Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – For cleaning a specific substrate or removing a specific...
Reexamination Certificate
2001-04-10
2003-08-05
Boyer, Charles (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
For cleaning a specific substrate or removing a specific...
C510S219000, C510S237000, C510S375000
Reexamination Certificate
active
06602836
ABSTRACT:
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 color 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 U.S. Pat. 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 in U.S. Pat. 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 nitrites in the presence of peroxide are also known (see, for example, U.S. Pat. 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). Other known cationic group containing organic bleach activators or bleach catalysts include, for example, cholyl(4-sulfophenyl)carbonate (CSPC, see, for example, U.S. Pat. No. 5,106,528 and EP 399,584 B1), quaternary imine salts (e.g. N-methyl-3,4-dihydroisoquinolinium p-toluenesulfonate, U.S. Pat. Nos. 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, U.S. Pat. Nos. 5,599,781, 5,520,835, the contents of which are incorporated herein by reference. Cationic peroxyacids, such as those described in U.S. Pat. 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
(&mgr;-O)
3
(Me
3
TACN)
2
](PF
6
)
2
(U.S. Pat. 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)](CIO
4
)
2
(EP 0 909 809) and [Co
III
(NH
3
)
5
(OAc)](OAc)
2
(U.S. Pat. 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 color 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; colorants; 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. Pat. 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:
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
In all examples, the following base formulation was used:
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
For simplicity, Table C sets forth several abbreviations used in the text of the present disclosure.
TABLE C
Abbreviations used in the text
APTAC
(3-Acrylamidopropyl) trimethylammonium
chloride
Cationic Nitrile
Cyanomethyl trimethylammonium
methylsulfate
CSPC
Cholyl(4-sulphophenyl)carbonate
DMDAAC
Dimethyl diallyl ammonium chloride
Imine Quat
N-methyl-3,4-dihydroisoquinolinium
p-toluenesulfonate
KMPS
Potassium monopersulfate, triple salt
MeN4py
N,N-bis(pyridin-2-yl-methyl)-1,
1-bis(pyridin-2-yl)-1-aminoethane
Me
3
TACN
1,4,7-trimethyl-1,4,7-triazacyclononane
OAc
Acetate
PC2 Polymer
Copolymer of acrylic acid and APTAC
P-15
Sodium benzoyloxybenzene sulfonate
SNOBS
Sodium nonanoyloxybenzene sulfonate
TAED
Tetraacetylethylenediamine
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 CaCO
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 melamine plate, 1 Teflon-coated fry
Chiou Catherine
Ghatlia Naresh Dhirajlal
Nicholson John Richard
Piatek Bozena Marianna
Boyer Charles
Koatz Ronald A.
Petruncio John M.
Unilever Home & Personal Care USA a division of Conopco, Inc.
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