EP1280881B1 - Bleichmittel und polymere enthaltende maschinengeschirrspülmittellzusammensetzungen - Google Patents

Bleichmittel und polymere enthaltende maschinengeschirrspülmittellzusammensetzungen Download PDF

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Publication number
EP1280881B1
EP1280881B1 EP01940397A EP01940397A EP1280881B1 EP 1280881 B1 EP1280881 B1 EP 1280881B1 EP 01940397 A EP01940397 A EP 01940397A EP 01940397 A EP01940397 A EP 01940397A EP 1280881 B1 EP1280881 B1 EP 1280881B1
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Prior art keywords
bleach
cationic
polymer
polymers
amphoteric
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French (fr)
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EP1280881A1 (de
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Catherine Chiou
Naresh Dhirajlal Ghatlia
John Richard Nicholson
Bozena Marianna Piatek
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Unilever PLC
Unilever NV
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Unilever PLC
Unilever NV
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3773—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3796—Amphoteric polymers or zwitterionic polymers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3915—Sulfur-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3925—Nitriles; Isocyanates or quarternary ammonium nitriles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds
    • C11D3/3927—Quarternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces

Definitions

  • the present disclosure relates to detergent compositions that contain both cationic bleaching agents and polymers incorporating cationic groups.
  • Cationic polymers are known to deliver glass corrosion protection and colour protection benefits in automatic dishwashing formulations. It is believed that the polymer forms a coating on the glass surface, protecting the surface from attack by other ingredients within the formulation.
  • Examples of cationic polymers that reduce corrosion of dishware in an automatic dishwashing machine include those described in US Patent No 5,981,456 (Unilever), the contents of which are incorporated herein by reference.
  • Amphoteric polymers (containing both cationic and anionic groups within the same structure) are known to provide anti-spotting benefits. It is believed that amphoterics suspend proteinaceous soil fragments that are thought to be responsible for spots.
  • amphoteric polymers include water-soluble aminoacryloyl-containing polymers, such those described in US Patent No. 5,308,532 and EP 0 560 519 B1 (both of Rohm and Haas Company).
  • Bleaching compositions and bleach systems are also well known and provide desired cleaning properties in many commercial detergents. Chlorine and N,N,N',N'-tetraacetylethylenediamine (TAED)/perborate, for example, are well known for their bleaching properties. Cationic bleach systems that include cationic nitriles in the presence of peroxide are also known (see, for example, US Patent Nos. 5,236,616 and 5,281,361, EP 0 303 520 B1 and WO 99/63038, the contents of which are incorporated herein by reference).
  • TAED N,N,N',N'-tetraacetylethylenediamine
  • cationic group containing organic bleach activators or bleach catalysts include, for example, cholyl(4-sulfophenyl)carbonate (CSPC, see, for example, US Patent No. 5,106,528 and EP 399,584 B1), quaternary imine salts (e.g. N-methyl-3,4-dihydroisoquinolinium p-toluenesulfonate, US Patent No's. 5,360,568, 5,360,569 and 5,370,826).
  • quaternary imine salts e.g. N-methyl-3,4-dihydroisoquinolinium p-toluenesulfonate
  • EP 0 699 745 US 5,599,781, US 5,520,835, the contents of which are incorporated herein by reference.
  • Cationic peroxyacids such as those described in US Patent Nos. 5,908,820, 5,422,028, 5,294,362 and 5,292,447, have also shown
  • Transition metal-containing bleach catalysts such as [Mn IV 2 (-O) 3 (Me 3 TACN) 2 ](PF 6 ) 2 (US Patent Nos. 4, 728, 455, 5,114,606, 5,153,161, 5,194,416, 5,227,084, 5,244,594, 5,246,612, 5,246,621, 5,256,779, 5,274,147, 5,280,117), [Fe II (MeN4py)(MeCN)](ClO 4 ) 2 (EP 0 909 809) and [Co III (NH 3 ) 5 (OAc)](OAc) 2 (US Patent No. 5,559,261, WO 96/23859, WO 96/23860, WO 96/23861), also exhibit cationic character under typical wash conditions.
  • machine dishwashing detergent formulations containing polymers having cationic monomeric units in combination with a bleaching agent can provide the desired bleaching benefit if the beaching agent also has a cationic group.
  • the present invention provides a machine dishwashing detergent formulation as specified in claim 1.
  • the invention also provides a kit comprising said formulation and further specified in claim 8.
  • the present disclosure primarily relates to detergent formulations that are suitable for use in machine dishwashers.
  • the formulations disclosed herein can be powder, tablet, block, gel, liquid, solid or semi-solid.
  • Suitable formulations generally include one or more of the following ingredients: both phosphate and nonphosphate (e.g. sodium citrate) builders, pH buffering agents; silicates; bleaches and bleaching systems including bleach catalysts; surfactants; enzymes; enzyme stabilization systems; thickeners; stabilizers and/or co-structures; fillers; defoamers; soil suspending agents; antiredeposition agents; anti-corrosion agents; ingredients to enhance décor care; anti-tarnish agents; rinse aids; colourants; perfumes; and other known functional additives. More specific examples of the above and other known machine dish detergent ingredients are disclosed, for example, in U.S. Patent Nos. 5,695,575, 5,705,465, 5,902,781, 5,904,161 and 6,020,294, the contents of which are incorporated herein by reference.
  • phosphate and nonphosphate e.g. sodium citrate
  • silicates e.g. sodium citrate
  • bleaches and bleaching systems including bleach catalysts
  • surfactants e
  • the cationic or amphoteric polymer is present in the formulation of the invention at a level of from about 0.1 to about 20 wt %.
  • the bleach system present in the formulation of the invention comprises a bleach activator, a bleach catalyst or combinations thereof.
  • said bleach system is preferably present at a level of from about 0.01 to about 10 wt % of the total composition.
  • the cationic group containing bleach is preferably selected from the group of organic cationic bleach activators or bleach catalysts consisting of: cationic nitriles; cationic peroxyacid bleach precursors; quaternary imine salts; and mixtures thereof. More preferably said bleach activators or bleach catalysts are selected from the group specified in claim 6.
  • the cationic group containing bleach is preferably selected from the group of transition metal bleach catalysts specified in claim 7.
  • Suitable phosphate and non-phosphate formulations in accordance with the present disclosure include the following: Table A. Formulation Ranges Component Wt % Sodium Carbonate 0-50 Sodium Bicarbonate 0-30 Sodium Disilicate 0-40 Sodium Citrate 0-70 Sodium Tripolyphospahte 0-70 Sodium Perborate or percarbonate 2-25 Bleach Activator/Catalyst 0.05-5 Anti-tarnishing agent 0-2 Polymer 0-10 Anti-scalant 0-5 Amylase 0-10 Protease 0-5 Nonionic Surfactant 0-5 Perfume 0-0.5 Sodium Sulfate Balance
  • Table B Base Formulation Components % wt Sodium Tripolyphosphate 60.6 Sodium Disilicate 19.4 Sodium Perborate Monohydrate 9.0 Amylase 1.7 Protease 2.7 Dispersant Polymer 3.3 Anti-scalant 1.1 Anti-Tarnishing Agent 0.05
  • Table C sets forth several abbreviations used in the text of the present disclosure. Table C.
  • All dishwashing machine tests were carried out using a Miele G656 dishwasher setting at the 55° Normal program, which accommodated main wash, pre-rinse and final rinse cycles.
  • Soil load includes 20 g of ASTM standard food soil (a 4:1 wt/wt ratio of margarine/powdered milk) spread on the dishwasher door and 5 g of raw egg yolk dosed at the dispenser cup opening during the main wash cycle.
  • 6 tea stained cups, 6 drinking glasses, 2 Tupperware containers, 1 melamine plate, 1 Teflon-coated frying pan and 16 clean plates were also present in the dishwasher to mimic the actual washing conditions.
  • tea cups were scores based on area covered by and intensity of residual tea stain, expressed on a 0 to 5 scale, 0 being completely cleaned.
  • Drinking glasses and plastic ware were also visually assessed and scored according to extent of spotting and filming. Both spotting and filming scores were recorded based on area covered by and intensity of spots/film, and also expressed on a 0 to 4 scale for spotting and a 0 to 5 scale for filming, 0 being completely free of spots or film.
  • Examples 1-3 detail the negative effect on tea stain removal caused by an amphoteric polymer (PC2 Polymer) in the presence of a neutral or anionically charged bleach activator, such as TAED, SNOBS and P-15.
  • PC2 Polymer amphoteric polymer
  • TAED sodium TAED
  • SNOBS sodium TABS
  • P-15 a neutral or anionically charged bleach activator
  • Examples 4-6 illustrate the beneficial effect of peroxyacid bleach incorporating a cationic group into an automatic dishwashing detergent formulation that contains a glass appearance improving polymer.
  • Examples 7-9 demonstrate the synergistic effect of combining transition metal bleaching systems that are cationically charged, and PC2 Polymer, giving both tea stain removal and glassware despotting benefit.
  • Example 10 further teaches the effect of cationic polymer (e.g. Celquat H-100) against tea stain removal. Similar to previous examples, the deficiency in tea stain removal caused by the cationic polymer can be mitigated by the use of a cationic peroxyacid bleaching agent (e.g. cationic nitrile) or a transition metal-containing bleach catalyst.
  • a cationic peroxyacid bleaching agent e.g. cationic nitrile
  • Example 11 expands the use of a dishware care-enhancing cationic polymer (Merquat 3331).
  • the combination of such polymer and a cationic bleaching system provides multifunctional benefits in machine dishwashing applications, including dishware fading and corrosion prevention, glass appearance-enhancing and cleaning efficacy on tea stains.
  • Wt % is calculated based on weight percentage of the ingredient in the base formulation.
  • SNOBS suffers the same problem as TAED.
  • the use of both SNOBS and PC2 polymer provides improved glass appearance, but at the expense of tea stain removal. This tea stain removal deficiency cannot be overcome even when the amount of SNOBS was increased three (3) times.
  • Wt % is calculated based on weight percentage of the ingredient in the base formulation.
  • PC2 polymer in P-15 (benzoyloxybenzene sulfonate) bleaching system provides improved glass appearance, but at the expense of tea stain removal. This tea stain removal deficiency cannot be overcome even when the amount of P-15 was doubled, but was improved when level of P-15 was increased three (3) times.
  • Wt % is calculated based on weight percentage of the ingredient in the base formulation.
  • imine quat was used as bleach catalyst and was dosed at a concentration of 50 M in each test.
  • concentration of 50 M As can be seen from the table above, with the combination of PC2 with KMPS-containing bleaching system, the negative effect on tea stain removal is significantly reduced compared to that of TAED-containing system. Without being bound by theory, it is believed that KMPS/imine quat can more efficiently generate the cationically charged oxaziridinium compound than TAED/perborate/imine quat system.
  • this cationic bleaching species can mitigate the tea stain removal negative caused by the use of an amphoteric polymer (e.g. PC2 Polymer).
  • an amphoteric polymer e.g. PC2 Polymer
  • Wt % is calculated based on weight percentage of the ingredient in the base formulation.
  • This Example illustrates the effect of a cationic group-containing peroxyacid bleach activator, CSPC.
  • CSPC/perborate system gives rise to completely cleaned tea cups and improved glass appearance in the presence of PC2 polymer.
  • CSPC can be reduced to 1.8 % and still maintain the bleaching performance on tea stain removal.
  • the lowest dosage for CSPC to provide tea stain removal benefit in this base formulation (Table B) in the presence of 5% PC2 Polymer is between 1.2 % to 1.8%.
  • Wt % is calculated based on weight percentage of the ingredient in the base formulation.
  • the manganese-containing bleach catalyst has the following chemical formula: [Mn IV 2 (-O) 3 -(Me 3 TACN) 2 ](PF 6 ) 2 , where Me 3 TACN is 1,4,7-trimethyl-1,4,7-triazacyclononane. c. Giving a final catalyst concentration of 3.2 M in the wash liquor. d. Giving a final catalyst concentration of 1.6 M in the wash liquor.
  • the levels of manganese-containing bleach catalyst are chosen to give an almost equal performance on tea stain removal achieved by an otherwise identical formulation containing 2.4 wt % of TAED.
  • combination of manganese-containing bleach catalyst and PC2 polymer preserves the improved glass appearance benefit without the negative effect on tea stain removal.
  • the iron-containing bleach catalyst has the following chemical formula: [Fe II (MeN4py)(MeCN)](ClO 4 ) 2 , where MeN4py is N , N -bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)-1-ethylamine. c. Giving a final catalyst concentration of 3.0 M in the wash liquor. d. Giving a final catalyst concentration of 1.5 M in the wash liquor.
  • the iron catalyst can be dosed at a 3.0 M level to provide excellent tea stain bleaching benefit.
  • Addition of PC2 polymer provides improvement of glass appearance without negative effect on tea stain removal.
  • concentration of the iron catalyst is further decreased to a half of the initial dosage, the iron catalyst gives a similar tea stain removal performance similar to that of a bleaching system containing 2.4 wt % of TAED.
  • the tea stain removal performance is much less affected in the iron catalyst-containing bleach system than that of TAED system.
  • Wt % is calculated based on weight percentage of the ingredient in the base formulation.
  • the cobalt-containing bleach catalyst has the following chemical formula: [Co III (NH 3 ) 5 (OAc)]-(OAc) 2 , where OAc is an acetate anion.
  • c Giving a final catalyst concentration of 10 M in the wash liquor.
  • d Giving a final catalyst concentration of 20 M in the wash liquor.
  • e Giving a final catalyst concentration of 40 M in the wash liquor.
  • Cobalt-containing bleach catalyst is not as efficient as other transition metal-containing catalyst, such as manganese and iron (see previous Examples) on a per-molar basis. Nevertheless, the reduction on the tea stain removal negative is noted compared to TAED bleaching system.
  • the minimal concentration of the cobalt catalyst required to match the tea stain removal performance of TAED/perborate system is around 20 M. It is noted that the negative effect on tea stain removal caused by PC2 polymer is about 1 unit smaller with the cobalt bleaching system than that containing TAED. Further increasing the concentration of cobalt catalyst to 40 M in the wash liquor, the negative influence of PC2 polymer on tea stain removal becomes minimal.
  • This Example illustrates the effect of a cationic polymer (e.g. Celquat H-100 polymer) against tea stain removal.
  • Celquat H-100 polymer is a cationically modified hydroxyethylcellulose and is commercially available from National Starch and Chemical Company.
  • Wt % is calculated based on weight percentage of the b ingredient in the base formulation.
  • the manganese-containing bleach catalyst has the following chemical formula: [Mn IV 2 (-O) 3 -(Me 3 TACN) 2 ](PF 6 ) 2 , where Me 3 TACN is 1,4,7-trimethyl-1,4,7-triazacyclononane.
  • d. Giving a final catalyst concentration of 3.2 M in the wash liquor.
  • cationic polymer negatively affects tea stain bleaching performance, most noticeably in a TAED/perborate bleaching system. Even when the amount of cationic polymer is reduced to a half or the level of bleach activator (i.e. TAED) is increased twice, the resulting tea stain removal performance is still worse than that of a bleaching system using cationic bleach, for example cationic nitrile or manganese containing bleach catalyst.
  • Example 11 illustrates the effect of a glass care-enhancing polymer, Merquat 3331, against tea stain removal.
  • the care enhancing properties of Merquat 3331, including dishware fading and corrosion prevention, are described by Tartakovsky et al. in US Patent No. 5,981,456.
  • Merquat 3331 polymer (INCI designation: Polyquaternium-39) is an amphoteric terpolymer consisting of 17 % acrylic acid, 45 % dimethyl diallyl ammonium chloride (DMDAAC) and 38 % acrylamide, and is commercially available from Calgon Corporation.
  • DMDAAC dimethyl diallyl ammonium chloride
  • the manganese-containing bleach catalyst has the following chemical formula: [Mn IV 2 (-O) 3 -(Me 3 TACN) 2 ](PF 6 ) 2 , where Me 3 TACN is 1,4,7-trimethyl-1,4,7-triazacyclononane c. Giving a final catalyst concentration of 3.2 M in the wash liquor.
  • the care-enhancing polymer (Merquat 3331) negatively affects tea stain bleaching performance in a TAED/perborate bleaching system.
  • the amount of the polymer is reduced from 5 % to 1.5 % of total composition, the resulting tea stain removal performance is worsened, while the despotting benefit on glasses maintained.
  • a bleaching system using cationic bleach for example, CSPC or manganese-containing bleach catalyst, and Merquat 3331, provides the multifunctional benefits of dishware care, glass appearance-enhancing and cleaning efficacy on tea stains.
  • kits containing the disclosed formulations can include printed instructions on the packaging or other enclosure stating that no rinse aid is to be added to the dishwashing machine.

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Claims (8)

  1. Maschinengeschirrspülmittelformulierung, umfassend:
    a) ein amphoteres oder kationisches Polymer,
    b) ein Bleichsystem mit mindestens einer kationischen Gruppe,
    worin das amphotere oder kationische Polymer ausgewählt ist aus:
    (i) amphoteren Polymeren, die wasserlösliche Polymere sind, enthaltend als polymerisierte Einheiten
    a) etwa 92 bis etwa 30 Gew.-% von einer oder mehreren monoethylenisch ungesättigten C3-C6-Carbonsäuren;
    b) etwa 5 bis etwa 50 Gew.-% von einem oder mehreren quaternisierten Aminoacryloylderivaten und
    c) etwa 0 bis etwa 25 Gew.-% von einem oder mehreren monoethylenisch ungesättigten Monomeren, die mit (a) und (b) polymerisierbar sind;
    (ii) kationischen Polymeren, die kationisch modifizierte Hydroxyethylcellulose sind;
    (iii) amphoteren oder kationischen Polymeren, die ein Diallyldimethylammoniumsalz als polymerisierte Einheiten enthalten, und
    (iv) amphoteren oder kationischen Polymeren, die ausgewählt sind aus der Gruppe, bestehend aus Polyquaternium-4, Polyquaternium-22, Polyquaternium-24, Polyquaternium-39 und Polyquaternium-47.
  2. Zusammensetzung nach Anspruch 1, wobei das Polymer bei einem Gehalt von etwa 0,1 bis etwa 20 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung, vorliegt.
  3. Zusammensetzung nach Anspruch 1, wobei das Bleichsystem einen Bleichaktivator, einen Bleichkatalysator oder eine Kombination davon umfaßt.
  4. Zusammensetzung nach Anspruch 3, wobei das Bleichsystem bei einem Gehalt von etwa 0,01 bis etwa 10 Gew.-%, bezogen auf die Gesamtzusammensetzung, vorliegt.
  5. Zusammensetzung nach Anspruch 1, wobei die kationische Gruppe, die das Bleichmittel enthält, aus der Gruppe aus organischen kationischen Bleichaktivatoren oder Bleichkatalysatoren ausgewählt ist, bestehend aus: kationischen Nitrilen; kationischen Peroxysäurebleichpräkursom; Quartäriminsalzen und Gemischen davon.
  6. Zusammensetzung nach Anspruch 1, wobei die Bleichaktivatoren oder Bleichkatalysatoren aus der Gruppe ausgewählt sind, bestehend aus: Cyanomethyltrimethylammoniummethylsulfat; Cholyl-(4-sulfophenyl)carbonat; N-Methyl-3,4-dihydroisochinolinium-p-toluolsulfonat und Gemischen davon.
  7. Zusammensetzung nach Anspruch 1, wobei die kationische Gruppe, die das Bleichmittel enthält, aus der Gruppe von Übergangsmetallbleichkatalysatoren ausgewählt ist, bestehend aus: [MnIV 2(-O)3(Me3TACN)2](PF6)2; [FeII(MeN4py)(MeCN)](ClO4)2 und [CoIII(NH3)5(OAc)](OAc)2 und Gemischen davon.
  8. Kit, umfassend:
    a) eine Maschinengeschirrspülmittelformulierung nach Anspruch 1;
    b) eine Beilage für a), wobei die Beilage gedruckte Instruktionen umfaßt, die angeben, daß kein Geschirrspülmittel zu der Geschirrspülmaschine zugegeben werden muß.
EP01940397A 2000-05-11 2001-05-04 Bleichmittel und polymere enthaltende maschinengeschirrspülmittellzusammensetzungen Revoked EP1280881B1 (de)

Applications Claiming Priority (3)

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US20341000P 2000-05-11 2000-05-11
US203410P 2000-05-11
PCT/EP2001/005014 WO2001085890A1 (en) 2000-05-11 2001-05-04 Machine dishwashing compositions containing bleaching agents and polymers

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EP1280881B1 true EP1280881B1 (de) 2006-09-13

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EP (1) EP1280881B1 (de)
AR (1) AR033372A1 (de)
AT (1) ATE339493T1 (de)
AU (1) AU2001273988A1 (de)
DE (1) DE60123039D1 (de)
WO (1) WO2001085890A1 (de)
ZA (1) ZA200208532B (de)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2839977B1 (fr) * 2002-05-27 2005-08-12 Rhodia Chimie Sa Utilisation, dans une composition lavante et rincante de la vaisselle en machine, d'un copolymere amphotere comme agent anti-redeposition des salissures
DE10342631B4 (de) 2003-09-15 2006-04-13 Henkel Kgaa Maschinelle Geschirrspülmittel mit spezieller Polymermischung
DE10342632A1 (de) 2003-09-15 2005-04-07 Henkel Kgaa Maschinelle Geschirrspülmittel mit speziellen Polymeren
DE10359099A1 (de) * 2003-12-17 2005-07-14 Henkel Kgaa Verringerung der Farb- und Oberflächenschädigung beim Waschen von Textilien und beim Reinigen von harten Oberflächen
AU2006242305B2 (en) 2005-05-04 2011-10-27 Diversey, Inc. Warewashing system containing low levels of surfactant
EP1845152A1 (de) * 2006-04-14 2007-10-17 The Procter and Gamble Company Verfahren zur Reinigung einer harten Oberfläche mit zwitterionischem Polymer
EP2014757A1 (de) 2007-07-05 2009-01-14 JohnsonDiversey, Inc. Spülhilfe
WO2010065482A1 (en) * 2008-12-02 2010-06-10 Diversey, Inc. Method to prevent or inhibit ware corrosion in ware washing
AU2009322574B2 (en) 2008-12-02 2014-05-15 Diversey, Inc. Ware washing system containing cationic starch
US20110240510A1 (en) * 2010-04-06 2011-10-06 Johan Maurice Theo De Poortere Optimized release of bleaching systems in laundry detergents

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Publication number Priority date Publication date Assignee Title
US4915863A (en) * 1987-08-14 1990-04-10 Kao Corporation Bleaching composition
GB8910725D0 (en) * 1989-05-10 1989-06-28 Unilever Plc Bleach activation and bleaching compositions
US5308532A (en) * 1992-03-10 1994-05-03 Rohm And Haas Company Aminoacryloyl-containing terpolymers
US5360569A (en) * 1993-11-12 1994-11-01 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with catalytic imine quaternary salts
US5578136A (en) * 1994-08-31 1996-11-26 The Procter & Gamble Company Automatic dishwashing compositions comprising quaternary substituted bleach activators
EP0800570B1 (de) * 1994-12-29 2002-10-02 The Procter & Gamble Company Waschmittelzusammensetzung mit wasserunlöslichem, entfärbungshemmendem polymerwirkstoff
US5981456A (en) * 1997-07-23 1999-11-09 Lever Brothers Company Automatic dishwashing compositions containing water soluble cationic or amphoteric polymers
WO1999050382A1 (en) * 1998-03-30 1999-10-07 The Procter & Gamble Company Detergent compositions
DE19824687A1 (de) * 1998-06-03 1999-12-09 Henkel Kgaa Amylase und Acetonitril-Derivate enthaltende Wasch- und Reinigungsmittel
WO2000023646A1 (en) * 1998-10-22 2000-04-27 The Procter & Gamble Company Bleach containing compositions for stain removal and methods of heat activation of the bleach
DE60032487T2 (de) * 1999-07-16 2007-10-04 The Procter & Gamble Company, Cincinnati Mittelseitenkettige tenside und zwitterionische polyamine enthaltende wäschewaschmittelzusammensetzungen

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ATE339493T1 (de) 2006-10-15
WO2001085890A1 (en) 2001-11-15
AU2001273988A1 (en) 2001-11-20
EP1280881A1 (de) 2003-02-05
DE60123039D1 (de) 2006-10-26
ZA200208532B (en) 2003-10-22

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