AU668936B2 - Acidic activated bleaching compositon - Google Patents

Description

Ir r OPI DATE 08/11/93 APPLN. ID AOJP DATE 13/01/94 PCT NUMBER 39399/93 PCT/US93/02944 S1111AU 11111111111 lllll I l933939 ll I AU9339399 (51) International Patent Classification 5 (11) International Publication Number: WO 93/20167 C09K 3/00, 15/00 Al (43) International Publication Date: 14 October 1993 (14.10.93) (21) International Application Number: PCT/US93/02944 (74) Agents: REED, David et al.; The Procter Gamble Company, 5299 Spring Grove Avenue, Cincinnati, OH (22) International Filing Date: 29 March 1993 (29.03.93) 45202 (US).

Priority data: (81) Designated States: AU, BB, BG, BR, CA, CZ, FI, HU, JP, 92200961.8 3 April 1992 (03.04.92) EP KP, KR, KZ, LK, MG, MN, MW, NO, NZ, PL, RO, (34) Countries for which the regional RU, SD, SK, UA, US, VN, European patent (AT, BE, or international application CH, DE, DK, ES, FR, GB, GR, IE, IT, LU, MC, NL, wasfiled: BE et al. PT, SE), OAPI patent (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG).

(71) Applicant (for all designated States except US): THE PROC- TER GAMBLE COMPANY [US/US]; One Procter Published Gamble Plaza, Cincinnati, OH 45202 With international search report.

(72) Inventors; and Inventors/Applicants (for US only): HARDY, Frederick, Edward [GB/GB]; 8 Woodend Darras Hall, Newcastle upon Tyne NE20 9ES SCOCCIANTI, Raffaele [IT/ IT]; Viale Trastevere, 26, 1-00153 Rome SCIALLA, Stefano [IT/IT]; Viale de Caduti Liberazione, 131, 1- 00128 Rome MANFREDI, Barbara [IT/IT]; Via Salento, 14, 1-00162 Rome i (54)Title: ACIDIC ACTIVATED BLEACHING COMPOSITON (57) Abstract Aqueous bleaching compositions are disclosed which comprise hydrogen peroxide is well as an organic peracid precursor selected from a specific class of glycol and glycerin esters. The compositions have a pH in the range of from about 3.5 to about 6.

The disclosed compositions are both physically and chemically stable.

~~~l~bl WO 93/20167 PGr/US93/02944 Ac 4 lic activated bleaching composition Technical field The present invention relates to bleaching compositions, mainly for use in laundry applications.

The compositions according to the present invention, which comprise hydrogen peroxide as well as peracid precursors, are stable upon storage.

Background Bleaching compositions using hydrogen peroxide have been extensively described in the art. Such hydrogen peroxide bleaches have an advantage over chlorine bleaches in that they are environmentally more compatible. Another advantage is that they are "milder" bleaches. This latter advantage is especially I' PQ WO 93/20167 pCT'/US93/02944 -2significant in laundry applications as hydrogen peroxide bleaches are safer to fabrics.

A major drawback of hydrogen peroxide bleaches is that they are less active than chlorine bleaches at low temperatures which are often encountered in modern laundering applications. Thus, hydrogen peroxide bleach activators have been developed and have been extensively described in the art. These activators are mainly transition metals or peracid precursors.

Peracid precursors react with hydrogen peroxide to yield peracids. Peracids are the "activated" bleaching compounds which are efficient at low temperatures.

A problem which occurs in the formulation of such "activated" hydrogen peroxide bleaching compositions is the difficulty to obtain a composition which is both chemically and physically stable. Indeed, such compositions of the prior art are either turbid suspensions of insoluble activators with good chemical stability, or clear compositions with poor chemical stability which causes significant and undesired oxygen release.

It has now been found that this problem could be addressed by formulating a bleaching composition comprising hydrogen peroxide, an organic peracid precursor selected from a specific class, e.g. glycol and glycerin esters, and by formulating said composition in a narrow, acidic pH range. The mildly acidic pH range allows for adequate chemical stability of both the hydrogen peroxide and the organic peracid precursor. The activation of hydrogen peroxide trough the formation of a peracid is enhanced by the pH raise

I,(

-3which occurs upon dilution in the wash water, especially when a detergent composition bringing further alkalinity is also present in the wash water.

Glycol esters have been often described as solvents in detergent and bleaching compositions. Such compositions are described for instance in US 3 956 159.

These compositions have a pH of 6.5 and above.

J 62252500 (abstract) discloses bleaching compositions which comprise a bleach activator, including triacetin. These compositions are formulated at neutral or weakly basic pH.

Bleaching compositions for various applications, comprising triacetin are also disclosed in J62001792, J62001794 J62001796, and J61042600 (abstracts).

Throughout the description and claims of this specification, the word "comprise" and variations of the word, such as "comprising" and "comprises", is not intended to exclude other additives or components or integers.

0000 0 0 oe Summary of the Invention 0 0 a 0The compositions according to the present invention are clear aqueous bleaching o e0 compositions comprising hydrogen peroxide as well as an organic peracid precursor, wherein the compositions have a pH in the range of from 3.5 to 6, and 0e 0that the organic peracid precursor is a compound according to the formula:

CH

2 CH CH 2 I: RR2 R3 x i b 4 oi' k

I^

WO 93/20167 PCT/US93/02944 -4wherein x is 0 or 1, R 1

R

2 R3 are independently selected from -OH, -C-0-R 4 or -O-C-R 4 where R 4 is II II 0 0

C

1

-C

4 alkyl, with the proviso that at least two of R 1 R2 or R 3 are -O-C-R 4 or mixtures thereof.

SI

0 Detailed description of the invention The compositions according to the present invention are clear aqueous liquid compositions which comprise hydrogen peroxide. Preferably, the compositions according to the present invention comprise from about to about 20 by weight of the total composition of hydrogen peroxide, more preferably from about 2 to about 15 most preferably from about 4 to about 9%.

The compositio.s according to the present invention further comprise a specific organic peracid precursor according to the formula: CH2- CH CH 2 R1 R2 R3 x wherein x is 0 or 1, R 1

R

2

R

3 are independently selected from -OH, -C-0-R 4 or -O-C-R 4 where R 4 is I 1I 0 0

C

1

-C

4 alkyl, with the proviso that at least two of R 1 R2 or R 3 are -0-C-R 4 or mixtures thereof. All these 0 0 l~l~ r -L i I WO 93/20167 PCT/US93/02944 compounds are well known chemicals which are commercially available or can be synthesized according to the cbemical literature.

Preferred such peracid precursors for use in the compositions according to the present invention are selected from ethylene glycol diesters, triacetin and diacetin, or mixtures thereof. Particularly preferred compounds are triacetin and ethylene glycol diacetate.

Tributyzin also displays excellent stability in the compositions according to the present invention but is less preferred because it is less soluble in the compositions acccrding to the present invention.

The compositions according to the present invention typically comprise from about 1 to about 15 by weight of the total composition of such an organic peracid precursor, or mixtures thereof. The desired amount of organic peracid precursor can also be defined in relation to the amount of hydrogen peroxide in the composition. Accordingly, the compositions according to the present invention preferably comprise from about 0.1 to about 2 moles of organic peracid precursor per mole of hydrogen peroxide.

The compositions according to the present invention have a pH in the range of from about 3.5 to about 6, most preferably from about 3.5 to about 5, most preferably about 4. The pH of the composition can be adjusted and buffered with such chemicals as organic and inorganic acids which are stable to oxidation, citric acid, sulphuric acid, sodium hydroxide, ammonia and amines. Preferred buffer for use in the

I

I_ r WO 93/20167 PCT/US93/02944

I

compositions according to the present invention is citric acid. It is essential that the pH of the composition remains within the above range as said range is critical to ensure adequate chemical stability of the hydrogen peroxide ar,3 of the specific organic peracid precursors used in the compositions according to the present invention.

The compositions according to the present invention may comprise surfactants. Preferred surfactants for use herein are well known anionic surfactants such as alkyl benzene sulphonates and alkyl sulfates, and/or nonionic surfactants such as ethcxylated and/or propoxylated alcohols. All surfactants for use herein must be resistant to oxidation by peracids and hydrogen peroxide, and are preferably water-soluble. The compositions according to the present invention can comprise from 0% to about 30% by weight of the total composition of surfactants, preferably from about 0.5 to about 15 most preferably from about 2 to 8 The compositions according to the present invention may further comprise peroxide stabilizers such as stannates, 8-hydroxyquinoline, pyrophosphates and phosphonates. Chelating agents may also be useful in the context of the present invention; suitable chelants include EDTA, NTA and DETPA, picolinic and dipicolinic acids and amino polyphosphonates, although some of these are poorly environmentally compatible. Radical scavengers can also be used herein, such as butylated hydroxy toluene and other hindered hydroxy benzenes, or sodium benzoate. Butylated hydroxy toluene is a highly preferred ingredient as it has been observed that it 9, I anll~ WO 93/20167 PCr/US93/02944 -7stabilizes the peracid precursors according to the present invention, as well as hydrogen peroxide.

The compositions according to the present invention can also comprise such optional ingredients as whitening agents, dyes, builders, thickeners, hydrotropes, perfumes, all of which need to be compatible with the mildly acidic pH and the oxidizing environment of the compositions according to the present invention.

The compositions according to the present invention are further illustrated in the following examples.

Examples The following compositions are made by mixing together the listed ingredients in the listed proportions.

Ingredients: Hydrogen peroxide Na alkyl sulphate Triacetin Citric acid Na Stannate Na hydroxide Water minors 6.0 2.8 4.0 1.0 0.0015 pH 4

II

6.0 2.8 5.0 1.0 0.0010 pH 4 by weight: III IV 6.0 2.8 2.8 4.0 1.0 0.0015 0.0015 pH 3.5 pH 5 up to 100 pH 4 -r -s -L Mer-n- WVO 93/20167 PTU9/24 PCr/US93/02944 Ingredients: by weight: Hydrogen peroxide Na alkyl sulphate Triacetin Ethylene glycol diacetate Citric acid Na stannate Na hydroxide water minors 6.0 2.8 4.0 1.0 0. 0015 PH 4 8 1 2.0 3.0 1.0 0.0015 pH 4

VII

3.5 4.0

VIII

1.0 0.0010 0.0015 pH 4 pH 4 up to 100

Claims (12)

1. An aqueous bleaching composition comprising hydrogen peroxide and an organic peracid precursor, wherein the compositions have a pH in the range of from 3.5 to 6, and that the organic peracid precursor is a compound according to the formula: CH 2 CH CH 2 R1 R2 R3 x wherein x is 0 or 1, R 1 R 2 R 3 are independently selected from -OH, -C-O-R 4 or -O-C-R 4 where R 4 is CI-C4 alkyl, with the proviso that at least two of 0 0 R 1 R 2 or R 3 are -O-C-R 4 or mixtures thereof. 0

2. A composition according to claim 1 which has a pH in the range of from about 3.5 to about 15

3. A composition according to either claim 1 or claim 2 which has a pH of 0 0o °o about 4.

4. A composition according to any one of claims 1 to 3 wherein the organic 0 0 0 peracid precursor is selected from ethylene glycol diesters, triacetin, diacetin, or mixtures thereof.

5. A composition according to any one of claims 1 to 4 wherein the organic peracid precursor is selected from triacetin and ethylene glycol diacetate. i

6. A composition according to any one of claims 1 to 5 which comprises from about 0.5% to about 20% by weight of the total composition of hydrogen peroxide. S 25

7. A composition according to any one of claims 1 to 6 which comprises from about 1% to about 15% by weight of the total composition of said organic peracid precursor. L:

8. A composition according to claim 6 which comprises from about 0.1 to about 2 moles of said organic peracid precursor per mole of hydrogen peroxide.

9. A composition according to any one of claims 1 to 8 which comprises from about 0.5% to about 15 by weight of the total composition of a surfactant.

10. A composition according to any one of claims 1 to 9 which comprises citric acid.

11. A composition according to any one of claims 1 to 10 which comprises butylated hydroxy toluene.

12. A composition according to claim 1 substantially as hereinbefore described with reference to any one of the examples. DATED: 18 March, 1996 o o 0 ou o o o00 o o 0 o eo o0 0 0o 0 0 0 o 0o 00 0 0 0 0 0 0 0 0 o o oa 00 0 So Q 00 0 0 0 S 0 o Q 0 0 0 0 C 0 f 0 0 0 0 ao o o o o a o~o o~o o a i 0 C o 6 a THE PROCTER GAMBLE COMPANY Patent Attorneys for: 20 PHILLIPS ORMONDE FITZPATRICK r T c r i~--l Iv V INERNATIONAL SEARCH REPORT PCmrA.S93/02944 A. CLASSIFICATION OF SUBJECT MATTER :CO9K 3/00, 15100 US CL :252/116.28,196.29,186.38 According to International Patent Classification (IPC) or to both national classification and IPC B. FIELDS SEARCHED Minimumn documentation searched (classification system followed by classification symbols) U.S. :252/186.28,186.29,186.38 Documentation searched other than minimum documentation to the extent that such documents are included in the fields searmhed Electronic data base consulted during the international search (name of data base and, where practicable, search terms used) APS C. DOCUMENTS CONSIDERED TO BE RELEVANT Category* f Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. X PA, J62252500 (Kao Corp.) 04 Noveim.ber 1987 See Derwent I-. Y Abstract 9-11 XJP,A, J62001792 (-Kao Corp.) 01 July 1987 See Derwent 1-10 Y Abstract I1I XJP,A, J62001794 (Kao Corp.) 01 July 1987 See Derwent 1-10 YAbstract I I X JP,A, J62001796 (Kao Corp.) 01 July 1987 See Derwent 1-10 Y Abstract I1I1 X JP,A, J61042600 (Kao, Corp.) 03 J~anuary, 1986 See Derwent 1-8 Y Abstract 9-1 1 Further documents are listed in the continuation of Box C. D1 See patent family annex. Special categories of cited documents: Wat document published after the insetcr-monal fiding date or unonty dale and nom in conflict with the application but cited to unlerstand the documcmdeflan the general stte of the ant which is no cosideredpioik or th~eory unlying thu.i invetion to be part of pariailadr relevance E' earlier documesnt publishe an o te h nen tioa iig daft X. docment of Particular relevance. the claime invention -nonot be considered novel or cannot be coeidered to involve an invenotvc step L' t ot which may throw doubts o priority claim(s) ot which is whon the documnit a taken alone cited to establish the pub~lication date tf ather citation or other. special rean (m speiied) Y* document of particular relevance; the clai..v invention cannot be considered to involve an inventive ste when the document w .0 docmnt~ referring to an oMa ditelosurc. tue. exhbrtion or other combined with one or more other such documnents. such combinjuton mm being obvious to a person sktilled in the art .11 doctanena published prior to the internatonal filing date bt lae tha docuent member of the same patent family the priority dame claimned Date of the actual completion of thes international search Date of mailing of the international search report 21 JUNE 1993 1JLL1993 Name and mailing address of the ISA/US Authorized officer Cotmmissionser of Patents and Trademarks Box PCT JOSEPH D. ANTHONY ,.2 Facsimiile No. NOT APPLICABLE Telephone No. (703) 308-0446 Form PCT/ISAt210 (second sheet)(July 1992)* q INTERNATIONAL SEARCH REPORT International application No. PCTIUS93/0294-4 C (Continuation). DorijMENTS CONSIDERED TO BE RELEVANT Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. US,A, 4,800,038 (Broze et ad.) 24 January 1989 See Abstract and Claims USA, 5,047,168 (Broze et al.) 10 September 1991 See Abstract and Claims US,A, 5,151,212 (Bell et ad.) 29 September 1992 See Abstract and Claims USA, 3,956,159 (Jones) 11 May 1976 See "Summary of Invenltion" and Claims 1-Il 1-11 1-11 1-11 Formr PCTIAI21O (continuation of second sheet)(Juiy 1992)* L