MACHINE DISHWASHING COMPOSITIONS CONTAINING BLEACHING AGENTS AND POLYMERS

Abstract: Detergent formulations containing cationic bleaching agents and water-soluble polymers having cationic groups improve tea stain removal in machine dishwashing applications.

Description: H :NE DISHWASHING COMPOS ITIONS CONTAINING BLEACHING AGEN S ]T " Γ ' ^ S Field of the Disclosure The present disclosure relates to detergent compositions that contain both cationic bleaching agents and polymers incorporating cationic groups. Background 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. In addition, the cationic portion of the amphoteric polymer structure can cause the polymer to be adsorbed onto glass surfaces, thereby providing a sheeting action to the water and contributing to spotless glasses. Examples of amphoteric polymers include water-soluble aminoacryloyl -containing polymers, such those described m US Patent No. 5,308,532 and EP 0 560 519 Bl (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 Bl and WO 99/63038, the contents of which are incorporated herein by reference) . Other known 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 Bl) , 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) . Several different types of cationic peracid bleach activators have been disclosed in 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 good bleaching activity over a wide range of pH conditions. Transition metal -containing bleach catalysts such as [Mn IV 2 ( -0) 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 11 (MeN4py) (MeCN) ] (C10 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. In machine dishwashing applications, removal of bleachable stains, e.g. tea stains, is a particularly desirable property. Incomplete removal of such stains is readily noticeable and can lead to consumer dissatisfaction with the responsible detergent. During the course of investigating various machine dishwashing compositions, it was unexpectedly discovered that the addition of polymers containing cationic monomeric units to formulations having known bleaching systems negatively affected tea stain removal. For example, when water-soluble amphoteric polymers, such as quaternized aminoacryloyl -containing polymers, were added to formulations containing TAED/perborate, the ability of the formulation to remove tea stains was significantly reduced. Therefore, it was discovered that there is a need for machine dishwashing formulations that have both bleach and sheeting/anti-spotting ingredients or ingredients that provide colour protection and/or corrosion prevention (i.e. care enhancing) properties, wherein the formulation does not negatively impact the ability of the bleach to reduce tea stains. Summary It has been found that 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. A preferred formulation has a bleach system having at least one cationic group and a polymer having at least one monomer unit having a cationic charge over a portion of the pH range 2-11. Detergent formulations that do not combine a cationic polymer portion with a cationic bleach exhibit the discovered undesirable bleaching properties . Detailed Description 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; anti- redeposition agents; anti -corrosion agents; ingredients to enhance decor 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. Suitable phosphate and non-phosphate formulations in accordance with the present disclosure include the following : In all examples, the following base formulation was used: Table B. Base Formulation For simplicity, Table C sets forth several abbreviations used in the text of the present disclosure. Table C. Abbreviations used in the text Experimental Conditions 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. Water hardness was adjusted to contain 300 ppm of total hardness (Ca 2+ :Mg 2+ = 4:1, expressed as CaC0 3 ) and 320 ppm of temporary hardness expressed as sodium bicarbonate (i.e. 300/320 ppm water hardness) . 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. In addition, 6 tea stained cups, 6 drinking glasses, 2 Tupperware containers, 1 melamme plate, 1 Teflon-coated frying pan and 16 clean plates were also present m the dishwasher to mimic the actual washing conditions . In a typical machine test, 18 g of the base formulation (Table B, excluding bleach activator or glass appearance/care enhancing polymers) was used, unless noted otherwise. Bleach activator and/or glass appearance/care enhancing polymers were introduced separately at the dispenser cup opening during the main wash cycle. At the end of each test, 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) m the presence of a neutral or aniomcally charged bleach activator, such as TAED, SNOBS and P-15. 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 despottmg 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 m 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 . 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 m machine dishwashing applications, including dishware fading and corrosion prevention, glass appearance-enhancing and cleaning efficacy on tea stains. Example 1. TAED as Bleach Activator a . Wt % is calculated based on weight percentage of the ingredient m the base formulation. The use of both TAED and PC2 polymer gives improved glass appearance, but at the expense of tea stain removal. This tea stain removal deficiency cannot be overcome even when the amount of TAED was increased three (3) times. Example 2. SNOBS as Bleach Activator a Wt % is calculated based on weight percentage of the ingredient m 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. Example 3. P-15 as Bleach Activator a Wt % is calculated based on weight percentage of the ingredient m the base formulation. Similarly, the use of PC2 polymer m 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. Example 4. Cationic Nitrile as Bleach Activator a ' Wt % is calculated based on weight percentage of the ingredient in the base formulation. Glass appearance was noticeably improved with PC2 polymer in both TAED/perborate and cationic nitrile/perborate systems. However, as disclosed in Example 1, tea stain removal was negatively affected by the addition of PC2 polymer. Contrarily, no negative effect was found on tea stain removal in the cationic nitrile/perborate bleaching system containing PC2 polymer. Further, even when cationic nitrile was reduced to a half weight percent of TAED level, the result was a relatively small increase in residual tea score . Example 5. I ine Quat as Bleach Activator Wt % is calculated based on weight percentage of the ingredient m the base formulation. Giving a final concentration of 50 M m the wash liquor . TAED was dosed at 2.4 wt % and sodium perborate was dosed at 9.0 wt % (51 ppm a.o.) . KMPS was dosed at 10 wt % (20 ppm a.o.) and sodium perborate was dosed at 9.0 wt % (51 ppm a.o.) . KMPS was dosed at 10 wt % (20 ppm a.o.) . No perborate was used. KMPS was dosed at 15 wt % (30 ppm a.o.) . No perborate was used. In this example, imme quat was used as bleach catalyst and was dosed at a concentration of 50 M m each test. As can be seen from the table above, with the combination of PC2 w th KMPS-containing bleaching system, the negative effect on tea stain removal is significantly reduced compared to that of TAED-containmg system. Without being bound by theory, it is believed that KMPS/imme quat can more efficiently generate the cationically charged oxaziridinium compound than TAED/perborate/imme quat system. As a mam theme of the present disclosure, this cationic bleaching species can mitigate the tea stain removal negative caused by the use of an amphoteric polymer (e.g. PC2 Polymer). Example 6. CSPC as Bleach Activator a Wt % is calculated based on weight percentage of the ingredient the base formulation. This Example illustrates the effect of a cationic group- containing peroxyacid bleach activator, CSPC. At the equal wt % of TAED (2.4 %) , CSPC/perborate system gives rise to completely cleaned tea cups and improved glass appearance the presence of PC2 polymer. CSPC can be reduced to 1.8 % and still maintain the bleaching performance on tea stam removal . The lowest dosage for CSPC to provide tea stam removal benefit m this base formulation (Table B) the presence of 5% PC2 Polymer is between 1.2 % to 1.8%. Example 7. Manganese-Containing Bleach Catalyst Wt % is calculated based on weight percentage of the ingredient in the base formulation. b. 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-l , 4 , 7-triazacyclononane . 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. In this example, 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. As can be seen in the above Table, combination of manganese-containing bleach catalyst and PC2 polymer preserves the improved glass appearance benefit without the negative effect on tea stain removal . Example 8. Iron-Containing Bleach Catalyst Wt % is calculated based on weight percentage of the ingredient in the base formulation. The iron-containing bleach catalyst has the following chemical formula: [Fe 11 (MeN4py) (MeCN) ] (C10 4 ) 2 , where MeN4py is N, N-bis (pyridin-2 -yl -methyl) -bis (pyridin-2 -yl) -1- ethylamine . 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 . When the 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. However, with regard to the addition of PC2 polymer the tea stain removal performance is much less affected in the iron catalyst- containing bleach system than that of TAED system. Example 9. Cobalt-Containing Bleach Catalyst ingredient m the base formulation. b The cobalt-containing bleach catalyst has the following chemical formula: [Co 111 (NH 3 ) 5 (OAc) ] - (OAc) 2 , where OAc is an acetate anion. c Giving a final catalyst concentration of 10 M m the wash liquor. d Giving a final catalyst concentration of 20 M the wash liquor . e Giving a final catalyst concentration of 40 M m the wash liquor. Cobalt-contammg 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 stam removal negative is noted compared to TAED bleaching system. The minimal concentration of the cobalt catalyst required to match the tea stam removal performance of TAED/perborate system is around 20 M. It is noted that the negative effect on tea stam 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 m the wash liquor, the negative influence of PC2 polymer on tea stam removal becomes minimal . Example 10. Cationic Polymer and Cationic Bleach This Example illustrates the effect of a cationic polymer (e.g. Celquat H-100 polymer) against tea sta removal. Celquat H-100 polymer is a cationically modified hydroxyethylcellulose and is commercially available from National Starch and Chemical Company. ingredient the base formulation. b The manganese-containing bleach catalyst has the following chemical formula: [Mn IV 2 ( -0) 3 - (Me 3 TACN) 2 ] (PF 6 ) 2, where Me 3 TACN is 1 , 4 , 7-trιmethyl - 1 , 4 , 7-trιazacyclononane . c Giving a final catalyst concentration of 1.6 M m the wash liquor. d Giving a final catalyst concentration of 3.2 m the wash liquor. e Giving a final catalyst concentration of 6.4 M m the wash liquor. As demonstrated m the above Table, cationic polymer (Celquat H-100) negatively affects tea stam bleaching performance, most noticeably m 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 stam 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. Glass Care-Enhancing Polymer and Cationic Bleach Example 11 illustrates the effect of a glass care-enhancmg polymer, Merquat 3331, against tea stam removal. The care enhancing properties of Merquat 3331, including dishware fading and corrosion prevention, are described by Tartakovsky et al . US Patent No. 5,981,456. Merquat 3331 polymer (INCI designation: Polyquaternιum-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. a Wt % is calculated based on weight percentage of the ingredient m the base formulation. b The manganese-containing bleach catalyst has the following chemical formula: [Mn IV 2 ( -O) 3 - (Me 3 TACN) 2 ] (PF 6 ) ■ _ , where Me 3 TACN is 1 , 4 , 7-tπmethyl-l , 4 , 7-trιazacyclononane c Giving a final catalyst concentration of 3.2 M m the wash liquor. As shown m the above Table, the care-enhancmg polymer (Merquat 3331) negatively affects tea stam bleaching performance m a TAED/perborate bleaching system. Interestingly, when 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 despottmg benefit on glasses maintained. Similar to previous examples, the combination of 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 . Therefore, the above examples show that the combination of a polymer having a catiomc charge (catiomc or amphoteric) with a bleach activator that also has a catio c charge results m a solution to the problem of removing bleachable stains . A particular advantage of the above-disclosed formulations is that the need to regenerate internal water softeners and or the use of separate rmse aids can be reduced or eliminated. This would be perceived as a benefit to the consumer due to simplification of the machine dishwashing process. As such, kits containing the disclosed formulations can include printed instructions on the packaging or other enclosure stating that no rmse aid is to be added to the dishwashing machine. All component percentages are based on weight, unless otherwise indicated. All numerical values are considered to be modified by the term "about" and should be given the broadest available range of equivalents when construing the claims . Although the illustrative embodiments of the present disclosure have been described herein, it is to be understood that the disclosure is not limited to those precise embodiments, and that various other changes and modifications may be affected therein by one skilled m the art without departing from the scope or spirit of the disclosure .

Claims: CLAIMS 1. A method of removing bleachable-stams from dishware m a machine dishwashing process, the method comprising: a) providing a detergent composition comprising a bleach system having at least one catiomc group, and a polymer having at least one monomer unit having a catio c charge over a portion of the pH range 2-11, b) providing stained dishware a machine dishwasher, and c) contacting said dishware with said detergent composition in a machine dishwashing process. 2. A machine dishwashing detergent formulation comprising: a) an amphoteric or catiomc polymer, b) a bleach system having at least one cationic group, 3. A composition according to claim 2, wherein the polymer is present at a level from about 0.1 to about 20 wt % of the total weight of composition. 4. A composition according to claim 2, wherein the bleach system comprises a bleach activator, a bleach catalyst or combination thereof. 5. A composition according to claim 4, wherein the bleach system is present at a level of from about 0.01 to about 10 wt . % of the total composition. 6. A composition according to claim 2, wherein the polymer is an amphoteric polymer. 7. A composition according to claim 6, wherein the polymer is a water-soluble polymer containing as polymerized units, a) from about 92 to about 30 percent by weight of one or more C 3 -C 6 monoethylenically unsaturated carboxylic acids; b) from about 5 to about 50 percent by weight of one or more quaternized aminoacryloyl derivatives; and c) from about 0 to about 25 percent by weight of one or more monoethylenically unsaturated monomers polymerizable with (a) and (b) . 8. A composition according to claim 2, wherein the polymer is a cationic polymer. 9. A composition according to claim 8, wherein the polymer is a cationically modified hydroxyethylcellulose . 10. A composition according to claim 2, wherein the amphoteric or catiomc polymer contains a diallyldimethylammonium salt as polymerized units. 11. A composition according to claim 2, wherein the amphoteric or catiomc polymers are selected from the group consisting of Polyquaternιum-4 , Polyquaternium-22 , Polyquatermum-24 , Polyquaternium-39 , and Polyquatermum-47. 12. A composition according to claim 2, wherein the cationic group containing bleach is selected from the group of organic catio c bleach activators or bleach catalysts consisting of: catiomc mtriles, ■ catiomc peroxyacid bleach precursors; quaternary imme salts; and mixtures thereof. 13. A composition according to claim 2, wherein the bleach activators or bleach catalysts are selected form the group consisting of: cyanomethyl trimethylammonium methylsulfate ; cholyl (4-sulphophenyl) carbonate; N-methyl-3 , 4- dihydroisoqumolmium p-toluenesulfonate and mixtures thereof. 14. A composition according to claim 2, wherein the catiomc group containing bleach is selected from the group of transition metal bleach catalysts consisting of: [Mn IV 2 ( - 0) 3 (Me 3 TACN) 2 ] (PF e ) 2 ; [Fe 11 (MeN4py) (MeCN) ] (C10 4 ) 2 ; and [Co 111 (NH 3 ) 5 (OAc) ] (OAc) 2 ; and mixtures thereof. 15. A kit comprising: a) a detergent formulation as set forth m claim 2 ; and b) an enclosure for a) , said enclosure including printed instructions stating that no rmse aid is to be added to the dishwashing machine. 16. Use of a composition according to any one of claims 2 to 14 to remove team stains from dishware.

Inventors: CHIOU CATHERINE, GHATLIA NARESH DHIRAJLAL, NICHOLSON JOHN RICHARD, PIATEK BOZENA MARIANNA, CHIOU, CATHERINE, GHATLIA, NARESH, DHIRAJLAL, NICHOLSON, JOHN, RICHARD, PIATEK, BOZENA, MARIANNA
Applicants: LEVER HINDUSTAN LTD, UNILEVER NV, UNILEVER PLC, HINDUSTAN LEVER LIMITED
Application year: 2001
Main classification: C11D3
IPC codes: C11D3, C11D11, C11D17