Search Images Maps Play YouTube News Gmail Drive More »
Sign in
Screen reader users: click this link for accessible mode. Accessible mode has the same essential features but works better with your reader.


  1. Advanced Patent Search
Publication numberUS3398096 A
Publication typeGrant
Publication dateAug 20, 1968
Filing dateJul 23, 1965
Priority dateJul 24, 1964
Also published asDE1280456B
Publication numberUS 3398096 A, US 3398096A, US-A-3398096, US3398096 A, US3398096A
InventorsDas Balaram, Karel Gerhard Van Senden
Original AssigneeLever Brothers Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Low temperature bleaching composition
US 3398096 A
Abstract  available in
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

-ABSTRACT OF THE DISCLOSURE A stable dry catalyst powder fore-nhan-cing the bleaching action of water-soluble inorganic p'ercompounds at 'low temperatures of 2050 C. Comprising a metal-ion of a transition element and a water-insoluble or hardly solu'ble powdered carrier, processes for the preparation thereof and percompound bleaching compositions containing the catalyst powder.

The invention relates to ion/carrier catalysts, to .processes for the preparation of ion/carrier catalysts and to bleaching compositions containing these catalysts. In particular, the invention relates to ion/ carrier catalysts which affect the bleaching actionof inorganicprecompounds to such an extent that effective bleaching at relatively low temperatures, e.g. 2050 C., can be achieved and to their preparation in a suitable and stable form andto their use in bleaching compositions. Such catalysts can be ad vantageously used 'in bleaching compositions containing inorganic percompounds, e.g. perborates or persulphates, to obtain low-temperature bleaching and find particular use in scouring powder formulations containing inorganic percompounds.

It isknown that certain cobalt and manganese salt solutions when freshly adsorbed on asuitable carrier, such as the alkaline carbonates of calcium,-magnesium, zinc or cadmium, exercise ahighly catalysing effect on the bleaching action of hydrogenperoxide. Such freshly prepared systems when mixed with a hydrogen peroxide solution have a bleaching effect on certain-dyestuff solutions at room temperature.

Known low-temperature bleaching compositions generally contain a chlorine-releasing compound, such as dichlorocyanuric or trichlorocyanuricacid, which has the disadvantageuof spreading a disagreeable chlorine smell, which persists for .some time after use, especially on the skin, and the further disadvantage of sometimes attacking the fibres of textiles, especially of some finished fabrics.

Another disadvantageconnected with compositions based on chlorine bleache-s is their instability on storage, resulting in a decrease of bleaching effect. These disadvantages are not presentto the same extent with bleaching compositions based on inorganic percompounds, such as perborates or persulphates. However, inorganic percompounds are relatively inactive bleaching agents at low temperatures, e.g. 20-50" C. Their bleaching effect increases with increasing temperature and attains its maximum at the boil. e

It is an object of the invention to prepare stable catalysts as a dry powder having a free moisture content of less than 15%, preferably 15%, which can be incorporated in bleaching compositions containing inorganic percompounds and particularly in scouring powder bleach formulations containing inorganic percompounds.

It is also an object of the invention to provide low-temperature bleaching compositions which are effective in the removal of persistent stains, e.g. tea stains, from hard surfaces, such as dishes, tiles and the like, and. which are r d, S ate P te ice also useful for bleaching stains on fibrous materials, such as finished and unfinished textile fabrics.

Another object is to provide detergent compositions especially for dishwashing containing inorganic percompounds having low-temperature bleaching properties A further object is to provide scouring powder compositions containing inorganicpercompounds, e.g. sodium perborate, having a bleaching effect comparable with those compositions containing chlorine bleaches.

The catalysts according to the invention comprise a metal ion adsorbed on a suitable inorganic carrier. The metal ions themselves in a non-adsorbed form may or may not have any effect on the bleaching activity of the inorganic percompound. However, when suitably adsorbed on suitable carriers these metal ions increase the bleaching activity to a large extent. It has been found that the metal ions of the transition elements in the periodic system especially those having an unpaired electron spin, such as Co Mn Ni Cr M0, or Ca are particularly-etfective. The carriers which can be advantageously used may be any water-insoluble or slightly soluble compound of Zn, Cd, Ca, Mg, Al, Sn, Be, Ti, Sb, Bi or SiO Of these possible combinations the most active catalysts are found when Co is adsorbed on: zinc silicate; titanium dioxide or hydroxide; tin dioxide; antimony trioxide; aluminium oxide, hydroxide or silicate; alkaline zinc carbonate; alkaline cadmium carbonate; cadmium carbonate, silicate or oxide. The metal-ion content may be from 1-100 mg. or more per gram catalyst, and preferably from 20-60 mg./ g. It goes without saying that the catalysts according to the invention are also effective to aid the bleaching action of inorganic percompounds on coloured solutions at low temperature.

The catalysts according to the invention may be prepared in the following ways:

(a) By dry-mixing a finely-divided powdered salt, e.g. CoCl containing the metal ion, with the finely-divided carrier in such a way that a homogeneous mixture is obtained, in which both substances are in very good contact.

(b) By adding an aqueous solution containing the metal ion, e.g. CoCl solution, to the required amount of finely powdered carrier. Water is then added and the whole mixture is stirred until a paste-like substance is obtained. The product is then dried at temperatures up to about C.vacuum may or may not be applied preferably at temperatures of 4060 C. in a vacuum of 1-15 mm. Hg. Much higher temperatures may also be applied, depending on the type of catalyst, although it is not advisable since it would affect the catalysts activity.

(0) By freeze-drying the paste-like substances as described in (b), at temperatures of 50 to 0 C. in a vacuum of 001-1 mm. Hg.

The catalysts obtained by the aforementioned methods assist bleaching at low temperatures (20 C. or even lower), as well as at higher temperatures, with sodium perborate and/ or with other inorganic percom-pounds including percompounds, such as Du Ponts Oxone (a triple salt consisting of potassium permonosulphate, potassium hydrogen sulphate and potassium sulphate in the approximate molecular ratio of 2:1:1).

It is desirable that the bleaching compositions should give an alkaline solution, preferably one having a pH value of between 7 and 11 It has been found that catalysts prepared according to the process of the present invention can be stored for some time without losing their activity. They can be drymixed with inorganic percompounds to form low-temperature bleaching compositions, preferably at weight ratios of between 1: 1 and 1:8. Such mixtures when incorporated in normal detergent compositions enable the latter to bleach effectively at relatively low temperatures. It has also been surprisingly found that the catalysts obtained from the freeze-drying process (process (c)), especially those with zinc compound carriers, are much more ac- These compositions were tested at room temperature for the bleaching of tea stains on unglazed tiles (Royal Sphinx Maastricht, 15 x 15 cm.) by applying them as a paste-like substance to the tile surface. The following test tive than the catalysts prepared from the same com- 5 method was used: pounds according to process (a) or (b)- Their ac ivity, The reflectance of a tea-stained tile was measured. however, decreases on storing under normal room condigrams powder were mixed with 7 ml. distilled water and tions to values approaching those of catalysts prepared stirred for 30 seconds. The mixture was poured on the tile according to the other processes of the invention. By a surface. After a contact time of 1 or 2 minutes the paste suitable coating of the particles it would be possible to 10 was rinsed from the tile surface with running tap water retain his extremely high activity originally obtained. Catfor at least 10 seconds. After standing in the air for about alysts prepared with carriers havingaparticle size of 30-52 24 hrs. the reflectance of the tile was measured again. mesh (British Standard Sieve) are especially suitable for In the following table the increase in reflectance of the tile coating. surface after treatment is given. From this table it can be The catalysts prepared according to the processes of seen that the type of carrier used is an important factor. the invention can be mixed with inorganic percompounds e.g. sodium perborate, to form stable low-temperature TABLE H bleaching compositions. They can also be incorporated in Increase inreflectance detergent powder formulations having a percompound Commsitlon Carrier Percent after time content of up to 30% and also in scouring powder com- 1min. 2min. positions with a percompound content of 120%, pref- I Zinc Silicate 27 42 erably 5-15 of sodium perborate. When used in scour- Cadmium carbonate 27 29 ing powder formulations it is preferable that the catalyst ififgggggagzz 3; 3 be added to the powder as the last component under Zincsilicate 26 30 thorough mixing. It is also preferable that the moisture Zmc g content of the detergent powder or scouring powder be 0 5 as low as possible. a

In order to avoid unwanted colouring of the bleaching by pf s 21 0 pared by dry mixmg' The othel catalysts were prepared solution and of the object to be bleached, which may be caused by the catalysing metal ion, sequestering agents Example 3 Y be incorporated in the bleaching composition The first four of the compositions referred to in Table sodlilm hexametfllhmRhateother Condensed phosphates II above were stored at room temperature in closed vessels particularly sod um tripolyphosphate, app reduce for two months and their bleaching effect again deterthe catalysts, actwlty' mined in the same way as described in Example 2. The Example 1 following results show that the compositions retained their bleaching activity during storage: Catalysts having a cobalt content of approximately 4% mg./ g. catalyst) were prepared in the following TABLE III wags; 100 fl 1 d d H t (100 h 40 [Results obtained after storage for 2 months] a g. ne y pow ere zinc s rca e mes British Standard Sieve) and 19 g. Co'Cl -6H 0 were Composition Carrier iii d iliiififii c t tih fii mixed together in a mortar so that a homogeneous mixture was obtained. The zinc silicate was previously dried in an oven at 80 C. under vacuum for one hour. 4 I gg g f f ig g (b) To 200 g. finely powdered ZlIlC silicate (100 mesh I Stannlc oxide 22 23 British Standard Sieve) a solution of 38 g. CoC1-6H O Antlmony oxlde 27 28 was added in 180 ml. Water and the mixture was stirred so that a homogeneous paste was obtained. Part of the What is claimed is, ji thenhdned li g z g 1. A process for the preparation of a stable dry catalyst E g Ours t e E a t y g; i i powder for enhancing the bleaching action of water solue graim es m mm at a a CB mols me C n en 0 ble inorganic percompounds at low temperatures in which 'approxlmately an aqueous solution of a salt containing a metal-ion (c) The other part of E paste was dned at gg selected from the group consisting of the transition eleperature of less i 20 and at a pressure 0 merits in the periodic system is added to a powdered car- The molsture content of the product was aprier selected from the group consisting of water-insoluble proxlmalwly or hardly soluble compounds of Zn, Cd, Ca, Mg, Al, Sn,

Examp 1e 2 Be, Ti, Sb, Bi and SiO; to form a homogeneous mixture A number f scouring Powder compositions were and the mixture is thereafter dried to a moisture content pared containing sodium perforate and catalyst prepared 60 of l n according to Example 1. For purposes of comparison two A Process for the p pf 0f 3 f y Powder compositions were also prepared, one without catalyst according Claim in Whlch the drymg 1S earned out and the other containing the metal ion without a carrier. at temperatures not exceeding C.

TABLE I Parts by Weight I II III IV Sodium dodecylbenzenesulphonate i% 5;.an;6:;:;::::::::::::" 815 1530 8:5 gggggg g gg%%ggjgg Catalyst, containing 4% 00 4. 0 4. 0 C0 012 without a carrier 3. A process according to claim 1, in which the drying is carried out under a vacuum of 1 to 15 mm. Hg and at a temperature of 40-60 C.

4. A process according to claim 1, in which the drying is carried out in the form of freeze-drying at a temperature of 50 to (l C. and at a vacuum of 0.01 to 1 mm. Hg.

'5. A low temperature bleaching composition consisting essentially of a mixture of the catalyst powder con sisting essentially of metal-ion selected from the group consisting of the transition elements in the periodic system which is adsorbed on or intimately mixed with a powdered carrier selected from the group consisting of water-insoluble or hardly soluble compounds Zn, Cd, Ca, Mg, A1, Sn, Be, Ti, Sb, Bi and SiO the metal-ion content being from about 1 to milligrams per gram of catalyst powder, and a water-soluble inorganic percompound, the weight ratio between the catalyst powder and the water-soluble inorganic percompound being from about 1:1 to about 1:8.

6. A detergent powder bleach and cleansing composi tion, for use in the presence of water, consisting essentially of the composition defined by claim 5 in amounts such that the water soluble inorganic percompound con tent is up to about percent by weight of said composition.

7. A detergent and scouring composition, for use in the presence of water, consisting essentially of the low temperature bleaching composition defined by claim 5 in an amount such that the water soluble inorganic percompound content is from about 1 percent to about 20 percent by weight of said composition.

References Cited UNITED STATES PATENTS 3,156,654 11/1964 Konecny et a1. 25299 3,207,696 9/ 1965 Shephard et a1. 252-186 3,211,658 10/1965 Hertz et a1. 252-99 LEON D. ROSDOL, Primary Examin r.

M. WEINBLATT, Assistant Examiner.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3156654 *Jun 19, 1961Nov 10, 1964Shell Oil CoBleaching
US3207696 *Jan 18, 1963Sep 21, 1965Shepherd Chemical CompanyComposition and method of forming an extended lead dioxide activator
US3211658 *Mar 12, 1962Oct 12, 1965Colgate Palmolive CoDetergent composition with improved bleaching efficiency
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3474037 *Nov 14, 1966Oct 21, 1969United States Borax ChemStabilization of organic bleaching compositions
US4478733 *Dec 8, 1983Oct 23, 1984Lever Brothers CompanyDetergent compositions
US4536183 *Apr 9, 1984Aug 20, 1985Lever Brothers CompanyManganese bleach activators
US4539132 *May 3, 1984Sep 3, 1985Lever Brothers CompanyBleaching and cleaning composition
US4568477 *Dec 5, 1984Feb 4, 1986Lever Brothers CompanyDetergent bleach compositions
US4578206 *Jun 13, 1984Mar 25, 1986Lever Brothers CompanyDetergent bleach compositions
US4601845 *Apr 2, 1985Jul 22, 1986Lever Brothers CompanyBleaching compositions containing mixed metal cations adsorbed onto aluminosilicate support materials
US4623357 *Apr 2, 1985Nov 18, 1986Lever Brothers CompanyBleach compositions
US4626373 *Nov 5, 1984Dec 2, 1986Lever Brothers CompanyManganese adjuncts, their preparation and use
US4655782 *Dec 6, 1985Apr 7, 1987Lever Brothers CompanyBleach composition of detergent base powder and agglomerated manganese-alluminosilicate catalyst having phosphate salt distributed therebetween
US4655953 *Dec 5, 1984Apr 7, 1987Lever Brothers CompanyDetergent bleach compositions
US4711748 *Nov 12, 1986Dec 8, 1987Lever Brothers CompanyPreparation of bleach catalyst aggregates of manganese cation impregnated aluminosilicates by high velocity granulation
US4731196 *Oct 28, 1986Mar 15, 1988Ethyl CorporationProcess for making bleach activator
US5560748 *Jul 11, 1994Oct 1, 1996The Procter & Gamble CompanyDetergent compositions comprising large pore size redox catalysts
US5622646 *Feb 13, 1996Apr 22, 1997The Procter & Gamble CompanyBleach compositions comprising metal-containing bleach catalysts and antioxidants
US5686014 *Mar 24, 1995Nov 11, 1997The Procter & Gamble CompanyBleach compositions comprising manganese-containing bleach catalysts
US5703030 *Oct 25, 1996Dec 30, 1997The Procter & Gamble CompanyBleach compositions comprising cobalt catalysts
US5703034 *Oct 30, 1995Dec 30, 1997The Procter & Gamble CompanyBleach catalyst particles
US5705464 *Feb 6, 1997Jan 6, 1998The Procter & Gamble CompanyAutomatic dishwashing compositions comprising cobalt catalysts
US5798326 *Feb 10, 1997Aug 25, 1998The Procter & Gamble CompanyAutomatic dishwashing compositions comprising cobalt III catalysts
US5904734 *Nov 7, 1996May 18, 1999S. C. Johnson & Son, Inc.Method for bleaching a hard surface using tungsten activated peroxide
US5939373 *Feb 24, 1998Aug 17, 1999The Procter & Gamble CompanyPhosphate-built automatic dishwashing composition comprising catalysts
US5968881 *Dec 20, 1995Oct 19, 1999The Procter & Gamble CompanyPhosphate built automatic dishwashing compositions comprising catalysts
US6020294 *May 28, 1999Feb 1, 2000Procter & Gamble CompanyAutomatic dishwashing compositions comprising cobalt chelated catalysts
US6119705 *May 28, 1999Sep 19, 2000The Procter & Gamble CompanyAutomatic dishwashing compositions comprising cobalt chelated catalysts
EP0111963A2 *Dec 9, 1983Jun 27, 1984Unilever N.V.Detergent compositions
EP0111963A3 *Dec 9, 1983Nov 20, 1986Unilever NvDetergent compositions
EP0699745A2Aug 4, 1995Mar 6, 1996THE PROCTER & GAMBLE COMPANYAutomatic dishwashing compositions comprising quaternary ammonium compounds bleach activators and quaternary ammonium
EP0804528A1 *Jan 5, 1996Nov 5, 1997THE PROCTER & GAMBLE COMPANYMachine dishwashing compositions containing an oxygen bleach and a bismuth salt to reduce silver tarnishing
EP0804528A4 *Jan 5, 1996Oct 6, 1999Procter & GambleMachine dishwashing compositions containing an oxygen bleach and a bismuth salt to reduce silver tarnishing
EP2966161A1Jul 8, 2014Jan 13, 2016Dalli-Werke GmbH & Co. KGEnzyme-bleach catalyst cogranulate suitable for detergent compositions
EP3075832A1Mar 30, 2015Oct 5, 2016Dalli-Werke GmbH & Co. KGManganese-amino acid compounds in cleaning compositions
WO2000075270A1 *May 24, 2000Dec 14, 2000Henkel Kommanditgesellschaft Auf AktienProduction of a combination of active agents with a bleach catalyst action
U.S. Classification510/368, 510/108, 510/376, 252/186.3, 510/238, 252/186.25, 252/186.2, 510/508
International ClassificationB01J27/06, B01J21/08, C11D3/39, B01J21/00, B01J37/32, B01J37/04
Cooperative ClassificationC11D3/3932, B01J21/00, B01J27/06, C11D3/3935, B01J37/32, B01J21/08, B01J37/04, C11D3/3937
European ClassificationB01J27/06, B01J21/00, B01J37/04, C11D3/39B2F, B01J21/08, B01J37/32, C11D3/39B4, C11D3/39B2M