Europaisches Patentamt (19) European Patent Office Office europeenpeen des brevets EP 0 484 324 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.e: C11D 3/39 of the grant of the patent: 20.10.1999 Bulletin 1999/42 (21) Application number: 92101864.4 (22) Date of filing: 19.06.1985 (54) Cleaning compositions containing bleach activator compounds Reinigungsmittelzusammensetzungen enthaltend Bleichaktivatoren Compositions de nettoyage contenant des activateurs de blanchiment (84) Designated Contracting States: (72) Inventors: AT BE CH DE FR GB IT LI NL SE • Hardy, Frederick Edward Newcastle upon Tyne NE20 9ES (GB) (30) Priority: 21.06.1984 GB 8415909 • Ingram, Barry Thomas Tyne & Wear, NE26 1 JE (GB) (43) Date of publication of application: 06.05.1992 Bulletin 1992/19 (74) Representative: Peet, Jillian Wendy et al Procter & Gamble Technical Centres Limited, (62) Document number(s) of the earlier application(s) in Whitley Road, accordance with Art. 76 EPC: Longbenton 85304373.5/0 166 571 Newcastle upon Tyne NE12 9TS (GB) (73) Proprietors: (56) References cited: • THE PROCTER & GAMBLE COMPANY FR-A-2 187 983 FR-A- 2 313 445 Cincinnati, Ohio 45202 (US) FR-A- 2 353 634 GB-A- 1 445 299 Designated Contracting States: US-A- 2 955 905 US-A- 3 256 198 BE CH DE FR IT LI NL SE AT US-A- 3 272 750 US-A- 4 110 074 • Procter & Gamble Limited Gosforth Newcastle upon Tyne NE99 1EE (GB) Designated Contracting States: GB DO ^- CM CO ^- 00 ^- Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice the Patent Office of the Notice of shall be filed in o to European opposition to European patent granted. opposition a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. a. 99(1) European Patent Convention). LU Printed by Jouve, 75001 PARIS (FR) EP 0 484 324 B1 Description [0001] The present invention relates to a cleaning composition comprising a peroxide source and a bleach activator. 5 BACKGROUND [0002] Peroxyacids (herein "peracids") are a well-known class of organic compounds that can be prepared, for ex- ample, by the action of hydrogen peroxide on organic acids in the presence of an acid catalyst. See ORGANIC PER- OXIDES. E.G.E. Hawkins, D. Van Nostrand Company, Inc. (1961). Peracids have a variety of industrial uses, for ex- 10 ample, as catalysts and as oxidizing agents. [0003] Peracids also find use as cleaners and laundry bleaches. As such, the formulator typically prepares a relatively stable compound (a so-called "bleach activator") which decomposes in water in the presence of inorganic percarbonate or perborate to form the peracid in situ in a laundry liquor. See, generally, British 864 768; Canadian 635 620; U.S. 4 100 095; 4 119 660; 4 126 573; 4 412 934 and EPO published applications 0 068 547, 83 303 675.9. See especially 15 U.K. 1 382 594 for Quat-Activators. [0004] US-A-3,272,756 describes a detergent composition and process for bleaching textile materials. The bleaching composition comprising an inorganic persalt and an ester of carbonic acid or pyrocarbonic acid. US-A-3,256,198 de- scribes a detergent composition comprising an oxygen-releasing compound and an organic carbonate which bleaches and whitens textile and fabrics. GB-A-1 ,445,299 describes a bleaching composition containing an inorganic percom- 20 pound capable of releasing hydrogen peroxide and an activating agent. [0005] As can be seen from the extensive literature, there is a continuing search for new, more effective peracids and bleach activators. One major problem with some activators (or their degradation products, in-use) is poor odor quality. Another problem is that some activators are either rather complicated structures, or are made from rather expensive raw materials; in either event, many art -disclosed materials have remained laboratory curiosities rather than 25 viable commercial items. [0006] The present invention provides a cleaning composition comprising bleach activators which are readily pre- pared from inexpensive raw materials, and which do not suffer from the problems associated with many art-disclosed bleaching agents. [0007] The present invention encompasses a cleaning composition comprising a peroxide source and a bleach ac- 30 tivator compound of the formula [RX]mAL 35 wherein R is C6-C20 branched straight-chain or substituted, allyl, alkenyl, or alkyl-substituted aryl; X is O, S02, (R')P^O or (R')N^O and wherein for m = I, A is 40 0 0 45 or 50 or 55 0 „ II 2 EP 0 484 324 B1 or 0 0 -C-Oj<H-C- or 0 o n « , where x is an integer from 0 to 4; z is an integer from 0 to 2; (R1) is alkyl and R" is branched-chain alkylene and wherein for m = 2, A is 0 \ II CH-C- and wherein L is a leaving group, comprising a group selected from 0 -NCR2 (a) and(b) Y wherein x is an integer from 0 to 8, Z is H, R2 or halide, R2 is C1 to4 alkyl, and Y is selected from S03M, OS03M, C02M, N+(R2)3Q", N(R2)2->0 wherein M is H, alkali metal, alkaline earth metal, ammonium or substituted ammo- nium and Q is halide or methosulphate, the conjugate acid of which has a pKa in the range from 6 to 13. [0008] Preferred compounds herein are those wherein X is oxygen. [0009] The bleaching compositions of the invention comprising the bleach activator described above also comprise a peroxide source such as a perborate, percarbonate, or peroxide compounds. [0010] In general, 'R' in the above formulas can be branched or straight-chain or substituted C6-C20 alkyl or alkenyl or C6-C20 alkyl - substituted aryl. C6-C15 alkyl is especially preferred for oxidative stability. Also, 'R' can be optionally alkoxylated (i.e. linked to one or more ethyleneoxy or propyleneoxy groups or mixtures thereof). DETAILED DESCRIPTION OF THE INVENTION [0011] The compounds of this invention, and their synthesis, can best be understood by a consideration of the bleach activator compounds. It will be appreciated that the peracid compounds can be generated in situ from the activator compounds in aqueous media, in the presence of peroxide. [0012] The bleach activator compounds can be described as comprising three parts: (i) an optionally alkoxylated EP 0 484 324 B1 hydrocarbyl part (designated 'R' in the general formula) said hydrocarbyl part being linked via a heteroatom ('X' in the formula) to (ii) a bridging part ('A' in the formula) which contains a labile carbonyl group; said bridging part being attached to a leaving group ('L' in the formula) at the labile carbonyl group; as follows: 5 [RX] m-A-L [0013] In use, the activator forms the active, bleaching peracids, as follows: 10 00H~ [RX] AL > RXAOOH + L 15 Synthesis Schemes [0014] The synthesis of the herein-disclosed peroxy acids per se employs standard chemical reactions, and such 20 synthesis schemes form no part of the present invention. For example, the parent organic acid can be reacted with H202 in the presence of an inorganic acid catalyst to form an equilibrium aqueous mixture containing the organic peracid. Alternatively, the acid chloride or acid anhydride can be used with H202. Cationic ion-exchange resins may be used as the catalyst. Water-free peracids can be prepared by azeotropic distillation from alkyl acetate solvents. Dipicolinic acid can be used to reduce the danger of explosions when the pure acid is being isolated. 25 [0015] It is to be understood that there is no need to isolate the pure peracid in order to use it as a bleaching or cleaning agent ; indeed, to do so is generally wasteful, since the peracid is typically used in solution rather than as the pure compound. [0016] The peracids herein are most conveniently provided in situ when their respective bleach activator molecules are placed in the presence of a peroxide source (e.g. H202, sodium perborate or sodium percarbonate) and water at 30 alkaline pH. [0017] Having earlier considered the bleach activator molecules as comprising three parts, it becomes relatively simple to devise synthesis schemes for the various compounds herein, using well-known starting materials and chem- ical reactions. [0018] For example, portion "RX" of the activators (and the peracids) can comprise the commercially-available al- 35 cohols (ROH) and amines (RNH2). It will be appreciated that the N(H) hetero-atom will be more-or-less labile to self- oxidation unless limited to a carbonyl, i.e., amides. Hence in other cases substituent groups should preferably be alkyl (conveniently C-^-C^ rather than hydrogen and are designated R' in the general formula, shown above. [0019] The bridging group "A" of the activators (and the peracids) can comprise moieties derived from such com- monly-available materials as oxalic acid (-C(O)-C(O)-); maleic acid (-C(0)CH=CHC(0)): phthalic acid (-C(0)C6H4C 40 (O)-); adipic acid (-C(0)(CH2)4C(0)-); Such bridging moieties are all derivable by chemical reactions well known in the art [0020] The combination of "RXA" forms the parent acids from which the peracids can ben generated, as noted above, and also constitutes the parent acid of the bleach activators, which are formed from RXA acids and leaving groups "L". [0021] With regard to leaving group "L", it will be apppreciatedfrom even a cursory review of the cited patent literature 45 that there is a wide choice of chemical moieties which act as leaving groups and from which bleach activator molecules can be synthesized which are sufficiently stable for incorporation into a home laundry detergent or laundry bleach.