CA2273121A1 - Abrasive cleaning compositions - Google Patents
Abrasive cleaning compositions Download PDFInfo
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- CA2273121A1 CA2273121A1 CA 2273121 CA2273121A CA2273121A1 CA 2273121 A1 CA2273121 A1 CA 2273121A1 CA 2273121 CA2273121 CA 2273121 CA 2273121 A CA2273121 A CA 2273121A CA 2273121 A1 CA2273121 A1 CA 2273121A1
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- Prior art keywords
- abrasive
- constituent
- weight
- relative weight
- pumice
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Classifications
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/14—Fillers; Abrasives ; Abrasive compositions; Suspending or absorbing agents not provided for in one single group of C11D3/12; Specific features concerning abrasives, e.g. granulometry or mixtures
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/20—Water-insoluble oxides
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/265—Carboxylic acids or salts thereof
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
Abstract
Compositions and methods for removing rust stains from hard surfaces. The compositions contain acidic cleaning constituents, particularly oxalic acid, and abrasive constituents including pumice. The compositions contain reduced amounts of respirable silica.
Description
PATENT
ATTORNEY DOCKET No. 08295/42201 ABRASIVE CLEANING COMPOSITIONS
The invention relates to powdered abrasive clc;aning compositions that are particularly effective in the removal of rust from hard surfaces and methods for making and using such compositions in the cleaning of hard surfaces.
Anhydrous powdered abrasive compositions rave been used as so called 'all purpose' cleaners for a variety of surfaces including hard surfaces such as bathtubs, tile, sinks, countertops, painted surfaces, stove tops and the like. Some of these compositions have particular efficacy in the removal of rust stains from such surfaces.
Some of these 'all purpose' abrasive cleaning compositions contain microcrystalline silica as an abrasive. However, recent studies have implicated microcrystalline silica as a possible carcinogen. Certain governments, such as the State of California, have begun to take steps to limit, or educate their citizens as to, exposure to possible carcinogens. Producers are interested in modifying formulations to remove suspected carcinogens from their lists of ingredients which provides a clear benefit to users of products, and to satisfy regulations of such governments.
Therefore, there is a need in the field of hard surface cleaners for a composition that does not contain any substantial quantity of respirable microcrystalline silica that is higher than that allowed by regulations, and still retains effective hard surface cleaning ability.
In one aspect, the invention provides a powdered abrasive cleanser composition that serves as a hard surface cleaner and that has particular efficacy against rust stains. The composition contains substantially no respirable microcrystalline silica, a suspected carcinogenic agent, and is consistent with new environmental regulations in such jurisdictions as California.
_ In a second aspect, the invention provides a method of making a powdered abrasive cleanser composition. In a third aspect, the invention provides a method of cleaning a hard surface, particularly a hard surface that has rust stains.
The invention provides a powdered abrasive cleaning composition including an active cleaning constituent which contains oxalic acid, and an abrasive constituent which includes pumice and at least another abrasive material. This abrasive material can be sodium aluminosilicate, alumina trihydrate, hydrated aluminum silicate, calcium sulfate and barium sulfate. In another embodiment, the active cleaning constituent is present from 2 to 12% by weight, and the abrasive constituent is present from 70 to 95% by weight. In another embodiment, the abrasive constituent includes from 2: to 20% pumice by weight, and from 80 to 98% by weight of the above mentioned abrasive material. For example, the abrasive material can be hydrated aluminum silicate and calcium sulfate, each from 35 to 45% by weight in the abrasive constituent. Alternatively, the abrasive material can be alumina trihydrate with a loose bulk density of from 0.5 to 1.0 g/mL from 50 to 70% by weight of the abrasive constituent, and alumina trihydrate with a loose bulk density of from 1.0 to 1.5 g/mL from 20 to 30% by weight of the abrasive constituent. In another embodiment, the abrasive material is barium sulfate from 50 to 65% by weight of the abrasive constituent, and hydrated aluminum silicate from 15 to 35%
by weight of the abrasive constituent. Alternatively, the abrasive material is calcium sulfate, and barium sulfate each from 35 to 45% by weight of the abrasive constituent. In another embodiment, the abrasive material is barium sulfate from 5 to 25% by weight of the abrasive constituent, and alumina trihydrate from 55 to 75 % by weight of the abrasive constituent. In another embodiment, the abrasive material is alumina trihydrate from SS to 75%
by weight of the abrasive constituent, barium sulfate from 5 to 25% b5~ weight of the abrasive constituent, and G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 2 sodium aluminosilicate from 0.01 to 5% by weight of the abrasive constituent.
In another embodiment, the abrasive constituent includes pumice from 2 to 10% by weight of the abrasive constituent, alumina trihydrate from 80 to 99% by weight of the abrasive constituent, and sodium aluminosilicate from 0.01 to 20% by weight of the abrasive constituent. A
filler can also be included in the compositions of the invention. The invention also provides a method of making the powdered abrasive compositions described herein. The method includes combining the pumice, the abrasive constituent and the active constituent. The method can also include adding a filler constituent before the active constituent is added. The invention also provides a method of using the powdered abrasive compositions described herein. The method includes applying the composition to a surface to be cleaned, distributing the composition on the surface with a cleaning implement, and removing the composition from the surface. This method is also applicable to rust removal on such surfaces. The compositions are substantially free of respirable silica.
Unless otherwise defined, all technical and scientific terms used herein have the same 1 S meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or .equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other reference materials mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
The compositions of the invention described herein have a number of advantages. One such advantage is the absence of microcrystalline silica, which is suspected as being a G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 3 carcinogen. Replacement of this constituent with a non-carcinogenic substitute obviates the need for labelling the product in such jurisdictions as California. Another advantage is the particular efficacy of the composition in the removal of rust staiins from hard surfaces.
Another advantage is the simplicity of the composition, containing only very few essential ingredients. The ease of mixing the reduced number of constituents is a distinct advantage. There is no need for fragrances, surfactants or anionic salts of any kind, but these can be included as optional constituents. Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.
In a first preferred aspect, the powdered abrasive cleaning composition of the invention includes an active cleaning constituent, and an abrasive constituent which includes pumice.
Further optional constituents such as a fragrances, coloring agents, or flow processing aids, but these optional constituents need not be present or if present, need be included in only small amounts. This simplified composition provides excellent cleaning properties, particularly for hard surfaces, and especially for the removal of rust stains.
The active cleaning constituent of the invention is the constituent which exhibits efficacy in the removal of rust stains from a hard surface. Exemplary suitable active cleaning constituents include acids of all types including mineral acids and organic acids. Organic acids found useful for the invention include monocarboxylic acids and polycarboxylic acids. These compounds can be substituted or unsubstituted mono- or polycarboxylic acids preferably containing up to 6 carbons. They are preferably in their hydrated or pol:yhydrated states.
Preferred active ingredients are anhydrous solids which can be dissolved or dispersed in water, or aqueous based cleaning compositions which may contain a small amount of one or more organic solvents such as alcohols, glycols, and the like. These acids can be substituted or unsubstituted and can be G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 4 based on any of the following monocarboxylic acids (trivial names): methanoic (formic) acid, ethanoic (acetic) acid, propanoic (propionic) acid, butanoic (butyric) acid, pentanoic (valeric) acid and hexanoic acid and the iso-, sec-, neo-, or tert- isomers thereof, as well as dicarboxylic acids such as ethanedioic (oxalic) acid, propanedioic (malonic) acid, butanedioic (succinic) acid, S pentanedioic (glutaric) acid and hexanedioic (adipic) acids. As mentioned, polycarboxylic acids may also be used in the compositions of the invention. One or more mineral acids and organic acids may be used to form the active cleaning constituent of the invention.
A particularly good organic acid which is highly preferred for use in the invention is oxalic acid dehydrate, which has the capability of removing metal oxide stains, such as rust stains, is stable in its solid form, odorless, and is mildly acidic.
The active cleaning constituent of the compositions of the invention is present in an amount from about 0.01% to about 15% by weight, based on the total weight of the inventive composition. A preferred weight range is from about 2% to about 1 S% by weight. An especially preferred weight range is from about 5% to about 10°,% by weight.
The compositions of the present invention also contain an abrasive constituent. The abrasive constituent is necessary in order to provide sufficient friction between the cleaning implement and the hard surface to be cleaned, which facilitates in the removal of particularly stubborn or hard to remove stains from hard surfaces. The abrasive constituent of the invention includes pumice and at least one, preferably more than one, further abrasive material. The abrasive materials need to have sufficient hardness to assist the active ingredient in the removal of various soil deposits, especially rust stains. Preferably, the abrasive materials should have a hardness on the Moh's scale of at least 1 or more, preferably at least 2 to 7.
G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 5 . Pumice, an amorphous aluminum silicate is necessarily found in the inventive composition. Pumice is a light-colored, vesicular, glassy rock, is naturally occurring, chemically inert and environmentally safe, and is mainly an amorphous silica material with a low amount, typically 1 percent, of respirable free silica. Most relevant to the invention, pumice is non-carcinogenic. Typically pumice has a Moh's hardness of 4 -7.
The an abrasive constituent of the invention requires at least one, preferably a plurality of further abrasive materials other than pumice. Suitable further abrasive materials include those based on polymers, including polytetrafluoroethylene, organic materials such as walnut shells and corn cobs; various sulfate salts such as calcium sulfate, and barium sulfate; inorganic chemicals such as comminuted or small particulate sized rocks and minerals, including sand, glass beads, ruby garnet, feldspar, silicon dioxide, alumina trisilicate, magnesium hydroxide, feldspar, aluminum oxide, aluminosilicates, especially sodium aluminosilicate, tungsten carbide, aluminum trihydrate, zirconium silicate, silicon carbide, and hydrated aluminum silicate.
Especially preferred abrasive materials for the compositions of the present invention are sulfates, aluminum trihydrate, hydrated aluminum silicate, and sodium aluminosilicate.
Surprisingly, the inclusion of relatively low amounts of sodium aluminosilicate has been found to exhibit excellent rust removal benefits in the compositions of the invention.
particularly in compositions which include alumina trihydrate as the sole further abrasive constituent with the required pumice, and most particulary in compositions which include alumina trihydrate and barium sulfate as the sole further abrasives in conjunction with the required pumice.
Sodium aluminosilicate also provides useful processing and handling characteristics to the inventive compositions. Thus, the inclusion of sodium alumin~osilicate is an optional, but highly preferred abrasive material in the compositions of the invention.
G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 6 . The abrasive constituent to be used in the present invention can be made up of any combination of the above-mentioned abrasive materi~~ls. Pumice is a component of the abrasive constituent of the invention, as well as other abrasive materials discussed herein. In the representative examples given below, the relative weight percentages are relative between the abrasive materials cited, and do not reflect absolute weight percentages within the abrasive constituent, and do not reflect absolute weight percentages within the composition as a whole.
For example, the abrasive constituent could be an approximately equal mixture by weight of hydrated aluminum silicate and the calcium sulfate, or an approximately equal mixture by weight of calcium sulfate and barium sulfate, or an approxirriately 2:1 relative weight percent mixture of barium sulfate and hydrated aluminum silicate, or an approximately 4:1 relative weight percent mixture of alumina trihydrate and barium sulfate. Another especially preferred embodiment includes an approximately 20:1 relative weight percent mixture of alumina trihydrate and sodium aluminosilicate A relevant factor in selecting an abrasive is its particle size, as there is a relationship between particle size and cleaning efficacy. Particle aizes for the abrasive constituent of the present invention range from about 1 to about 150 microns. A preferred size range for the abrasive particles of the present invention is from about 3 to about 90 microns, and except for the pumice constituent which is typically larger, the mosl; preferred size range is from about 3 to about 20 microns.
The abrasive constituent can be present in the compositions of the invention in amount ranging from about 25% to 99% by weight, based on the weight of the composition as a whole.
A preferred weight range is from about 50% to about 98%. An especially preferred weight range is from about 80% to about 95%.
G:\Data\COMMON\ANPCMB\08295\422002\422C:A2\422PAT2.doc 7 It is desirable that the powdered abrasive cleaning composition of the present invention have a certain density. This is particularly important from a marketing standpoint, as the consumer has certain expectations as to the weight of a container of the cleaning composition of a given size. If the container is perceived as too light, the product will not meet the consumer's expectations for value. If the density of the product is too high, it may be perceived as a poor value by the consumer, since less surface coverage is obtained during application when compared to an equal weight of a less dense product. This is viewed as a detriment to the successful marketing of the product.
Some of the materials identified herein as abrasive materials can also act as bulking agents in the compositions of the invention. Thus, the loose bulk densities of the individual constituents of the compositions of the invention should be such that in combination, the overall bulk density of the composition is within a desired range. Table 1 shows the loose bulk densities for the components of the invention.
Constituent avg. particleloose bulk density size (g/mL) (microns) pumice 44.5 0.52-0.75 alumina trihydrate 15.5 0.75 alumina trihydrate 50 1.2 sodium aluminosilicate3.5 0.40-0.
hydrated aluminum 7.3 _ silicate 0.45 barium sulfate 8.5 - 1.60 calcium sulfate 14 0.50-0.70 It is desirable that the final compositions of the present invention have a bulk density of between 0.6 and 1.0 grams/milliliter (g/mL). A preferable range is from between 0.8 and 1.1 g/mL.
G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc g To achieve suitable bulk density for the final compositions, abrasive materials of varying loose bulk densities can be combined in various combinations. For example, combinations of 50-70% by weight of an abrasive material with loose bulk density of from 0.5-1.0 g/ml with 20-30% by weight of an abrasive material with loose bulk density of from 1.0 -1.5 g/ml are used in certain preferred embodiments. In another preferred embodiment, combinations of from 55-65%
by weight of an aluminum trihydrate with a loose bulk density of from 0.6-0.8 g/ml with an aluminum trihydrate with a loose bulk density of fronn 1.0 - 1.5 g/ml are used.
In a second aspect, the invention provides a method of making an abrasive cleansing composition. Although the cleaning compositions of the present invention can be prepared in a number of ways, one method will now be described. Although it is not believed that the order of the addition of the elements of the composition are critical to the properties of the resulting composition, the method of making the composition described below does have a specified order of steps.
Appropriate amounts of the elements of the abrasive cleansing composition are mixed except for the acid constituent, e.g., in a vertical ribbon blender. An appropriate amount of acid constituent is than added, with removal of clumped miaterial before this addition, if necessary.
This mixture can then be loaded into final packages.
In a third aspect, the invention provides a method of cleaning a hard surface, especially a hard surface having rust stains. The powdered abrasive cleaning composition of the present invention is typically combined with a cleaning solvent in the course of its use. Many cleaning preparations are available as hard surface cleaning preparations. The most common cleaning solvent is water, although commercially available cleaning prepartions can also be used. Of course, where a cleaning constituent is present and fo ms a part of the inventive composition, the G:\Data\COMMON\ANPCMB\08295\422002\422C:A2\422PAT2.doc c~
. use of a further cleaning solvent or a commercially available cleaning preparation may not be necessary. The powdered cleaning composition is normally spread over a hard surface or alternatively onto the surface of a cleaning implement such as a sponge, rag, cloth or like material, which may or may not be dampened. At such time as the surface is judged to be clean, the composition is removed by wiping with a cleaning implement, such as a sponge, rag, cloth, or like material, or by rinsing with cleaning solvent. This step can be repeated a number of times.
The invention will be further described in the following examples, which include certain particular preferred embodiments. These do not limil: the scope of the invention described in the claims.
Throughout this specification and in the accompanying claims, weight percentages of any constituent are to be understood as the weight percentage of the active portion of the referenced constituent, unless otherwise indicated.
Example::
The following examples illustrate the composition, methods of making and of using the powdered, abrasive cleaning composition described herein. Exemplary formulations illustrating certain preferred embodiments of the inventive compositions are described in more detail in Table 2 below.
G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 10 Ex.1 Ex.2 Ex.3 Ex.4 :Ex.SEx.6 Ex.7 Ex.8 Ex.9 sodium _____ __________ _____().5003.00 __________ _____ aluminosilicate alumina ----- ---------- 61.93ti1.4384.81 -----58.54 29.27 trihydrate SB
alumina -----29.27 58.54 trihydrate hydrated 38.47 23.08_____ _______________ __________ _____ aluminum silicate calcium sulfate38.47 -----38.47 --------------- ---______- _____ barium sulfate----- 53.8538.47 15.00It5.00----- ---------- -----pumice 15.38 15.3815.38 15.38115.384.50 4.50 4.50 4.50 oxalic acid 7.69 7.69 7.69 7.69 7.69 7.69 7.69 7.69 7.69 dihydrate loose bulk 0.85 N.D. 0.85 0.88 0.92 0.88 0.97 0.97 0.97 density (g/cc) tl.o .,t"..,.,:..".1,.." ~_~ ~_ 1..:1....7_,.1.... w.r_t,____~__ v muumuu. uiuyuaaw uaa a 1c~.7VlLCV lvlVtl J llit1V11GJJ Vl L.J-J.J
the hydrated aluminum silicate has a reported Moh's hardness of 2.0- 2.5 the barium sulfate has a reported Moh's hardness of 3-3.5 the pumice had a reported Moh's hardness of S.S
entry "N.D." was not determined Rust Removing Effica~r The compositions of the invention as indicated on Table 2 were tested for their rust removing efficacy as follows. A 1:1 dilution of the formulas according to Ex. 1-6 with deionized water was prepared. Aliquots of these diluvtions were dropped onto different areas of the surface of a rust-stained vitreous China tile for five minutes, after which the tile and the formulations were rinsed with water without rubbing or wiping. The efficacy of the rust removal ability was visually observed. This test was repeated., but permitting the aliquots to remain on the surface of the rust stained tiles for shorter full minute intervals, and then again removed by rinsing with water, without rubbing. The results of this test are reported on Table 3, where the "minutes" represent the minimum amount of time required which was judged necessary in order to effectively remove the stain from the vitreous China tile surface.
G:\Data\COMMON\P.NPCMB\08295\422002\422CA2\422PAT2.doc 11 Ex.l Ex.2 Ex.3 Ex.4 Ex.S Ex.
minutes required 5 5 5 ~ 5 2 3 Whereas all of the formulations provided good stain removal performance unexpectedly the formula of Ex. 5 and 6 were able to achieve removal of the rust stains within only two or three minutes. Thus, the addition of sodium aluminosilicate provided an additional, synergistic benefit with respect to the ability of the compositions to remove rust stains from model porcelain surfaces. This was particularly true for the formulation of Ex. 5, which had a lower amount of aluminum trihydrate with respect to Ex.6.
G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 12
ATTORNEY DOCKET No. 08295/42201 ABRASIVE CLEANING COMPOSITIONS
The invention relates to powdered abrasive clc;aning compositions that are particularly effective in the removal of rust from hard surfaces and methods for making and using such compositions in the cleaning of hard surfaces.
Anhydrous powdered abrasive compositions rave been used as so called 'all purpose' cleaners for a variety of surfaces including hard surfaces such as bathtubs, tile, sinks, countertops, painted surfaces, stove tops and the like. Some of these compositions have particular efficacy in the removal of rust stains from such surfaces.
Some of these 'all purpose' abrasive cleaning compositions contain microcrystalline silica as an abrasive. However, recent studies have implicated microcrystalline silica as a possible carcinogen. Certain governments, such as the State of California, have begun to take steps to limit, or educate their citizens as to, exposure to possible carcinogens. Producers are interested in modifying formulations to remove suspected carcinogens from their lists of ingredients which provides a clear benefit to users of products, and to satisfy regulations of such governments.
Therefore, there is a need in the field of hard surface cleaners for a composition that does not contain any substantial quantity of respirable microcrystalline silica that is higher than that allowed by regulations, and still retains effective hard surface cleaning ability.
In one aspect, the invention provides a powdered abrasive cleanser composition that serves as a hard surface cleaner and that has particular efficacy against rust stains. The composition contains substantially no respirable microcrystalline silica, a suspected carcinogenic agent, and is consistent with new environmental regulations in such jurisdictions as California.
_ In a second aspect, the invention provides a method of making a powdered abrasive cleanser composition. In a third aspect, the invention provides a method of cleaning a hard surface, particularly a hard surface that has rust stains.
The invention provides a powdered abrasive cleaning composition including an active cleaning constituent which contains oxalic acid, and an abrasive constituent which includes pumice and at least another abrasive material. This abrasive material can be sodium aluminosilicate, alumina trihydrate, hydrated aluminum silicate, calcium sulfate and barium sulfate. In another embodiment, the active cleaning constituent is present from 2 to 12% by weight, and the abrasive constituent is present from 70 to 95% by weight. In another embodiment, the abrasive constituent includes from 2: to 20% pumice by weight, and from 80 to 98% by weight of the above mentioned abrasive material. For example, the abrasive material can be hydrated aluminum silicate and calcium sulfate, each from 35 to 45% by weight in the abrasive constituent. Alternatively, the abrasive material can be alumina trihydrate with a loose bulk density of from 0.5 to 1.0 g/mL from 50 to 70% by weight of the abrasive constituent, and alumina trihydrate with a loose bulk density of from 1.0 to 1.5 g/mL from 20 to 30% by weight of the abrasive constituent. In another embodiment, the abrasive material is barium sulfate from 50 to 65% by weight of the abrasive constituent, and hydrated aluminum silicate from 15 to 35%
by weight of the abrasive constituent. Alternatively, the abrasive material is calcium sulfate, and barium sulfate each from 35 to 45% by weight of the abrasive constituent. In another embodiment, the abrasive material is barium sulfate from 5 to 25% by weight of the abrasive constituent, and alumina trihydrate from 55 to 75 % by weight of the abrasive constituent. In another embodiment, the abrasive material is alumina trihydrate from SS to 75%
by weight of the abrasive constituent, barium sulfate from 5 to 25% b5~ weight of the abrasive constituent, and G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 2 sodium aluminosilicate from 0.01 to 5% by weight of the abrasive constituent.
In another embodiment, the abrasive constituent includes pumice from 2 to 10% by weight of the abrasive constituent, alumina trihydrate from 80 to 99% by weight of the abrasive constituent, and sodium aluminosilicate from 0.01 to 20% by weight of the abrasive constituent. A
filler can also be included in the compositions of the invention. The invention also provides a method of making the powdered abrasive compositions described herein. The method includes combining the pumice, the abrasive constituent and the active constituent. The method can also include adding a filler constituent before the active constituent is added. The invention also provides a method of using the powdered abrasive compositions described herein. The method includes applying the composition to a surface to be cleaned, distributing the composition on the surface with a cleaning implement, and removing the composition from the surface. This method is also applicable to rust removal on such surfaces. The compositions are substantially free of respirable silica.
Unless otherwise defined, all technical and scientific terms used herein have the same 1 S meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or .equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other reference materials mentioned herein are incorporated by reference in their entirety. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.
The compositions of the invention described herein have a number of advantages. One such advantage is the absence of microcrystalline silica, which is suspected as being a G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 3 carcinogen. Replacement of this constituent with a non-carcinogenic substitute obviates the need for labelling the product in such jurisdictions as California. Another advantage is the particular efficacy of the composition in the removal of rust staiins from hard surfaces.
Another advantage is the simplicity of the composition, containing only very few essential ingredients. The ease of mixing the reduced number of constituents is a distinct advantage. There is no need for fragrances, surfactants or anionic salts of any kind, but these can be included as optional constituents. Other features and advantages of the invention will be apparent from the following detailed description, and from the claims.
In a first preferred aspect, the powdered abrasive cleaning composition of the invention includes an active cleaning constituent, and an abrasive constituent which includes pumice.
Further optional constituents such as a fragrances, coloring agents, or flow processing aids, but these optional constituents need not be present or if present, need be included in only small amounts. This simplified composition provides excellent cleaning properties, particularly for hard surfaces, and especially for the removal of rust stains.
The active cleaning constituent of the invention is the constituent which exhibits efficacy in the removal of rust stains from a hard surface. Exemplary suitable active cleaning constituents include acids of all types including mineral acids and organic acids. Organic acids found useful for the invention include monocarboxylic acids and polycarboxylic acids. These compounds can be substituted or unsubstituted mono- or polycarboxylic acids preferably containing up to 6 carbons. They are preferably in their hydrated or pol:yhydrated states.
Preferred active ingredients are anhydrous solids which can be dissolved or dispersed in water, or aqueous based cleaning compositions which may contain a small amount of one or more organic solvents such as alcohols, glycols, and the like. These acids can be substituted or unsubstituted and can be G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 4 based on any of the following monocarboxylic acids (trivial names): methanoic (formic) acid, ethanoic (acetic) acid, propanoic (propionic) acid, butanoic (butyric) acid, pentanoic (valeric) acid and hexanoic acid and the iso-, sec-, neo-, or tert- isomers thereof, as well as dicarboxylic acids such as ethanedioic (oxalic) acid, propanedioic (malonic) acid, butanedioic (succinic) acid, S pentanedioic (glutaric) acid and hexanedioic (adipic) acids. As mentioned, polycarboxylic acids may also be used in the compositions of the invention. One or more mineral acids and organic acids may be used to form the active cleaning constituent of the invention.
A particularly good organic acid which is highly preferred for use in the invention is oxalic acid dehydrate, which has the capability of removing metal oxide stains, such as rust stains, is stable in its solid form, odorless, and is mildly acidic.
The active cleaning constituent of the compositions of the invention is present in an amount from about 0.01% to about 15% by weight, based on the total weight of the inventive composition. A preferred weight range is from about 2% to about 1 S% by weight. An especially preferred weight range is from about 5% to about 10°,% by weight.
The compositions of the present invention also contain an abrasive constituent. The abrasive constituent is necessary in order to provide sufficient friction between the cleaning implement and the hard surface to be cleaned, which facilitates in the removal of particularly stubborn or hard to remove stains from hard surfaces. The abrasive constituent of the invention includes pumice and at least one, preferably more than one, further abrasive material. The abrasive materials need to have sufficient hardness to assist the active ingredient in the removal of various soil deposits, especially rust stains. Preferably, the abrasive materials should have a hardness on the Moh's scale of at least 1 or more, preferably at least 2 to 7.
G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 5 . Pumice, an amorphous aluminum silicate is necessarily found in the inventive composition. Pumice is a light-colored, vesicular, glassy rock, is naturally occurring, chemically inert and environmentally safe, and is mainly an amorphous silica material with a low amount, typically 1 percent, of respirable free silica. Most relevant to the invention, pumice is non-carcinogenic. Typically pumice has a Moh's hardness of 4 -7.
The an abrasive constituent of the invention requires at least one, preferably a plurality of further abrasive materials other than pumice. Suitable further abrasive materials include those based on polymers, including polytetrafluoroethylene, organic materials such as walnut shells and corn cobs; various sulfate salts such as calcium sulfate, and barium sulfate; inorganic chemicals such as comminuted or small particulate sized rocks and minerals, including sand, glass beads, ruby garnet, feldspar, silicon dioxide, alumina trisilicate, magnesium hydroxide, feldspar, aluminum oxide, aluminosilicates, especially sodium aluminosilicate, tungsten carbide, aluminum trihydrate, zirconium silicate, silicon carbide, and hydrated aluminum silicate.
Especially preferred abrasive materials for the compositions of the present invention are sulfates, aluminum trihydrate, hydrated aluminum silicate, and sodium aluminosilicate.
Surprisingly, the inclusion of relatively low amounts of sodium aluminosilicate has been found to exhibit excellent rust removal benefits in the compositions of the invention.
particularly in compositions which include alumina trihydrate as the sole further abrasive constituent with the required pumice, and most particulary in compositions which include alumina trihydrate and barium sulfate as the sole further abrasives in conjunction with the required pumice.
Sodium aluminosilicate also provides useful processing and handling characteristics to the inventive compositions. Thus, the inclusion of sodium alumin~osilicate is an optional, but highly preferred abrasive material in the compositions of the invention.
G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 6 . The abrasive constituent to be used in the present invention can be made up of any combination of the above-mentioned abrasive materi~~ls. Pumice is a component of the abrasive constituent of the invention, as well as other abrasive materials discussed herein. In the representative examples given below, the relative weight percentages are relative between the abrasive materials cited, and do not reflect absolute weight percentages within the abrasive constituent, and do not reflect absolute weight percentages within the composition as a whole.
For example, the abrasive constituent could be an approximately equal mixture by weight of hydrated aluminum silicate and the calcium sulfate, or an approximately equal mixture by weight of calcium sulfate and barium sulfate, or an approxirriately 2:1 relative weight percent mixture of barium sulfate and hydrated aluminum silicate, or an approximately 4:1 relative weight percent mixture of alumina trihydrate and barium sulfate. Another especially preferred embodiment includes an approximately 20:1 relative weight percent mixture of alumina trihydrate and sodium aluminosilicate A relevant factor in selecting an abrasive is its particle size, as there is a relationship between particle size and cleaning efficacy. Particle aizes for the abrasive constituent of the present invention range from about 1 to about 150 microns. A preferred size range for the abrasive particles of the present invention is from about 3 to about 90 microns, and except for the pumice constituent which is typically larger, the mosl; preferred size range is from about 3 to about 20 microns.
The abrasive constituent can be present in the compositions of the invention in amount ranging from about 25% to 99% by weight, based on the weight of the composition as a whole.
A preferred weight range is from about 50% to about 98%. An especially preferred weight range is from about 80% to about 95%.
G:\Data\COMMON\ANPCMB\08295\422002\422C:A2\422PAT2.doc 7 It is desirable that the powdered abrasive cleaning composition of the present invention have a certain density. This is particularly important from a marketing standpoint, as the consumer has certain expectations as to the weight of a container of the cleaning composition of a given size. If the container is perceived as too light, the product will not meet the consumer's expectations for value. If the density of the product is too high, it may be perceived as a poor value by the consumer, since less surface coverage is obtained during application when compared to an equal weight of a less dense product. This is viewed as a detriment to the successful marketing of the product.
Some of the materials identified herein as abrasive materials can also act as bulking agents in the compositions of the invention. Thus, the loose bulk densities of the individual constituents of the compositions of the invention should be such that in combination, the overall bulk density of the composition is within a desired range. Table 1 shows the loose bulk densities for the components of the invention.
Constituent avg. particleloose bulk density size (g/mL) (microns) pumice 44.5 0.52-0.75 alumina trihydrate 15.5 0.75 alumina trihydrate 50 1.2 sodium aluminosilicate3.5 0.40-0.
hydrated aluminum 7.3 _ silicate 0.45 barium sulfate 8.5 - 1.60 calcium sulfate 14 0.50-0.70 It is desirable that the final compositions of the present invention have a bulk density of between 0.6 and 1.0 grams/milliliter (g/mL). A preferable range is from between 0.8 and 1.1 g/mL.
G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc g To achieve suitable bulk density for the final compositions, abrasive materials of varying loose bulk densities can be combined in various combinations. For example, combinations of 50-70% by weight of an abrasive material with loose bulk density of from 0.5-1.0 g/ml with 20-30% by weight of an abrasive material with loose bulk density of from 1.0 -1.5 g/ml are used in certain preferred embodiments. In another preferred embodiment, combinations of from 55-65%
by weight of an aluminum trihydrate with a loose bulk density of from 0.6-0.8 g/ml with an aluminum trihydrate with a loose bulk density of fronn 1.0 - 1.5 g/ml are used.
In a second aspect, the invention provides a method of making an abrasive cleansing composition. Although the cleaning compositions of the present invention can be prepared in a number of ways, one method will now be described. Although it is not believed that the order of the addition of the elements of the composition are critical to the properties of the resulting composition, the method of making the composition described below does have a specified order of steps.
Appropriate amounts of the elements of the abrasive cleansing composition are mixed except for the acid constituent, e.g., in a vertical ribbon blender. An appropriate amount of acid constituent is than added, with removal of clumped miaterial before this addition, if necessary.
This mixture can then be loaded into final packages.
In a third aspect, the invention provides a method of cleaning a hard surface, especially a hard surface having rust stains. The powdered abrasive cleaning composition of the present invention is typically combined with a cleaning solvent in the course of its use. Many cleaning preparations are available as hard surface cleaning preparations. The most common cleaning solvent is water, although commercially available cleaning prepartions can also be used. Of course, where a cleaning constituent is present and fo ms a part of the inventive composition, the G:\Data\COMMON\ANPCMB\08295\422002\422C:A2\422PAT2.doc c~
. use of a further cleaning solvent or a commercially available cleaning preparation may not be necessary. The powdered cleaning composition is normally spread over a hard surface or alternatively onto the surface of a cleaning implement such as a sponge, rag, cloth or like material, which may or may not be dampened. At such time as the surface is judged to be clean, the composition is removed by wiping with a cleaning implement, such as a sponge, rag, cloth, or like material, or by rinsing with cleaning solvent. This step can be repeated a number of times.
The invention will be further described in the following examples, which include certain particular preferred embodiments. These do not limil: the scope of the invention described in the claims.
Throughout this specification and in the accompanying claims, weight percentages of any constituent are to be understood as the weight percentage of the active portion of the referenced constituent, unless otherwise indicated.
Example::
The following examples illustrate the composition, methods of making and of using the powdered, abrasive cleaning composition described herein. Exemplary formulations illustrating certain preferred embodiments of the inventive compositions are described in more detail in Table 2 below.
G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 10 Ex.1 Ex.2 Ex.3 Ex.4 :Ex.SEx.6 Ex.7 Ex.8 Ex.9 sodium _____ __________ _____().5003.00 __________ _____ aluminosilicate alumina ----- ---------- 61.93ti1.4384.81 -----58.54 29.27 trihydrate SB
alumina -----29.27 58.54 trihydrate hydrated 38.47 23.08_____ _______________ __________ _____ aluminum silicate calcium sulfate38.47 -----38.47 --------------- ---______- _____ barium sulfate----- 53.8538.47 15.00It5.00----- ---------- -----pumice 15.38 15.3815.38 15.38115.384.50 4.50 4.50 4.50 oxalic acid 7.69 7.69 7.69 7.69 7.69 7.69 7.69 7.69 7.69 dihydrate loose bulk 0.85 N.D. 0.85 0.88 0.92 0.88 0.97 0.97 0.97 density (g/cc) tl.o .,t"..,.,:..".1,.." ~_~ ~_ 1..:1....7_,.1.... w.r_t,____~__ v muumuu. uiuyuaaw uaa a 1c~.7VlLCV lvlVtl J llit1V11GJJ Vl L.J-J.J
the hydrated aluminum silicate has a reported Moh's hardness of 2.0- 2.5 the barium sulfate has a reported Moh's hardness of 3-3.5 the pumice had a reported Moh's hardness of S.S
entry "N.D." was not determined Rust Removing Effica~r The compositions of the invention as indicated on Table 2 were tested for their rust removing efficacy as follows. A 1:1 dilution of the formulas according to Ex. 1-6 with deionized water was prepared. Aliquots of these diluvtions were dropped onto different areas of the surface of a rust-stained vitreous China tile for five minutes, after which the tile and the formulations were rinsed with water without rubbing or wiping. The efficacy of the rust removal ability was visually observed. This test was repeated., but permitting the aliquots to remain on the surface of the rust stained tiles for shorter full minute intervals, and then again removed by rinsing with water, without rubbing. The results of this test are reported on Table 3, where the "minutes" represent the minimum amount of time required which was judged necessary in order to effectively remove the stain from the vitreous China tile surface.
G:\Data\COMMON\P.NPCMB\08295\422002\422CA2\422PAT2.doc 11 Ex.l Ex.2 Ex.3 Ex.4 Ex.S Ex.
minutes required 5 5 5 ~ 5 2 3 Whereas all of the formulations provided good stain removal performance unexpectedly the formula of Ex. 5 and 6 were able to achieve removal of the rust stains within only two or three minutes. Thus, the addition of sodium aluminosilicate provided an additional, synergistic benefit with respect to the ability of the compositions to remove rust stains from model porcelain surfaces. This was particularly true for the formulation of Ex. 5, which had a lower amount of aluminum trihydrate with respect to Ex.6.
G:\Data\COMMON\ANPCMB\08295\422002\422CA2\422PAT2.doc 12
Claims (12)
1. A powdered abrasive cleaning composition comprising:
(a) an active cleaning constituent comprising oxalic acid; and (b) an abrasive constituent comprising pumice and at least one other abrasive material selected from the group consisting of sodium aluminosilicate, alumina trihydrate, hydrated aluminum silicate, calcium sulfate and barium sulfate.
(a) an active cleaning constituent comprising oxalic acid; and (b) an abrasive constituent comprising pumice and at least one other abrasive material selected from the group consisting of sodium aluminosilicate, alumina trihydrate, hydrated aluminum silicate, calcium sulfate and barium sulfate.
2. A composition according to claim 1, comprising:
(a) from 2 to 12% by weight of the active cleaning constituent;
(b) from 70 to 95% by weight of the abrasive constituent.
(a) from 2 to 12% by weight of the active cleaning constituent;
(b) from 70 to 95% by weight of the abrasive constituent.
3. A composition according to claim 2, wherein the abrasive constituent comprises from 2 to 20% by relative weight of pumice, and from 80 to 98% by relative weight of at least one other abrasive material selected from the group consisting of sodium aluminosilicate, alumina trihydrate, hydrated aluminum silicate, calcium sulfate and barium sulfate.
4. A composition according to claim 3, wherein the abrasive constituent consists of:
(a) from 2 to 20% by relative weight of pumice;
(b) from 35 to 45% by relative weight of hydrated aluminum silicate; and (c) from 35 to 45% by relative weight of calcium sulfate.
(a) from 2 to 20% by relative weight of pumice;
(b) from 35 to 45% by relative weight of hydrated aluminum silicate; and (c) from 35 to 45% by relative weight of calcium sulfate.
5. A composition according to claim 3, wherein the abrasive constituent consists of (a) from 2 to 20% pumice;
(b) from 50 to 70% of an alumina trihydrate with a loose bulk density of from 0.5 to 1.0 g/ml; and (c) from 20 to 30% of an alumina trihydrate with a loose bulk density of from 1.0 to 1.5 g/ml.
(b) from 50 to 70% of an alumina trihydrate with a loose bulk density of from 0.5 to 1.0 g/ml; and (c) from 20 to 30% of an alumina trihydrate with a loose bulk density of from 1.0 to 1.5 g/ml.
6. A composition according to claim 3, wherein the abrasive constituent consists of (a) from 2 to 20% by relative weight of pumice;
(b) from 50 to 65% by relative weight of barium sulfate; and (c) from 15 to 35% by relative weight of hydrated aluminum silicate.
(b) from 50 to 65% by relative weight of barium sulfate; and (c) from 15 to 35% by relative weight of hydrated aluminum silicate.
7. A composition according to claim 3, wherein the abrasive constituent consists of (a) from 2 to 20% by relative weight of pumice;
(b) from 35 to 45% by weight of calcium sulfate; and (c) from 35 to 45% by weight of barium sulfate.
(b) from 35 to 45% by weight of calcium sulfate; and (c) from 35 to 45% by weight of barium sulfate.
8. A composition according to claim 3, wherein the abrasive constituent consists of:
(a) from 2 to 20% by relative weight of pumice;
(b) from 5 to 25% by relative weight of barium sulfate; and (c) from 55 to 75% by relative weight of alumina trihydrate.
(a) from 2 to 20% by relative weight of pumice;
(b) from 5 to 25% by relative weight of barium sulfate; and (c) from 55 to 75% by relative weight of alumina trihydrate.
9. A composition according to claim 3, wherein the abrasive constituent consists of (a) from 2 to 20% by relative weight of pumice;
(b) from 55 to 75% by relative weight of alumina trihydrate;
(c) from 5 to 25% by relative weight of barium sulfate; and (d) from 0.01 to 5% by relative weight of sodium aluminosilicate.
(b) from 55 to 75% by relative weight of alumina trihydrate;
(c) from 5 to 25% by relative weight of barium sulfate; and (d) from 0.01 to 5% by relative weight of sodium aluminosilicate.
10. A composition according to claim 3, wherein the abrasive constituent consists of:
(a) from 2 to 10% by relative weight of pumice (b) from 80 to 99% by relative weight of alumina trihydrate; and (c) from 0.01 to 20% by relative weight of sodium aluminosilicate.
(a) from 2 to 10% by relative weight of pumice (b) from 80 to 99% by relative weight of alumina trihydrate; and (c) from 0.01 to 20% by relative weight of sodium aluminosilicate.
11. A composition according to any of the foregoing claims which further comprises a filler constituent.
12. A composition according to any of the foregoing claims, wherein said composition is substantially free of respirable silica.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2273121 CA2273121A1 (en) | 1999-05-27 | 1999-05-27 | Abrasive cleaning compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2273121 CA2273121A1 (en) | 1999-05-27 | 1999-05-27 | Abrasive cleaning compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2273121A1 true CA2273121A1 (en) | 2000-11-27 |
Family
ID=29589076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2273121 Abandoned CA2273121A1 (en) | 1999-05-27 | 1999-05-27 | Abrasive cleaning compositions |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2273121A1 (en) |
-
1999
- 1999-05-27 CA CA 2273121 patent/CA2273121A1/en not_active Abandoned
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