Cleaning and liquid contact with solids – Processes – For metallic – siliceous – or calcareous basework – including...
Reexamination Certificate
2000-04-27
2001-11-13
Carrillo, Sharidan (Department: 1746)
Cleaning and liquid contact with solids
Processes
For metallic, siliceous, or calcareous basework, including...
C134S002000, C134S022190, C134S026000, C134S034000, C134S036000, C134S041000, C134S042000, C510S108000, C510S180000, C510S238000, C510S245000, C510S254000, C510S434000, C510S475000, C510S477000
Reexamination Certificate
active
06315835
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates generally to hard surface cleaners. In particular, the present invention relates to hard surface cleaners that are effective to clean soils normally found in bathroom and outdoors environments.
BACKGROUND AND SUMMARY OF THE INVENTION
Hard surface cleaners that perform to clean soils commonly found in bathroom and outdoors environments are known. For example, U.S. Pat. Nos. 5,252,245; 5,437,807 and 5,468,423 disclose reduced residue hard surface cleaner compositions based on solvents, blends of amphoteric, nonionic and anionic surfactants and nitrogenous buffering agents.
U.S. Pat. No. 5,454,984 discloses a cleaning composition comprised of quaternary ammonium compounds, tetrasodium EDTA, a mixture of surfactants and a glycol ether. U.S. Pat. No. 5,585,342 discloses reduced residue hard surface cleaner compositions based on a solvent with a vapor pressure of at least 0.001 mm Hg at 25° C., at least one semi-polar nonionic surfactant and a nitrogenous buffering agent. U.S. Pat. Nos. 5,536,452 and 5,587,022 disclose an aqueous rinsing solution for shower surfaces consisting essentially of a nonionic surfactant having an HLB of 13 or less, a chelating agent and, optionally, an alcohol and/or ammonium hydroxide and/or morpholine. U.S. Pat. No. 5,814,591 discloses an aqueous hard surface cleaner based on either a nonionic surfactant with, optionally, a quaternary ammonium surfactant present in a cleaning effective amount, an organic solvent with a vapor pressure of at least 0.001 mm Hg and ammonium ethylenediamine tetraacetate.
1
The entire content of each cited patent is expressly incorporated hereinto by reference.
While at least some of the conventional formulations described in the prior-issued U.S. patents cited above are effective at removing soils and inhibiting the adsorption and coalescence of soils, calcium soaps and/or calcium carbonate on ceramic tile surfaces found in a bathroom environment, they do not demonstrate a high level of efficacy on other non-tile hard surfaces (e.g., glass, metal, vinyl and fiberglass surfaces) commonly found in bathroom and outdoor environments. In fact, some of these conventional cleaning formulations actually dull the finish of glass, metal and/or vinyl surfaces thereby reducing their effectiveness from a consumer's point of view.
It would therefore be highly desirable if cleaning formulations could be provided which are effective at cleaning universally a variety of hard surfaces commonly found in bathroom and outdoors environments. It is towards providing such a needed formulation that the present invention is directed.
Broadly, the present invention is embodied in cleaning formulations and methods by which solid deposition is inhibited on hydrophobic hard surfaces typically encountered in bathroom and outdoor environments without detrimentally affecting the appearance of such surfaces. In this regard, the formulations of the present invention have been found to exhibit reduced spotting and filming.
The formulations of the present invention most preferably include an aqueous mixture of a nonionic copolymer, a polyacrylic acid homopolymer, and a nonionic surfactant. Optionally, a hydrotrope may also be present in the formulation. Preferably, the formulations of this invention have a pH between about 4.0 to about 7.0, more preferably around neutral (i.e., about 7.0). In specific embodiments, the formulations of the present invention include an aqueous mixture of (a) a graft copolymer of polyalkylene oxide with vinyl ester, the graft copolymer having a molecular weight within the range of about 5,000 to 50,000, (b) at least one polycarboxylate selected from the group consisting of acrylic acid/maleic acid copolymers, having a molecular weight within the range of about 1,000 to 100,000 and polyacrylic acid having a molecular weight of from about 1,000 to about 100,000, (c) at least one nonionic surfactant selected from the group consisting of alcohol alkoxylates, alcohol block alkoxylates, and polyoxyethylene/polyoxypropylene triblock surfactants, and (d) one or more water soluble organic solvents.
These and other aspects and advantages will become more apparent after careful consideration is given to the following detailed description of the preferred exemplary embodiments thereof.
DETAILED DESCRIPTION OF THE INVENTION
As noted previously, the formulations of the present invention are usefully employed to clean universally a variety of hard surfaces commonly found in bathroom and outdoors environments. Exemplary hard surfaces that can be advantageously cleaned by the formulations of the present invention without dulling or otherwise significantly adversely affecting the surface finish include ceramic tile, glass, metal, vinyl and fiberglass surfaces.
The formulations of the present invention will necessarily include a polymer blend comprised of a graft copolymer and at least one polycarboxylate. The graft copolymer employed in the formulations of the present invention will have a molecular weight (all MW's herein are expressed in terms of weight average molecular weight, unless otherwise specified) of about 5,000 to 50,000. More preferably, the graft copolymer will have a molecular weight within the range of about 10,000 to 35,000, more preferably within the range of about 15,000 to 30,000. In one especially desirable embodiment of the invention, the graft copolymer of polyalkylene oxide (preferably polyethylene oxide) with vinyl acetate will have a molecular weight of about 24,000. This graft copolymer is commercially available from BASF Corporation under the trademark SOKALAN® HP 22.
The graft copolymer as one component of cleaning formulations of the present invention may be synthesized in accordance with the procedures set forth in Holland et al., U.S. Pat. No. 4,999,869, incorporated herein by reference. The polyalkylene oxide component of the graft copolymer may be selected from the group consisting of polyethylene oxide, polypropylene oxide and polybutylene oxide, including mixtures thereof. In a preferred embodiment herein, vinyl acetate is grafted onto polyethylene oxide.
The polycarboxylate component of the polymer blend employed in the formulations of the present invention is selected from the group consisting of acrylic/maleic acid copolymers having a molecular weight within the range of about 1,000 to 100,000, and polyacrylic acid having a molecular weight of from about 1,000 to 100,000. The preferred acrylic/maleic acid copolymers are selected from the group of compounds with the following formula:
wherein z is hydrogen or an alkali metal, preferably sodium, and x and y are numbers such that the molecular weight of the acrylic/maleic acid copolymer is within the range of about 1,000 to 100,000, more preferably from about 2,000 to about 85,000, and even more desirably within the range of about 2,500 to about 75,000. In one especially preferred embodiment of the invention, the acrylic/maleic acid copolymer will have a molecular weight within the range of about 1,000 to 100,000, more desirably from about 1,000 to 20,000, and even more preferably from about 1,000 to 10,000. In a more preferred embodiment, the polyacrylic acid has a molecular weight of about 8,000. This component may be obtained from BASF under the trademark SOKALAN® PA30CI.
The nonionic surfactant employed in the formulations of the present invention is preferably at least one selected from the group consisting of alcohol alkoxylates, alcohol block alkoxylates, polyoxyethylene polyoxypropylene block surfactants, and mixtures thereof. Surfactants with a wide range of hydrophile-lipophile balance (HLB) can be used in the invention. As is well known in the art, the alcohol alkoxylates are made by using an alcohol as an initiator molecule, and polymerizing an alkylene oxide or a mixture of alkylene oxides onto the initiator molecule to form a first block. Thereafter, a second alkylene oxide or mixture of alkylene oxides can optionally be added to form a second block. Third and subsequent blocks can als
Gessner Suzanne M.
Holland Richard J.
Kerobo Charles O.
Patterson Sonia J.
Welch Michael C.
BASF Corporation
Carrillo Sharidan
Nixon & Vanderhye P.C.
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