaproic acid) 1,2,4,5-tetracarboxybenzene dianhydride (20 g, 0.0917 mol) and 6-aminocaproic acid (24.6 g, 0.188 mol) were suspended in 200 ml of DMF and heated to 120 0 C. The solids dissolved when heated. After 3 hours, the solution was cooled, poured onto ice-water and filtered. The solids were purified by stirring in 500 ml of hot methanol and allowing to cool; yield 30 g of a white solid; IR (nujol) 1770, 1705 1055 cm-1; 1 H NMR (200 MHz, DMSOd 6 5 12.0 (2 H, 8.15 2 3.61 (2 H, 2.2 (2 15 H, 1.8-1.2 (6 H, "C NMR (50 MHz, DMSO-d) 8 175.0, 166.6, 137.2, 118.0, 38.1, 33.7, 27.8, 26.0, 24.3.

N,NN',N'-1,2,4,5-tetracarboxybenzovl-di(6aminopercarboxycaproic acid) (DIPAP) The dimide dicarboxylic acid (7.0 g, 0.0224 mol) above was dissolved in 55 ml of methanesulphonic acid and treated with 70% hydrogen peroxide (5.0 ml, 0.134 mol). After a short time, the reaction mixture became very thick and it 25 was necessary to use a mechanical stirrer. The mixture was poured onto ice-water after 5 hours at room temperature and isolated as described previously. The activity was 98%; IR (nujol) 3270, 1760, 1740, 1710, 1155, 1055 cm- 1 26 C6167 (C) Example 13 N,N'-Terephthaloyl-di(6-aminoperoxvcaproic acid) (TPCAP) N,N'-Terephthaloyl-di(6-aminocaproic acid)* (5.01 g, 0.0127 mol) was dissolved in 30 ml of methanesulfonic acid and treated with hydrogen peroxide (4.33 ml of 70%, 0.114 mol) at 0°C. The mixture was stirred at room temperature for 5.5 hours then worked-up as usual. Yield 4.91 g activity 88% theory IR (nujol) 330, 3200, 1760, 1740, 1630, 1545 cm-.

*Zinner, Sych, Ludwig, W. J. Prakt. Chem. 17, 147- 153 (1962).

Example 14 N,N'-Di(4-carboxyaniline)terephthalate 20 4-Aminobenzoic acid (2.1 eq, 14.11 g, 0.103 mol) and sodium carbonate (5 eq, 25.92 g, 0.245 mol) were stirred rapidly in 4000 ml water. Ground terephthaloyl chloride was added portionwise at room temperature. After stirring for 72 hours, the solution was poured onto 10% HC1. The 25 solids were collected by filtration and washed with water to give 16.6 g (83% yield) of a white powder. An impurity in this product is N-(4-carboxybenzoyl)4-aminobenzoic acid, which is the monoaddition adduct (less than iH NMR (200 MHz, DMSO-d) 8 10.74 (2 H, 8.15-7.90 (12 H, 3.4 (2H, br IR (nujol) 3360, 1690, 1660, 1610 cm 1 N,N'-Di(4-Percarboxvaniline)terephthalate (DPCATL N,N'-Di(4-carboxyaniline)terephthalate (4.98 g, 0.012 mol) was suspended in 60 ml of methanesulfonic acid and treated 27 C6167 (C) with hydrogen peroxide (4.09 ml of a 70% solution, 0.108 mol). The mixture was heated at 30 0 C for 4.5 hours, then isolated as usual. Activity 91%, 6.7% a.o. (theoretical 7.3% IR (nujol) 3380, 3200, 1740, 1660, 1600 cm- 1 Example N,N-Phthaloyl-4-aminobenzoic acid Phthalic anhydride (10.0 g, 0.0675 mol) and 4-aminobenzoic acid (9.35 g, 0.0682 mol) were dissolved in 100 ml of anhydrous DMF and heated to 120 0 C for 4.5 hours. The mixture was cooled, poured onto ice water and filtered.

Recrystallization from ethanol-water provided 6.6 g (37%) of a fluffy white solid; mp 189-190; IR (nujol) 1780-1745, 1725, 1695, 1605 cm- 1 1 H NMR (200 MHz, DMSO-d 6 8 13.1 (1H, 8.2-7.58 (4H, aa'bb'), 8.06-7.9 (4H, "C NMR MHz, DMSO-d) 8 166.69, 166.65, 135.81, 134.82, 131.48, S 129.88, 129.82, 126.99, 123.54.

N,N-Phthaloyl-4-aminoperbenzoic acid (Phenyl PAP) To a suspension of N,N-phthaloyl-4-amino-benzoic acid (4.03 g, 0.0151 mol) in 60 ml methanesulfonic acid was S 25 added 70% hydrogen peroxide (2.29 ml, 0.0605 mol) at room temperature. After 6 hours the reaction was worked-up as usual and stored as a wet filter cake (6.23 A dried sample contained 84% peracid; mp 173 (discolour); IR 3305, 1785, 1760, 1730, 1700, 1600, 1510, 1075 cm- 1 1H NMR (200 MHz, DCD1 3 8 11.7 (1H, s) 8.4-7.55 (8H, m).

28 Example 16 Peracid Stability in a Heav-Dutv Liauid C6167 (C) a The formulation used for this study contained 35% surfaceactives and had a pH of 4.5 which was obtained with a borax/sorbitol pH jump system. The peracid was dosed at 2,500 ppm. Table I contains the base formulation. The tested formulations (base including peracid) were stored at 40 0 C and aliquots were removed periodically and titrated for the percent of remaining peracid. Half-lives of the tested formulations are reported in Table II.

Table 1 BASE FORMULATION OF PH-JUMP LIQUIDS* Water 38.1 Sorbitol (100%) 19.6 Borax 10 aq NaOH (100%) 2.9 Decoupling polymer (100%) Neodol 25-9 10.5 LAS-acid 22.9 0 0 00 0 0 0 0 *0 0 00 *Initial pH 29 9 -C6167 (C) Table 11 PERACID STABILITY IN A HEAVY-DUTY LIQUID Peracid 40 0 C (days)- PCBPIP 79 DPCAT Phenyl. PAP 48 SDPCA 43 POBED 34 1,2-PCBPD 33 DPAPD 32 DI PAP 29 TPCAP PCBBD 15 SBPB 11 PCBA 8 DPDA PAP 3 All the amido peracids were more stable than DPDA in the heavy-duty liquid. Five of these had half-lives of greater than 30 days. PCBPIP had a remarkable 79-day half-life at 40 0

C.

*4,4'-sulfonylbisperoxybenzoic acid described in EP 267 175.

S

S S S. 55

S

S

S

S.

S

S S S 5* 30 C6167 (C) For purposes of the present invention, it is advantageous to achieve a peroxide stability half-life at 40 0 C of at least 10 days, preferably at least 15 days, more preferably at least 30 days, and optimally beyond 50 days.

Example 17 Water Solubility A basic premise of this invention is that the solubility of a peracid affects its stability in a formulation.

Consequently, the water solubility value of various peracids has been measured and these values correlated with peroxide stability.

S The solubility experiments were conducted by rapidly Sstirring 0.2 g of the finely ground peracid in 50 ml of Milli-Q water containing 0.01 gl 1 of a phosphonic acid Dequest 2041. The solution was heated to 40 0 C for minutes then equilibrated to 25.0 0 C(+1 0 C) using a water circulating bath. After 2 hours, the stirring was stopped and the solids were allowed to settle. An aliquot was filtered using a polypropylene disposable syringe fitted with a Millex-HA 0.45 pm filter unit. The pH of the filtrate was between 4.5 and 5.0. The clear filtrate was treated with potassium hydrogen phthalate buffer and potassium iodide and the concentrate of triiodide determined spectrophotometrically according to the method of Davies (Davies, Deary, M.E. Analyst (1988}, 113, 1477-1479.) This procedure was repeated one hour later to be sure an equilibrium value had been obtained. The reproducibility of the method was found to be 31 C6167 (C) The results are presented in Table III. The monoperacids and diperacids are listed separately because the errors in measuring the two types are believed to be different. The analysis of the solubility of the diperacids may be dependent on the purity of the sample used for the measurement, but the analysis of the solubility of the monoperacids should be independent of purity. This is because the measurement is an active oxygen determination.

Whereas contaminants such as unreacted carboxylic ester or acid will not interfere in the measurement of a monoperacid, a low purity diperacid will contain species with one carboxylic ester (or acid) group and one peracid group. These molecules may have different solubility properties than the desired molecule and the active oxygen 15 content per molecule will be only half of that for the diperacid.

Thus, two concentrations are listed in Table III, the titratable percarboxyl groups and the concentration of the 20 molecule.

o* *e 32 C6167 (C) Table III 0 0 SOLUBILITY OF SELECTED PERACIDS IN WATER (pH 4.5 to Concentration Concentration Peracid of a.o. in of Molecule solution in solution (10-1M) (1 0 5 m) Mono-peracids Phenyl. PAP 1.2 1.2 84 PCBA 6.8 6.8 BP-PABA 8.8 8.8 79 0 PAP 62.0 62.0 89 Di-peracids PCBBD 1.9 0.9 68 PCBED 1.9 0.9 69 1, 2-PCBPD 2.0 1.0 DIPAP 2.2 1.1 98 PCBPIP 2.3 1.2 79 SBPB 4.8 2.4 61 DPAPD 7.4 3.7 92 TPCAP 9.0 4.5 88 0 DPDA 21.7 10.8 0 .4 0*e* .4.

00 .4 0 .4 .4 .4.0* .4 .4 0000 0 .4 0* .4 *0

Claims (8)

1. A cleaning composition comprising: i) an amido or imido organic peroxyacid having a water solubility of less than 1 x 10- 4 M, present in an effective amount for bleaching; ii) a surfactant, present in an effective amount for suspending the peroxyacid; and iii) an effective amount of a pH-adjusting system present for maintaining pH from 3.5 to 8.5 during storage and, upon dilution with a wash water, causing pH to rise by at least 0.5 pH units the pH-adjusting system comprising a borate and a polyol, the borate to polyol '5 ratio ranging from 1:10 to about 10:1.

2. A composition according to claim 1 wherein the peroxyacid is selected from the groups consisting of: O O S. *0 0 R (R 1 N) nC (NR 2 R COOM wherein: e R is selected from the group consisting of CI-C 1 alkyl, Ci-C 1 6 cycloalkyl and C 6 aryl radicals; R 1 is selected from the group consisting of hydrogen, Ci-C16 alkyl, CI-C16 cycloalkyl and C,-C 12 aryl radicals; R 2 is selected from the group consisting of hydrogen,Ci-Clg alkyl, Ci-C16 cycloalkyl and C6-C, aryl radicals 34 C6167 (C) and a carbonyl radical that can form a ring together with R when R 3 is arylene; R 3 is selected from the group consisting of Cl-C 16 alkylene, Cs-C 1 cycloalkylene and C 6 -C 12 arylene radicals; n and m are integers whose sum is 1; and M is selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, ammonium and alkanolammonium cation and radicals and 0 0 0 MOOCR 4 (RsN) n, C(NR 6 n.-R 3 m.C (N1 5 m, R 4 COOM 15 wherein: R 4 is selected from the group consisting of C 1 -C, alkylene, C 5 -C, 2 cycloalkylene, C 6 -C, 1 arylene and radical combinations thereof; R 5 is selected from the group consisting of hydrogen, CI-C 16 alkyl and C 6 -C 12 aryl radicals and carbonyl radical that can form a ring together with R 3 25 R 6 is selected from the group consisting of hydrogen, CI-C 1 6 alkyl and C 6 -C 1 aryl radicals and a radical that can form a C 3 -C 12 ring together with R 3 R 3 is selected from the group consisting of C 1 -C 12 alkylene, Cs-C 12 cycloalkylene and C 6 -C,1 arylene radicals; n' and n" each are an integer chosen such that the sum thereof is 1; 35 C6167 (C) m' and m" each are an integer chosen such that the sum thereof is 1; and M is selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, ammonium and alkanolammonium cations and radicals.

3. A composition according to claim 1 wherein the amido or imido organic peroxyacid is present in an amount from 0.1 to 40% by weight.

4. A composition according to claim 1 wherein the pH- adjusting system is present in an amount from about 1 to about 40% by weight.

5. A composition according to claim 1 wherein the surfactant is present in an amount from about 1 to about 50% by weight. S

6. A composition according to claim 1 wherein the peroxyacid is selected from 'ii N,N'-di(4-percarboxybenzoyl)-1,4-butanediamine; N,N'-di(4-percarboxybenzoyl)-1,2-phenylenediamine; N,N'-succinoyl-di(4-percarboxy)aniline; 4-percarboxybenzoyl aniline; N,N-phthaloyl-4-aminoperbenzoic acid; N,N,N',N'-1,2,4,5-tetracarboxybenzoyl-di(6- aminopercarboxycaproic acid); 36 C6167 (C) N,N'-di (4-percarboxybenzyl) ethylenediamine; N,N'-di- (4-percarboxyaniline) terephthalate; N,N'-di (4-percarboxybenzoyl)piperazine; N,N'-di (4.,percarboxybenzoyl) 4-diamine-cyclohexane; N,N' -di (percarboxyadipoyl) phenylenediamine; N, N'-di (percarboxyadipoyl) ethylenediamine; 0613 N,N'-terephthaloyl-di(6-aminoperoxycaproic acid).

7. A composition according to claim 1 further comprising a deflocculating polymer.

8. A method for cleaning stained substrates which comprises treating the substrate with a composition according to claim 25 DATED 26 October, 1995 Signed for and on behalf of UNILEVER PLC by Unilever Australia Limited B. F. JONES, in'- ecretary