CA1336670C - Thickened pourable aqueous cleaner - Google Patents
Thickened pourable aqueous cleanerInfo
- Publication number
- CA1336670C CA1336670C CA000595432A CA595432A CA1336670C CA 1336670 C CA1336670 C CA 1336670C CA 000595432 A CA000595432 A CA 000595432A CA 595432 A CA595432 A CA 595432A CA 1336670 C CA1336670 C CA 1336670C
- Authority
- CA
- Canada
- Prior art keywords
- cleaner
- weight
- present
- colloidal alumina
- effective amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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
- C11D3/395—Bleaching agents
- C11D3/3956—Liquid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
-
- 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
- C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
-
- 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
- C11D3/43—Solvents
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Abstract
This invention provides a thickened aqueous hard surface cleaner composition comprising colloidal alumina as the thickener in an aqueous cleaner which comprises a surfactant, electrolyte/buffer, soap and organic solvent system. These cleaner composition systems, which are the fluent, all-purpose type of cleaners, have surprising properties when thickened with the colloidal alumina. Such cleaners when thickened with colloidal alumina have a smoothly flowable or plastic consistency, and in their most preferred form, are pourable at room temperature, which consistency is not thixotropic in nature.
Description
1 336~70 Patent FIELD OF THE INVENTION
The present invention relates to thickened aqueous hard 6urface cleaners and more particularly to 6uch cleaners which are characterized by being smoothly flowable or plastic, preferably pourable at room temperature.
BACKGROUND OF THE INVENTION
Various hard surface cleaners or cleansers have been disclosed which contain soaps or surfactants in combination with various hydrocarbon type solvents. Examples of such cleansers are di~closed in U.S. Patents 4,414,128 to Goffinet:
4,455,250 and 4,540,505 to Frazier; 4,533,487 to 13 Jones and 4,576,738 to Calodney. ln aeneral these cleaners or cleansers are fluent, do not contain thickening agents and are not particularly adapted to have properties of thickened aqueous cleansers.
The present invention relates to thickened aqueous hard 6urface cleaners and more particularly to 6uch cleaners which are characterized by being smoothly flowable or plastic, preferably pourable at room temperature.
BACKGROUND OF THE INVENTION
Various hard surface cleaners or cleansers have been disclosed which contain soaps or surfactants in combination with various hydrocarbon type solvents. Examples of such cleansers are di~closed in U.S. Patents 4,414,128 to Goffinet:
4,455,250 and 4,540,505 to Frazier; 4,533,487 to 13 Jones and 4,576,738 to Calodney. ln aeneral these cleaners or cleansers are fluent, do not contain thickening agents and are not particularly adapted to have properties of thickened aqueous cleansers.
A variety of thicXened aqueous 6couring cleansers are known in the art and these cleansers exhibit various characteristics. Eor example, in U.S. Patents 4,599,186, 4,6S7,692 and 4,695,394 to Choy et al., thickened aqueous abrasive cleansers are disclosed which use colloidal alumina thickeners to provide abrasive cleansers which exhibit little or no syneresis over time. Similar cleansers containing organic c~lvents are disclosed in co-pending Canadian application serial no. 595,430 of Choy et al., filed on March 3l, 1989.
Other abrasive cleansers are disclosed in U.S. Patent 4,676,920 to Culsh2w and published patent applications EP 126545 to Buzzaccarini and EP 216416 to Iding, which contain clay type thickeners. While these cleansers contain hydrocarbon 601vents, the clay thickeners do not provide the desired p~operties in terms of flowability and pourability. The disclosure of Iding indicates that including solvents in abrasive cleanser compositions contributes to the instability and syneresi6 of these cleansers.
1 336b70 Other abrasive cleansers are disclosed in U.S. patents 4,158,553 and 4,240,919 to Chapman, 4,396,525 and 4,129,423 to Rubin; 4,005,027 to Hartman; 4,4S7,856 to Mitchell: and Japanese Patent Application 60-108499 to Watanabe et al. None of these cleansers disclosed in these references provide the desired cleaning efficacy for certain ~pplications together with the desired flowable or plastic consistency as exhibited by the Choy et al.
cleanser5. A specialized emulsion type skin cleaner composition for removing paint i6 disclosed in U.S.
4,508,643 to Elepano et al. as containing surfactants, solvents, an optional mild abrasive, and a protective colloid thickener, which protective colloid can be colloidal alumina.
In view of the above it has been found that there rem2ins the need for a thickened aqueous cleane- having the characteristics of:
(a) having a s~oothly flowable or plastic consistency, preferably pourable, and maintaining these properties over long periods of time; and 1 33667~
(b) having improved cleaning efficacy for certain applications.
In the context of this lnvention the term s "plastic" means that the cleaner is of a consistency which can undergo continuous deformation without rupture or relaxation of that consistency and the term "pourable" means that the cleaner is of a consistency which can be poured from an open container without the need for application of any force other than gravity, thus eliminating any need to shake, agitate or stir the cleaner before use.
SUMMARY OF THE INVENTION
It has now been determined that it is desirable to provide sn aqueous cleaner containing ~n organic solvent characterized by having a thickened smoothly flowable or plastic, preferably pourable, consistency. It ha~ surpr~singly been found that a thickened ac~eous cleaner having the desired thickened consistency can be made including a colloidal A lumina thickener in a hydrocarbon ~o~vent containing cleaner and, when used in combination with a fatty acid soap together with conventional electrolyte/buffers and surfactants, a cleaner is provided which has the above ~entioned desirable properties of having a 6moothly flcwable or plastic, preferably pourable, con6i6tency. Thi6 improved cleaner may also contain bleac~ when desired. This improved cleaner i6 described below in detail.
It i5 an ob~ect of the invention to provide a thickened aqueous cleaner characterized by a rheology and a consistency which remains 6moothly flowable or plastic over long periods of time.
It is another ob;ect of this invention to provide a thickened aqueous cleaner characterized by having improved cleaning efficacy.
This invention provides a thickened aqueous hard ~urface cleaner characterized by being 6moothly flowable or plastic comprising:
(a) at least one of An anionic, nonionic, amphoteric or zwitterionic ~urfactant being present in at least a cleaning-effective amount;
(b) an el2stroly-e/buffer form~ng about 0.1 to absut ~OS by weight of the cleaner;
(c) a f2tty acid 60ap being present from an effective amount to about 5% by weight of the cleaner;
(d) an organic solvent present from a cleaning-effective amount to about 10% by weight of the cle2ner; and (e) a colloidal alumina thickener having an aver2ge particle size, in dispersion, of no ~ore than about one micron, the colloidal alumina thickener forming from about 1 to about 15~ by weight of the cleaner.
The hard surface cleaner of the present invention as summarized above provides an excellent thickened consistency which aids in the ease of use of the cleaner on vertical surfaces. Because of the resulting consistency, cleaners provided by the present invention do not require shaking or agitation before use in order to pour formulation from a container. Rather, the cleanerc of the present invention maintain a uniform rheology and have a smoothly flowable or plastic consistency and preferably a pourable consistency, preferably at room te~perature, even after extended per,ods of shelf life. Acco_dingly, the cleaners of the present invention have Eubstantial esthetic 2ppeal while being useful in the ~ense of being easy to dispense and giving good coverage by flowing down while clinging to vertical surfaces.
_7_ 1 33667Q
In another aspect, this invention provides a method for preparing a thickened aqueous hard surface cleaner having a Emoothly flowable or plastic consistency, preferably a pourable consistency, comprising the step of combining:
(a) at least one of an anionic, nonlonic, amphoteric or zwitterionic surfactant being present in at least a cleaning-effective amount;
(~) an electrolyte/buffer forming about 0.1 to about 10~ by weight of the cleaner;
(c) a fatty acid soap being present from an effective amount to about 5S by weight of the cleaner;
(d) an organic solvent present from cle~ning-effective amount to about 10% by weight of the cleaner; and (e) a colloidal alumin2 thickener having an aver2ae pzrticle size, in dispersion, of no more than about one m~cron, the colloidal alumina thickener for~ing from about 1 to about 15~ by weight of the cleane In another aspect, this invention provides a method for cleaning a surface with a thickened, aqueous cleaner characterized by a smoothly flowable or plastic consistency, preferably pourable consistency, compr~sing contacting the surface having a stain thereon with the thickened, aqueous cleaner comprising:
(a) at least one of an anionic, nonionic, amphoteric or zwitterionic surfactant being present in at least a cleaning-effective;
(b) an electrolyte/buffer forming about 0.1 to about 10% by weight of the cleaner:
(c) a fatty acid soap being present from an effective amount to about 5% by weight of the cleaner.
(d) an organic Eolvent present from cleaning-effective amount to about 10% by weight of the cleaner; and (e) a colloidal alumina thickener having an average particle ~ize, in dispersion, of no more than about one micron, the colloidal alumina thickener forming from ~bout 1 to about 15% by weight of the cleaner.
The p_esent invention has surprisingly demonstrated the ability of the colloidal alumina in a surfactant, electrolyte/buffer, s02p and organic solvent system to provide a cleaner which is smoothly g flowable or plastic, preferably pourable, and provides superior cleaning properties.
DESCRIPTION OF EMBODIME~S OF TXE INVENTION
In one aspect, the present invention provides a thickened aqueous cleaner characterized by being pourable and having a smooth flowable consistency, these characteristics being retained by the cleaner even over long periods of time.
Accordingly, in at least one embodiment of the invention, a thickened, aqueous cleaner having desirable characteristics of a pourable And ~mooth flowing consistency comprises:
(a3 at least one of an anionic, nonionic, ampnoteric or zwitterionic surfactant being present from ~bout 0.1 to about 10% by weight of the cleaner;
(b) an electrolyte/buffer for2ing from about 0.1 to about 10% by weisht of the cleaner;
(c) a fatty acid soap being present from about 0.1 tO about ~% by weight of the cleaner;
(d) an orsanic 601vent presen. from ~bout 0.1 to ~bout 10% by we~ght of the cleaner; ~nd (e) a colloidal alumina thic~ener having an average particle size, in dispersion, of no more than - 1 33~670 about one micron, the colloiàal alumina thickener forming about 1 to about 15% by weight of the cleaner.
The essential ingredient in the composition of the invention as summ2rized above is the colloidal alumina thickener in combination with the surfactant, the soap and the organic ~olvent, because this combination tends to provide the smoothly flowable or plastic (preferably pourable) consistency of the cleaner and not provide thixotropic characteri6tics.
In order to provide a more complete understanding of the invention, a ~ummary as to each of the individual components in the composition of the present invention is set forth in greater detail below.
Surfactants As mentioned herein above, the surfactants suitable for use ~n this invention are selected from anionic, nonionic, amphoteric, zwitterionic surfactants and mixtures thereof, which are in general the non-soap type of surfactants. It is especially preferred to use a combination of ~nionics ~ 3366~0 and bleach-stable nonionics, which are usually more ~aturated to provide stability ln the presence of the bleach. However, when the cleaners of this invention ære used as non-bleach formulations, more unsaturation may be present in the surfactants 5 elected.
The anionic surfactant6 useful in this invention can be selected from surfactants such as alkali metal alkyl sulfates, secondary alkane sulfonates, linear alkyl benzene ~ulfonates, and mixtures thereof. These anionic surfactants will preferably have alkyl chain groups averaging about 8 to about 20 carbon atoms. In practice, it is freguently desirable to have a bleach present in the cleaner. When the bleach is present, the surfactant can be any other anionic surfactant which does not degrade chemically when in contact with a hypohalite, e.g., hypochlorite, bleaching species. An example of a particularly preferred ~econdary alkane sulfonate is HOSTAPUR SAS*, manufactured by Farbwerke Hoeschst A.G., ~rankfurt, West Germany. Another example of an alkane ~ulfonate is Mersolat*, which has an alkyl group of about 13-15 carbon atoms and is sold by Mobay Chemical Company. An example of typical alkali metal alkyl sulfates is Conco Sulfate WR, which has *Trade Mark an alkyl group of about 16 carbon ~toms, and is sold by Continent~l Chemical Company. When the electrolyte used i5 an ~lkali metal silicate, it 16 most preferable to include with the surfactant a soluble alkali metal soap of a fatty acid, such as a C6 18~ more preferably C10_16~ fatty acid ~o p Especially preferred are sodium and potassium ~oaps of lauric and ~yristic acid.
Examples of preferred bleach-stable nonionic ~urfactants are zmine oxides, especially trialkyl amine oxides. A representative ~tructure is set forth below:
R' R--N;~ O
Rn In the structure above, R' and R" can be alkyl of 1 to 3 carbon atoms, and are most preferably methyl, and R i5 aikyl of about 10 to about 20 carbon atoms.
When R' and R~ are both CX3- and R i~ alkyl aver2ging about 12 carbon atoms, the structure for 2 dimethyldodecylamlne oxide, a particularly preferreà
amine oxide, is obtained. These amine oxides can be straight or branched cha~n structures (see U.S.
Patent 4,299,313 to Joy) and can be functionalized - 1 33667~
when desired ~ith various ~ubstituent groups, ~uch as hydroxyethyl groups, ethoxylate groups ~nd the like, which ~re compatible with the cleaner sy~tem and will provide the properties desired. Representative examples of these particular type of bleach-6table nonionic ~urfactants include the di~ethyldodecylamine oxides sold under the trademark Ammonyx LO by Stepan Chemical Company, Chicago, ILL. Yet other preferred amine oxides are those sold under the trademark Barlox, by Baird Chemical Industries, Inc. Still others include the Conco XA series, 601d by Continental Chemical Company, the Aromax*6eries sold by Armour Industrial Chemical Company, the Schercamox*
6eries, sold by Scher Brothers, Inc., the Synprolam*
series ~old by ICI Americas Inc., and the 6pecialty amine oxides ~old by Ethyl Corporation. These amine oxides preferably have main alkyl chain groups averaging about 10 to 20 carbon atoms. Other types of ~uitable surfactants include amphoteric 6urfactants, exemplary of which are bet2ines, imidazolines ~nd certain quaternary phosphoniu~ ~nd tertiary sulfonium compounds. ~articularly prefe~-ed zre betaines ~uc~ ~s N-carboxymethyl-N-dimethyl-N-(9-octzdecenyl)a~onium hydroxide and N-carboxymethyl-N-cocoalkyl-N-dimethyl ammonium hydroxide, the latter of which is ~old under the trademarX Lonzaine by *Trade Mark Lonza Corporation. Other acceptable 6urfactants are the zwitterionic surfactant6 exemplified in U.S. Pat.
No. 4,005,029, to Jones (see columns 11-15).
It is preferred in some instances to combine at lea6t two of these surfactants, most preferably the anionics and the bleach-stable nonionic6. Combinations of these types of surfactant6 appear to be particularly desired when a bleach is present in the cleaner for maintaining hypochlorite half-life stability at elevated temperatures for long periods of time.
The surfactant is generally present in the cleaner in a range of about 0.1 to about 10% by weight, based on the total weight of the cleaner, more preferably about 0.5 to about 10% and most preferably about 1 to about 5%.
Electrolytes/~uffers The electrolyte/buffer used in the present invention should be selected in combinaticn with the surfactant or surfactants and the colloidal alumina thickener in order to produce the pourable and smooth ! ~66/~
flowing consistency desired for the composition of the present invention. In broad terms, electrolytes/buf~er~ employed within the present invention are generally s21ts of various inorganic S acids, including the alkali metal phosphates, polyphosphates, pyrophosphates, triphosphates, tetrapyrophosphates, silicates, metasilicates, polysilicates, carbonates, hydroxides, chlorides, sulfates and mixtures of the above. Certain divalent salts, for example, alkaline earth phosphate, carbonate, hydroxide, etc., salts can function singly as buffers. If such compounds were used, they normally would be combined with at least one other appropriate electrolyte/buffer to provide the appropriate pH adjustment. It may al60 be desirable to use as a buffer such materials as aluminosilicates (zeolites), borates, aluminates and bleach-stable organic materials such as gluconates, succinates, maleates, and their alkali metal 6alt5. These electrolytes/buffer6 function, particularly in bleach containing formulation, to maintain the pH range of the inventive cleaner compounds preferAbly above 7.0, ~ore preferably above 8.0 o- g.o and most prefera~ly at between about 7 0 . 0 and 13Ø The amount of electrolyte/buffer employed with the composition of the present lnvention can vary from about 0.1% to ` 1 336670 about 15% by weight of the cleaner, preferzbly from about 0.5 to about lOS and more preferably from about 1 to about 5%.
The silicate electrolytes/buffers useful in the present invention are formed by a combination of sodium oxide and ~ilicon dioxide and may preferably be a sodium silicate having a weight ratio of ~ilicon dioxide to ~odium oxide of about 3.75/1 and about 1/1, preferably between about 3/1 and about 1.5/1.
More preferably, the electrolyte/buffer i~ in the form of sodium silicate having a weight ratio of silicon dioxide to sodium oxlde of about 2.4/1.
A ~ilicate a6 described above is available, for example, fro~ the PQ Corporation, Philadelphia, PA.
Fatty Acid Soap The 502p useful in the present invention can be 6traight chain or brznched chzin fatty acids having Ç to 24 car~on groups with ur.lv2lent or multivalent catior.s whic~. rende- the ~oap solubie or dispersible in the a~ueoua cleane-. The ~02p ~Zy be Pn alkali metal salt of such a fatty acid, such as Li, Na or X, or may be ammonium or alkylammonium 1 33~670 salts thereof. Soaps which are conventionally used as ~uds 6uppressors will generally be useful in the present invention. While soap6 are selected for use in prior art cleaners for either suds control or for bleach ~tability, it i5 also important in the present invention that the 60Zp be compatible with and solubilize the organic Eolvent in the cleaner of the present invention, and also be compatible with the colloidal alumina thickener in the cleaner of the present invention. The soap which may be ~aturated or unsaturated, provides in combination with the alumina colloid thickener and hydrocarbon solvent, the characteristics of improved cleaning properties while still maintaining the plastic consistency or pourable flow characteristics of the cleaner of this invention. As indicated above relative to the surfactants, a saturated soap is usually preferred when a bleach is present in order to maintain bleach stability, but an unsaturated soap may be preferred in 60me instances when a bleach is r.ot included in the cleaner of the present inver.tion.
The S02p useful in the present invention is generally limited to a molecular weight range characterized by having from about 8 to about 20 carbon groups, either in a straight or branched chain configuration. More preferably, the soap is of a type having from about 10 to about 18 carbon groups, even more preferably about 12 to about 14 carbon groups. The amount of soap employed in a cleaner according to the present invention will be from an effective amount to about 5% by weight of the - cleaner, preferably from about 0.1 to about 5%, more preferably from about 0.5 to about 4% and most preferably up to about 3%.
Suitable fatty acid ~oaps useful in the present invention may be selected from the class consisting of potassium laurate, sodium laurate, sodium stearate, potassium stearate, ~odium oleate, etc. Similar soap6 containing ammonium ion a~ a cation may also be used particularly if the cleaner does not contain a bleach. Suitable soaps for use within the present invention are disclosed in Chemical Publishing Co., Inc., Encyclopedia Of Surface-Active Agents, Vol. I (1952), page 39 etc., Xirk-Othmer, Encyclopedia of Chemical Technology 3d, Vol. 21 pp. 162-181 re "502psn ~nd Vol. 22, re "Surf2ctants".
The manner in which the fatty acid anionic surfactant or soap functions in combinations with the colloidal alumina thic~ener and the hydrocarbon 601vent according to the present invention is not fully understood. It is believed that the soap may aid in 601ubilizing the organic solvent present in the cleaners of the present invention because it probably helps to mix or emulsify the solvent.
Organic Solvents The organic solvent~ useful in the present invention are alkyl or aryl hydrocarbons containing at lea6t 2 carbon atoms, preferably about 4 to about 18 carbon atoms and can include ether~, alcohols, esters, ketones and other hydrocarbons which are compatible with the fatty acid goap surfactant and colloidal aluminum present in the composition o~ the cleaner of the present invention. Examples of ~uch organic solvents include d-limonene, terpinolene, pine oil, glycol ethers such as butoxyethanol (bu~yl "Cellosolve"), straight or branched chain glycol ethers; glycols, such as polye.hylene glycol;
zlcohols ~uch as phencl, ethyl alcchol, benzyl alcohol, geraniol, citronellol, 6antalol, menthol, borneol, carveol, ethylhexelcarbonyl, vetiverol, linalol, terpineol, myrcenol, cetrol; and esters 6uch as linalyl acetate, benzyl acetate, isobornyl 1 33~670 acetate, ethyl acetoacetate and isoamylacetate.
Other examples of organic 601vents which may be useful in the cleaners of the present invention include 6aturated derivatives of terpenes, isoprenes, mineral spirits, such as the Isopar and ~orpar*series of mineral spirit6 and mineral oils sold by Exxon Corporation, and mineral oils, such as available from Penseco Company. Of course, mixtures of various organic solvents ~re useful in the cleaners of the present invention.
As understood with respect to the surfactants and soaps, saturated organic solvent6 should be used when ~A bleach i8 included in the cleaners of this invention to promote bleach stability as recognized by those skilled in the art.
Conversely, unsaturated organic 601vents may be selected for use in the non-bleach formulAtions of the cleaners of this invention. ~oreover, it is further understood that the organic solvent is selected to be co~patible with the soap and surfactant useful in the present invention ~s outlined above.
The amount of organic solvent employed in the cleaner according to the present invention will *Trade Mark be from an effective amount up to about 10% by weight of the cleaner, preferably from about 0.1 to about 8%, more preferably from about 0.1 to about 6%, and most preferably up to about 4S. In addition, it appear6 desirable in the present invention that the ratio of organic solvent to the combined amount of soap and surfactant generally be within certain ranges for moct practical formulation. In general, the weight ratio of organic 601vent to soap plus lo 6urfactant 6hould be less than about 1:40, and usually between about 10:1 and about 1:20, preferably between about 2:1 and about 1:10, more preferably between about 1:1.5 and about 1:9, still more preferably between about 1:2 and ~bout 1:8, and most preferably between about 1:3 and about 1:7.
Colloidal Alumina Thickener The colloidal alumina thickener component of the present invention is preferably a hydrated aluminum oxide h2ving gualifying characteri6tics 6uch as particle size to cause it to function as a colloidal thickerer. In this 6en6e, the colloidal alumina thickener used in th~ invention is to be contrasted from abrasive alumin2 materi21s having substantially larger particle sizes, for example substantially greater than one micron. Accordingly, 1 33~67iU
the particle size of the colloidal alumina thickener is a particularly important fe~ture for that component of the invention.
Preferred hydrated aluminas within the present invention are derived from synthetic Boehmites. Of greater importance, the hydrated colloidal alumina thickener of the present invention is chemically insoluble, that is, it should not dissolve in reasonably acidic, basic or neutral media. However, it is noted that colloidal alumina will dissolve in strongly alkaline media, for example, 50% NaOH.
A typical alumina is distributed by Remet Chemical Corp., Chadwicks, N.Y.j under the trademark DISPERAL (formerly DISPURA~) and manufactured by Condea Chemie, Brunsbuettel, West Germany. DISPERAL
i6 an aluminum oxide monohydrate which commonly forms - 20 stable colloidal aqueous dispersion6. Al~ina products oi this type commonly exist as dry powder~
which can form thixotropic gel6, bind 6ilica And other cera2ic substrates, while possêssir.g a positive charge and being substantive to a va -ety of surfaces.
DISPERAL has a typical chemical composition of 90% ~lpha aluminum oxide monohydrate (Boehmite) 9%
water, 0.5% carbon (as primary alcohol), 0.008%
6ilicon dioxide, 0.005% ferric oxide, 0.004% sodium silicate, ~nd 0.05% sulfur. It has a surface area (BET) of about 320 m2/gm, an undispersed averase particle 6ize (as determined by ~ieving) of lS% by weight being greater than 45 microns and 85% being less than 45 microns, an average particle ~ize, in - 10 dispersion, of 0.0048 microns as determined by X-ray diffraction, and a bulk density of 45 pounds per cubic foot (loose bulk) and 50 pounds per cubic foot (packed bulk). Yet another alumina suitable for use within the present invention, although not as preferred, is manufactured by Vista Chemicals Company, Houston, Texas and sold under the trademark CATAPAL ~lumina. CATAPAL has a typic21 chemical composition of 74.2% aluminum oxide (Boehmite), 25.8%
water, 0.36% carbon, 0.008% silicon dioxide, 0.005%
2G ferric oxide, 0.004% sodium oxide and less than 0.01%
~ulfur. It has a surface area (3ET) of 280 m2/gm, an undi6per~ed average p2rticle size (2s deter~ined by sieving) of 38% by weight being less than 45 mic_ons and 19% being gre2ter than 90 microns.
These colloidal alumina thickeners, used in 1 33667~
dispersed form in the invention, generally have exceedingly ~mall average particle size in dispersion (i.e., generally less than one micron). In point of fact, the average particle size diameter of these thickeners when dispersed is likely to be around 0.0048 micron. Thus, a preferred a~erage particle size range in dispersion is preferably less than one micron, more preferably less than about 0.5 micron and most preferably less than 0.1 micron. ~ue to their small particle 6ize, little or substantially no abrasi~e action i8 provided by these types of thickeners even though they are chemically insoluble, inorganic particles. Additlonally, these colloidal aluminas are chemically quite different from aluminum oxide abrasives, such as corundum. Colloidal aluminas are produced from synthetic Boehmite. In general, they are 6ynthesized by hydrolyzing aluminum alcoholates, with the resulting reaction products being hydrated aluminum (colloidal alumina) and three fatty alcohols. The reaction eguation is set forth below:
OR
Al- OR + (2 + x)H2O
OR
Rl-OH,R2-OHR3-OH ~ AlOOH.xH2O
(From Condea Chemie, ~PURAL PURALOX
DISPERAL High Purity Aluminas" Brochuse (1984).
These hydrated aluminum oxides are called 6ynthetic Boehmites merely because their crystalline 6tructure appears ~imilar to that of naturally occurring Boehmite. Boehmite, which is the actual mineral, has 2 Mohs hardness of about 3. It thus may be expected that the ~ynthetic Boehmite would not have a hardnes6 greater than the naturally occurring Boehmite. Corundum, on the other hand, appears to have a Mohs hardness of at lea6t 8 and perhaps higher. Thus, any abrasive action provided by colloidal aluminum oxides may be ~everely mitigated due to their relatlve ~oftness. An important aspect of the hydrated aluminas used herein is that they 6hould be chemically insoluble, i.e., ~hould not dissolve in acidic, basic or neutral media in order to have effective thicXening AS well ~s stability properties. ~:owever, colloi~al Eoehmite a!uminas will dissolve in highly basic media, e.g., 50% NaOH.
A further important point is that these ,~
colloidal alumina thickeners, in order to be useful as thickeners in the cleaners of this invention, must be initizlly dispersed in ~queous dispersion by means of strong acids. Preferable acids used to disperse these colloidal aluminas include, but are not limited to, acetic, nitric and hydrochloric acids. Sulfuric or phosphoric acids are not preferred.
Generally, a 1-50%, more preferably are about 5-40%, and most preferably about 10-35%
dispersion is made up, although in some instances, percentages of colloidal alumina are calculated for 100% (i.e., as if non-dispersed) active content. In practice, the colloidal alumina may be added to water sufficier.t to make up the desired percent dispersion and then the acid may be added thereto. Or, the acid may be first added to the water and then the colloidal alumina is dispersed in the dilute acid solution. In either case; a substantial amount of shearing (i.e., mixing in a mixing vat) is required to ¢btain the proper rheology.
Usually, a relatively small amount of concentrated acid is added. For instance, for a 25 wt.% dispersion material, 25% alumina monohydrate is combined with 1.75% concentrated (12M) hydrochloric acid ~nd then dispersed in 73.75% water. The colloidal alumina thickener itself is generally present in the cleaner in the ranse of about 1 to about 15% by weight based on the total weight of the cleaner, preferably about 1 to zbout 10%, more preferably about 1 to 6%, and most preferably, about 1 to about 5.5. Many useful formulations will contain from about 2.5 to about 5~ colloidal alumina according to the present invention.
Neutralization of the acidified dispersed colloid is necessary to obtain the desired, finished product rheology (i.e., it thickens). Thus, the acidified, diluted colloid is neutralized, preferably by sodium hydroxide te.g., a 50~ solution), although if the electrolyte/bu~fer is so~dium carbonate or sodium silicate, it may be possible to forego the sodium hydroxide as a ~eparate component. Secondly, since a halogen bleach may be added, if desired, to the cleaner~ of this invention, and such bleaches are unstable in the presence of acid, neutralization is ~lso desirable when a bleach is used.
With respect to thickening, it should be noted that while there are many types of inorganic and organic thickeners, not all will provide the proper type of plastic, flowable rheolosy desired in the present invention, particularly the preferred pourable consistency. Common clays, for instznce, those used in U.S. Patent 3,985,668 and ~.S. Patent 3,558,496, will likely lead to a false body rheology.
False body rheology pertains to liquids which, 2t rest, turn very viscous, i.e., form gels.
Problematic with such false body liquids i6 that they appear to tend to thicken very rapidly and harden or set up so that flowability is a problem. A
thixotropic rheology is also not particularly desirable in this invention since in the thixotropic ~tate, a liquid at rest also thickens dramatically, but, theoreticslly, ~hould flow upon shearing. If the thixotrope has a high yield stress value, as typically found in clay-thickened liquid media, the fluid at rest may not re-achieve flowability without shaking or agitation. As a matter of fact, if colloidal alumina alone is used to thicken the liqu-d cleaners of this invention, A thixotrope with high yield str2ss values appears to result. This type OL
product is less preferred, ar.d therefore, the surfactants included in the formulas of thi~
invention are crucial towards schieving a desire~
creamy, flowable, plastic rheology, particularly the preferred pourable consistency. Ordinarily, a 1 33~670 thixotrope will flow from a dispenser only upon Ehaking or 6queezing. ~n example of a typlcal thixotrope is catsup, which Ecmetl~es requires quite a bit of ~haking and pounding of ~he bottom of the bottle containing it to induce flow.
The type of rheology desired in this invention is a plastic, flowable rheology. This sort of rheology does not require shearing to promote fluidity. Thus, a product made in accordance with the present invention will not require, in its preferred form, sgueezing (assuming a deformable plastic squeeze bottle), 6haking or agitation to flow out of the container or dispenser, but will have a pourable consistency. In a non-preferred form, the cleaners of the present lnvention ~ay not be pourable from a particular container, but nevertheles6 are a ~moothly flowabie, plastic consistency and are not thixotropes.
Attaining this rheology in the cleaners of the presen. inventicn containing o~ganic solvents was ~sur~risir,g since it h2s b en thougr.~ that the combination of thickeners in cleane-s containing organic solvents would result in a different rheology. It was al~o surprising that cleansers such as in Choy et al. U.S. Patent 4,695,394, which are thickened and stabilized with colloidal alumina, would have such plastic rheology and also such abrasive-suspending stability so as to not become unstable when organic solvents were included in such compositions in accordance with the invention in ~o-pending application Serial No. 595,430 filed on March 31, 1989.
Moreover, nothing in the art had ever disclosed that fluent, solvent-containing household hard surface cleaners could be thickened with colloidal alumina to a flowable or plastic, preferably pourable, consistency.
lS Other Inqredients As mentioned above, the cleaners of the present invention can, when desired, contain a bleach. A source of bleach is selected from various halogen bleaches. ~or the purposes of the present invention, halogen bleaches are particularly favored.
As examples thereof, the bleach can be selected from the group consisting escentially of the al~al$ metal and alkaline earth salts of hypohalite, hypohalite addition products, haloamines, haloimines, haloimides and haloamides. These ~lso produce hypohalous bleaching species in situ with hypochlorites being a I :3 3 6 6 7 0 preferred form of bleach. Representative hypochlorite producing compounds include sodium, pota~ium, lithium and calcium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potas~ium 2nd sodium dichloroisocyanurate, trichloroisocyanuric acid, dichlorodimethyl hydantoin, chlorobromo dimethylhydantoin, N-chlorosulfam'de, and chloramine.
As noted above, a preferred bleach employed in the present invention is sodium hypochlorite having the chemical formula NaOCl, in an amount ranging from about 0.1% to about 5%, more preferably about 0.25% to 4% and most preferably 0.5S to 2.0%.
The purpose for the bleach is evident in forming an oxidizing cleaning agent which~is very effective against oxidizable stains such as organic stains.
A principal problem with the use of bleach in such composltions is its tendency to be unst2ble or to cause instability of other components, particularly cert2in surfact2nts if they are present in s~bst2nti21 ~mounts. In ~ny event, because of the usP of co710idal alu~inz ~s a thickener in the present invention together with a fatty acid s02p, 2 surfactant, and organic solvent together with only limited amounts of additional surfactant components, the bleach stability of the composition of the present invention ~expressed in half-life stability) i8 ~urprisingly good resulting in a product capable of maintaining excellent flow characteristics and bleach strength even after considerable periods of shelf life.
Abrasives may be added to the cleaners of the present invention to form scouring abrasive cleansers. The abrasives suitable for use and the useful amounts thereof are disclosed in copending application Serial No. 595,430 filed on March 31, 1989.
The cleaners of the present invention are particularly 6uited to inclusion of abrasives, because the colloidal alumina/surfactant/soap/organic ~olvent system of the present cleaners provide stable suspensions of abrasives therein to provide scouring cleansers. The clear,ers of the present invention may contain small ~mounts of fine or mild a~rasives to enhance cleaning efficacy for some applications, without producing a scouring action typical of many abrasive cleansers.
3 3 ~ 6 7 C
In addition to the components for the cleaning composition of the present invention as set forth above, further desirable ad~uncts may include bleach-stable dyes (for example, ~nthraquinone dyes~, pigments (for example, phthalocyanine, Tio2 and ultramarine blue), colorants and fragrances in relatively low amounts, for example, about 0.001~ to 5.0% by weight of the cleaner composition.
Water Water i6 the medium used as the medium in which the various components of the cleaner of the present invention are dissolved, dispersed or mixed.
Some of these components may be added to the cleaner in a water base, thus contributing to the total water present in the cleaner. While watPr and the miscellanecus minor ingredients or additives make up the remainder of t~.e composition, water is generally present in amounts ranging from about 10 to about 90 by weight of the cleaner.
Method of Pre~arinq As previously mentioned, the method of preparing the liouid cle2ner of this invention comprises combining:
(a) an initial portion of the total water with a colloidal alumina thickener;
~b) a final portion of the total water and a discrete amount of a neutralizing ~gent;
(c) optionally, a halogen bleach;
(d) a fatty acid Eoap;
(e) a Eurfactant (bleach ~table nonionic when a bleach is used);
(f) a buffer/electrolyte which interacts with the Eurfactant6 recited in 6teps (d) and (e) and the thickener recited in step (a) to result in a plastic rheology; and (g) an organic solvent.
As similarly described in U.S. Patent 4,657,692 at column 13, to produce the cleaner, alumina i6 charged into a vat or Euitable mixing vessel which has been provided with a 6uitable mixing mezns, 6uch as an impeller, which is in constant agitation with Euitable angular velocity.
The alumina is acidl'ied and diluted with about 50%
of the total water used. ~n alkyl benzene Eulfonate phase stabilizer can be optionally added at this point. A neutralizer, such as a 50% NaOH Eolution, can be added with the remainder of the water. Next, optional ingredients, such zs halogen bleach, 2brasives, dyes, fragrances, etc., czn be added, if desired. Thereafter, the anionic surfactants are added. When ~ilicate is used as the electrolyte/buffer, it is necessary to have a fatty acid soap as one of the anionic surfactants ~ince, as explained in U.S. Patent 4,695,394, the ~oap appears to surprisingly break up any network which could form between the silicate and the colloidal slumina.
Next, the bleach-stable nonionic surfactant is added, which is generally a trialkyl amine oxide (although a betaine or other surfactant would likely be suitable). At this point any alkyl benzené sulfonate is most preferably, although optionally, added. The electrolyte/buffer is then added and finally, the organic ~olvent i6 added. Alternatively, the organic solvent can be premixed with surfactants if desired.
Note that at virtually any step in this method, the optional minor ingredients, such ~s fragrance and pigments could be added. However, since fragrance is an organic component which m2y be more susceptible to oxidation by the h~logen ble2ch, ~t is prefer2ble to add it last when a bleach is present.
The invention is further illustrated by the e~bodiment ~et forth below:
1 33667~
EX~PLE
The following embodiment illustrates the thic~ened cleaner of the present invention containing surfactant, soap and an organic solvent, thickened with colloidal alumina.
Materi21 Wt.
Water 71.06 HCl (38%1 0.21 Disperall 4.50 Pigment 0.7s Ter~itol2 * 2.70 LAS 2.80 sAS4 2.65 Soap SolutionS 7.33 Sodium Chloride 2.00 Terpinolene6 * 3.00 Silicate ~U7 3.00 100. 00 1. Alumina (A1203.H20) from Condea Chemie.
2. Tergitol*TMN-6 from Union Carbide.
3. Biosoft L~S*40-S(40%) from Stepan Chemical Company.
4. Hostapur SAS*, secondary zlkane 6ulfonate from Hoechst A.G.
5. S02p solutior, prepared from 13.62 parts by weight laurlc zcid, 13.62 parts 50% NaOH and 72.75 parts water.
Other abrasive cleansers are disclosed in U.S. Patent 4,676,920 to Culsh2w and published patent applications EP 126545 to Buzzaccarini and EP 216416 to Iding, which contain clay type thickeners. While these cleansers contain hydrocarbon 601vents, the clay thickeners do not provide the desired p~operties in terms of flowability and pourability. The disclosure of Iding indicates that including solvents in abrasive cleanser compositions contributes to the instability and syneresi6 of these cleansers.
1 336b70 Other abrasive cleansers are disclosed in U.S. patents 4,158,553 and 4,240,919 to Chapman, 4,396,525 and 4,129,423 to Rubin; 4,005,027 to Hartman; 4,4S7,856 to Mitchell: and Japanese Patent Application 60-108499 to Watanabe et al. None of these cleansers disclosed in these references provide the desired cleaning efficacy for certain ~pplications together with the desired flowable or plastic consistency as exhibited by the Choy et al.
cleanser5. A specialized emulsion type skin cleaner composition for removing paint i6 disclosed in U.S.
4,508,643 to Elepano et al. as containing surfactants, solvents, an optional mild abrasive, and a protective colloid thickener, which protective colloid can be colloidal alumina.
In view of the above it has been found that there rem2ins the need for a thickened aqueous cleane- having the characteristics of:
(a) having a s~oothly flowable or plastic consistency, preferably pourable, and maintaining these properties over long periods of time; and 1 33667~
(b) having improved cleaning efficacy for certain applications.
In the context of this lnvention the term s "plastic" means that the cleaner is of a consistency which can undergo continuous deformation without rupture or relaxation of that consistency and the term "pourable" means that the cleaner is of a consistency which can be poured from an open container without the need for application of any force other than gravity, thus eliminating any need to shake, agitate or stir the cleaner before use.
SUMMARY OF THE INVENTION
It has now been determined that it is desirable to provide sn aqueous cleaner containing ~n organic solvent characterized by having a thickened smoothly flowable or plastic, preferably pourable, consistency. It ha~ surpr~singly been found that a thickened ac~eous cleaner having the desired thickened consistency can be made including a colloidal A lumina thickener in a hydrocarbon ~o~vent containing cleaner and, when used in combination with a fatty acid soap together with conventional electrolyte/buffers and surfactants, a cleaner is provided which has the above ~entioned desirable properties of having a 6moothly flcwable or plastic, preferably pourable, con6i6tency. Thi6 improved cleaner may also contain bleac~ when desired. This improved cleaner i6 described below in detail.
It i5 an ob~ect of the invention to provide a thickened aqueous cleaner characterized by a rheology and a consistency which remains 6moothly flowable or plastic over long periods of time.
It is another ob;ect of this invention to provide a thickened aqueous cleaner characterized by having improved cleaning efficacy.
This invention provides a thickened aqueous hard ~urface cleaner characterized by being 6moothly flowable or plastic comprising:
(a) at least one of An anionic, nonionic, amphoteric or zwitterionic ~urfactant being present in at least a cleaning-effective amount;
(b) an el2stroly-e/buffer form~ng about 0.1 to absut ~OS by weight of the cleaner;
(c) a f2tty acid 60ap being present from an effective amount to about 5% by weight of the cleaner;
(d) an organic solvent present from a cleaning-effective amount to about 10% by weight of the cle2ner; and (e) a colloidal alumina thickener having an aver2ge particle size, in dispersion, of no ~ore than about one micron, the colloidal alumina thickener forming from about 1 to about 15~ by weight of the cleaner.
The hard surface cleaner of the present invention as summarized above provides an excellent thickened consistency which aids in the ease of use of the cleaner on vertical surfaces. Because of the resulting consistency, cleaners provided by the present invention do not require shaking or agitation before use in order to pour formulation from a container. Rather, the cleanerc of the present invention maintain a uniform rheology and have a smoothly flowable or plastic consistency and preferably a pourable consistency, preferably at room te~perature, even after extended per,ods of shelf life. Acco_dingly, the cleaners of the present invention have Eubstantial esthetic 2ppeal while being useful in the ~ense of being easy to dispense and giving good coverage by flowing down while clinging to vertical surfaces.
_7_ 1 33667Q
In another aspect, this invention provides a method for preparing a thickened aqueous hard surface cleaner having a Emoothly flowable or plastic consistency, preferably a pourable consistency, comprising the step of combining:
(a) at least one of an anionic, nonlonic, amphoteric or zwitterionic surfactant being present in at least a cleaning-effective amount;
(~) an electrolyte/buffer forming about 0.1 to about 10~ by weight of the cleaner;
(c) a fatty acid soap being present from an effective amount to about 5S by weight of the cleaner;
(d) an organic solvent present from cle~ning-effective amount to about 10% by weight of the cleaner; and (e) a colloidal alumin2 thickener having an aver2ae pzrticle size, in dispersion, of no more than about one m~cron, the colloidal alumina thickener for~ing from about 1 to about 15~ by weight of the cleane In another aspect, this invention provides a method for cleaning a surface with a thickened, aqueous cleaner characterized by a smoothly flowable or plastic consistency, preferably pourable consistency, compr~sing contacting the surface having a stain thereon with the thickened, aqueous cleaner comprising:
(a) at least one of an anionic, nonionic, amphoteric or zwitterionic surfactant being present in at least a cleaning-effective;
(b) an electrolyte/buffer forming about 0.1 to about 10% by weight of the cleaner:
(c) a fatty acid soap being present from an effective amount to about 5% by weight of the cleaner.
(d) an organic Eolvent present from cleaning-effective amount to about 10% by weight of the cleaner; and (e) a colloidal alumina thickener having an average particle ~ize, in dispersion, of no more than about one micron, the colloidal alumina thickener forming from ~bout 1 to about 15% by weight of the cleaner.
The p_esent invention has surprisingly demonstrated the ability of the colloidal alumina in a surfactant, electrolyte/buffer, s02p and organic solvent system to provide a cleaner which is smoothly g flowable or plastic, preferably pourable, and provides superior cleaning properties.
DESCRIPTION OF EMBODIME~S OF TXE INVENTION
In one aspect, the present invention provides a thickened aqueous cleaner characterized by being pourable and having a smooth flowable consistency, these characteristics being retained by the cleaner even over long periods of time.
Accordingly, in at least one embodiment of the invention, a thickened, aqueous cleaner having desirable characteristics of a pourable And ~mooth flowing consistency comprises:
(a3 at least one of an anionic, nonionic, ampnoteric or zwitterionic surfactant being present from ~bout 0.1 to about 10% by weight of the cleaner;
(b) an electrolyte/buffer for2ing from about 0.1 to about 10% by weisht of the cleaner;
(c) a fatty acid soap being present from about 0.1 tO about ~% by weight of the cleaner;
(d) an orsanic 601vent presen. from ~bout 0.1 to ~bout 10% by we~ght of the cleaner; ~nd (e) a colloidal alumina thic~ener having an average particle size, in dispersion, of no more than - 1 33~670 about one micron, the colloiàal alumina thickener forming about 1 to about 15% by weight of the cleaner.
The essential ingredient in the composition of the invention as summ2rized above is the colloidal alumina thickener in combination with the surfactant, the soap and the organic ~olvent, because this combination tends to provide the smoothly flowable or plastic (preferably pourable) consistency of the cleaner and not provide thixotropic characteri6tics.
In order to provide a more complete understanding of the invention, a ~ummary as to each of the individual components in the composition of the present invention is set forth in greater detail below.
Surfactants As mentioned herein above, the surfactants suitable for use ~n this invention are selected from anionic, nonionic, amphoteric, zwitterionic surfactants and mixtures thereof, which are in general the non-soap type of surfactants. It is especially preferred to use a combination of ~nionics ~ 3366~0 and bleach-stable nonionics, which are usually more ~aturated to provide stability ln the presence of the bleach. However, when the cleaners of this invention ære used as non-bleach formulations, more unsaturation may be present in the surfactants 5 elected.
The anionic surfactant6 useful in this invention can be selected from surfactants such as alkali metal alkyl sulfates, secondary alkane sulfonates, linear alkyl benzene ~ulfonates, and mixtures thereof. These anionic surfactants will preferably have alkyl chain groups averaging about 8 to about 20 carbon atoms. In practice, it is freguently desirable to have a bleach present in the cleaner. When the bleach is present, the surfactant can be any other anionic surfactant which does not degrade chemically when in contact with a hypohalite, e.g., hypochlorite, bleaching species. An example of a particularly preferred ~econdary alkane sulfonate is HOSTAPUR SAS*, manufactured by Farbwerke Hoeschst A.G., ~rankfurt, West Germany. Another example of an alkane ~ulfonate is Mersolat*, which has an alkyl group of about 13-15 carbon atoms and is sold by Mobay Chemical Company. An example of typical alkali metal alkyl sulfates is Conco Sulfate WR, which has *Trade Mark an alkyl group of about 16 carbon ~toms, and is sold by Continent~l Chemical Company. When the electrolyte used i5 an ~lkali metal silicate, it 16 most preferable to include with the surfactant a soluble alkali metal soap of a fatty acid, such as a C6 18~ more preferably C10_16~ fatty acid ~o p Especially preferred are sodium and potassium ~oaps of lauric and ~yristic acid.
Examples of preferred bleach-stable nonionic ~urfactants are zmine oxides, especially trialkyl amine oxides. A representative ~tructure is set forth below:
R' R--N;~ O
Rn In the structure above, R' and R" can be alkyl of 1 to 3 carbon atoms, and are most preferably methyl, and R i5 aikyl of about 10 to about 20 carbon atoms.
When R' and R~ are both CX3- and R i~ alkyl aver2ging about 12 carbon atoms, the structure for 2 dimethyldodecylamlne oxide, a particularly preferreà
amine oxide, is obtained. These amine oxides can be straight or branched cha~n structures (see U.S.
Patent 4,299,313 to Joy) and can be functionalized - 1 33667~
when desired ~ith various ~ubstituent groups, ~uch as hydroxyethyl groups, ethoxylate groups ~nd the like, which ~re compatible with the cleaner sy~tem and will provide the properties desired. Representative examples of these particular type of bleach-6table nonionic ~urfactants include the di~ethyldodecylamine oxides sold under the trademark Ammonyx LO by Stepan Chemical Company, Chicago, ILL. Yet other preferred amine oxides are those sold under the trademark Barlox, by Baird Chemical Industries, Inc. Still others include the Conco XA series, 601d by Continental Chemical Company, the Aromax*6eries sold by Armour Industrial Chemical Company, the Schercamox*
6eries, sold by Scher Brothers, Inc., the Synprolam*
series ~old by ICI Americas Inc., and the 6pecialty amine oxides ~old by Ethyl Corporation. These amine oxides preferably have main alkyl chain groups averaging about 10 to 20 carbon atoms. Other types of ~uitable surfactants include amphoteric 6urfactants, exemplary of which are bet2ines, imidazolines ~nd certain quaternary phosphoniu~ ~nd tertiary sulfonium compounds. ~articularly prefe~-ed zre betaines ~uc~ ~s N-carboxymethyl-N-dimethyl-N-(9-octzdecenyl)a~onium hydroxide and N-carboxymethyl-N-cocoalkyl-N-dimethyl ammonium hydroxide, the latter of which is ~old under the trademarX Lonzaine by *Trade Mark Lonza Corporation. Other acceptable 6urfactants are the zwitterionic surfactant6 exemplified in U.S. Pat.
No. 4,005,029, to Jones (see columns 11-15).
It is preferred in some instances to combine at lea6t two of these surfactants, most preferably the anionics and the bleach-stable nonionic6. Combinations of these types of surfactant6 appear to be particularly desired when a bleach is present in the cleaner for maintaining hypochlorite half-life stability at elevated temperatures for long periods of time.
The surfactant is generally present in the cleaner in a range of about 0.1 to about 10% by weight, based on the total weight of the cleaner, more preferably about 0.5 to about 10% and most preferably about 1 to about 5%.
Electrolytes/~uffers The electrolyte/buffer used in the present invention should be selected in combinaticn with the surfactant or surfactants and the colloidal alumina thickener in order to produce the pourable and smooth ! ~66/~
flowing consistency desired for the composition of the present invention. In broad terms, electrolytes/buf~er~ employed within the present invention are generally s21ts of various inorganic S acids, including the alkali metal phosphates, polyphosphates, pyrophosphates, triphosphates, tetrapyrophosphates, silicates, metasilicates, polysilicates, carbonates, hydroxides, chlorides, sulfates and mixtures of the above. Certain divalent salts, for example, alkaline earth phosphate, carbonate, hydroxide, etc., salts can function singly as buffers. If such compounds were used, they normally would be combined with at least one other appropriate electrolyte/buffer to provide the appropriate pH adjustment. It may al60 be desirable to use as a buffer such materials as aluminosilicates (zeolites), borates, aluminates and bleach-stable organic materials such as gluconates, succinates, maleates, and their alkali metal 6alt5. These electrolytes/buffer6 function, particularly in bleach containing formulation, to maintain the pH range of the inventive cleaner compounds preferAbly above 7.0, ~ore preferably above 8.0 o- g.o and most prefera~ly at between about 7 0 . 0 and 13Ø The amount of electrolyte/buffer employed with the composition of the present lnvention can vary from about 0.1% to ` 1 336670 about 15% by weight of the cleaner, preferzbly from about 0.5 to about lOS and more preferably from about 1 to about 5%.
The silicate electrolytes/buffers useful in the present invention are formed by a combination of sodium oxide and ~ilicon dioxide and may preferably be a sodium silicate having a weight ratio of ~ilicon dioxide to ~odium oxide of about 3.75/1 and about 1/1, preferably between about 3/1 and about 1.5/1.
More preferably, the electrolyte/buffer i~ in the form of sodium silicate having a weight ratio of silicon dioxide to sodium oxlde of about 2.4/1.
A ~ilicate a6 described above is available, for example, fro~ the PQ Corporation, Philadelphia, PA.
Fatty Acid Soap The 502p useful in the present invention can be 6traight chain or brznched chzin fatty acids having Ç to 24 car~on groups with ur.lv2lent or multivalent catior.s whic~. rende- the ~oap solubie or dispersible in the a~ueoua cleane-. The ~02p ~Zy be Pn alkali metal salt of such a fatty acid, such as Li, Na or X, or may be ammonium or alkylammonium 1 33~670 salts thereof. Soaps which are conventionally used as ~uds 6uppressors will generally be useful in the present invention. While soap6 are selected for use in prior art cleaners for either suds control or for bleach ~tability, it i5 also important in the present invention that the 60Zp be compatible with and solubilize the organic Eolvent in the cleaner of the present invention, and also be compatible with the colloidal alumina thickener in the cleaner of the present invention. The soap which may be ~aturated or unsaturated, provides in combination with the alumina colloid thickener and hydrocarbon solvent, the characteristics of improved cleaning properties while still maintaining the plastic consistency or pourable flow characteristics of the cleaner of this invention. As indicated above relative to the surfactants, a saturated soap is usually preferred when a bleach is present in order to maintain bleach stability, but an unsaturated soap may be preferred in 60me instances when a bleach is r.ot included in the cleaner of the present inver.tion.
The S02p useful in the present invention is generally limited to a molecular weight range characterized by having from about 8 to about 20 carbon groups, either in a straight or branched chain configuration. More preferably, the soap is of a type having from about 10 to about 18 carbon groups, even more preferably about 12 to about 14 carbon groups. The amount of soap employed in a cleaner according to the present invention will be from an effective amount to about 5% by weight of the - cleaner, preferably from about 0.1 to about 5%, more preferably from about 0.5 to about 4% and most preferably up to about 3%.
Suitable fatty acid ~oaps useful in the present invention may be selected from the class consisting of potassium laurate, sodium laurate, sodium stearate, potassium stearate, ~odium oleate, etc. Similar soap6 containing ammonium ion a~ a cation may also be used particularly if the cleaner does not contain a bleach. Suitable soaps for use within the present invention are disclosed in Chemical Publishing Co., Inc., Encyclopedia Of Surface-Active Agents, Vol. I (1952), page 39 etc., Xirk-Othmer, Encyclopedia of Chemical Technology 3d, Vol. 21 pp. 162-181 re "502psn ~nd Vol. 22, re "Surf2ctants".
The manner in which the fatty acid anionic surfactant or soap functions in combinations with the colloidal alumina thic~ener and the hydrocarbon 601vent according to the present invention is not fully understood. It is believed that the soap may aid in 601ubilizing the organic solvent present in the cleaners of the present invention because it probably helps to mix or emulsify the solvent.
Organic Solvents The organic solvent~ useful in the present invention are alkyl or aryl hydrocarbons containing at lea6t 2 carbon atoms, preferably about 4 to about 18 carbon atoms and can include ether~, alcohols, esters, ketones and other hydrocarbons which are compatible with the fatty acid goap surfactant and colloidal aluminum present in the composition o~ the cleaner of the present invention. Examples of ~uch organic solvents include d-limonene, terpinolene, pine oil, glycol ethers such as butoxyethanol (bu~yl "Cellosolve"), straight or branched chain glycol ethers; glycols, such as polye.hylene glycol;
zlcohols ~uch as phencl, ethyl alcchol, benzyl alcohol, geraniol, citronellol, 6antalol, menthol, borneol, carveol, ethylhexelcarbonyl, vetiverol, linalol, terpineol, myrcenol, cetrol; and esters 6uch as linalyl acetate, benzyl acetate, isobornyl 1 33~670 acetate, ethyl acetoacetate and isoamylacetate.
Other examples of organic 601vents which may be useful in the cleaners of the present invention include 6aturated derivatives of terpenes, isoprenes, mineral spirits, such as the Isopar and ~orpar*series of mineral spirit6 and mineral oils sold by Exxon Corporation, and mineral oils, such as available from Penseco Company. Of course, mixtures of various organic solvents ~re useful in the cleaners of the present invention.
As understood with respect to the surfactants and soaps, saturated organic solvent6 should be used when ~A bleach i8 included in the cleaners of this invention to promote bleach stability as recognized by those skilled in the art.
Conversely, unsaturated organic 601vents may be selected for use in the non-bleach formulAtions of the cleaners of this invention. ~oreover, it is further understood that the organic solvent is selected to be co~patible with the soap and surfactant useful in the present invention ~s outlined above.
The amount of organic solvent employed in the cleaner according to the present invention will *Trade Mark be from an effective amount up to about 10% by weight of the cleaner, preferably from about 0.1 to about 8%, more preferably from about 0.1 to about 6%, and most preferably up to about 4S. In addition, it appear6 desirable in the present invention that the ratio of organic solvent to the combined amount of soap and surfactant generally be within certain ranges for moct practical formulation. In general, the weight ratio of organic 601vent to soap plus lo 6urfactant 6hould be less than about 1:40, and usually between about 10:1 and about 1:20, preferably between about 2:1 and about 1:10, more preferably between about 1:1.5 and about 1:9, still more preferably between about 1:2 and ~bout 1:8, and most preferably between about 1:3 and about 1:7.
Colloidal Alumina Thickener The colloidal alumina thickener component of the present invention is preferably a hydrated aluminum oxide h2ving gualifying characteri6tics 6uch as particle size to cause it to function as a colloidal thickerer. In this 6en6e, the colloidal alumina thickener used in th~ invention is to be contrasted from abrasive alumin2 materi21s having substantially larger particle sizes, for example substantially greater than one micron. Accordingly, 1 33~67iU
the particle size of the colloidal alumina thickener is a particularly important fe~ture for that component of the invention.
Preferred hydrated aluminas within the present invention are derived from synthetic Boehmites. Of greater importance, the hydrated colloidal alumina thickener of the present invention is chemically insoluble, that is, it should not dissolve in reasonably acidic, basic or neutral media. However, it is noted that colloidal alumina will dissolve in strongly alkaline media, for example, 50% NaOH.
A typical alumina is distributed by Remet Chemical Corp., Chadwicks, N.Y.j under the trademark DISPERAL (formerly DISPURA~) and manufactured by Condea Chemie, Brunsbuettel, West Germany. DISPERAL
i6 an aluminum oxide monohydrate which commonly forms - 20 stable colloidal aqueous dispersion6. Al~ina products oi this type commonly exist as dry powder~
which can form thixotropic gel6, bind 6ilica And other cera2ic substrates, while possêssir.g a positive charge and being substantive to a va -ety of surfaces.
DISPERAL has a typical chemical composition of 90% ~lpha aluminum oxide monohydrate (Boehmite) 9%
water, 0.5% carbon (as primary alcohol), 0.008%
6ilicon dioxide, 0.005% ferric oxide, 0.004% sodium silicate, ~nd 0.05% sulfur. It has a surface area (BET) of about 320 m2/gm, an undispersed averase particle 6ize (as determined by ~ieving) of lS% by weight being greater than 45 microns and 85% being less than 45 microns, an average particle ~ize, in - 10 dispersion, of 0.0048 microns as determined by X-ray diffraction, and a bulk density of 45 pounds per cubic foot (loose bulk) and 50 pounds per cubic foot (packed bulk). Yet another alumina suitable for use within the present invention, although not as preferred, is manufactured by Vista Chemicals Company, Houston, Texas and sold under the trademark CATAPAL ~lumina. CATAPAL has a typic21 chemical composition of 74.2% aluminum oxide (Boehmite), 25.8%
water, 0.36% carbon, 0.008% silicon dioxide, 0.005%
2G ferric oxide, 0.004% sodium oxide and less than 0.01%
~ulfur. It has a surface area (3ET) of 280 m2/gm, an undi6per~ed average p2rticle size (2s deter~ined by sieving) of 38% by weight being less than 45 mic_ons and 19% being gre2ter than 90 microns.
These colloidal alumina thickeners, used in 1 33667~
dispersed form in the invention, generally have exceedingly ~mall average particle size in dispersion (i.e., generally less than one micron). In point of fact, the average particle size diameter of these thickeners when dispersed is likely to be around 0.0048 micron. Thus, a preferred a~erage particle size range in dispersion is preferably less than one micron, more preferably less than about 0.5 micron and most preferably less than 0.1 micron. ~ue to their small particle 6ize, little or substantially no abrasi~e action i8 provided by these types of thickeners even though they are chemically insoluble, inorganic particles. Additlonally, these colloidal aluminas are chemically quite different from aluminum oxide abrasives, such as corundum. Colloidal aluminas are produced from synthetic Boehmite. In general, they are 6ynthesized by hydrolyzing aluminum alcoholates, with the resulting reaction products being hydrated aluminum (colloidal alumina) and three fatty alcohols. The reaction eguation is set forth below:
OR
Al- OR + (2 + x)H2O
OR
Rl-OH,R2-OHR3-OH ~ AlOOH.xH2O
(From Condea Chemie, ~PURAL PURALOX
DISPERAL High Purity Aluminas" Brochuse (1984).
These hydrated aluminum oxides are called 6ynthetic Boehmites merely because their crystalline 6tructure appears ~imilar to that of naturally occurring Boehmite. Boehmite, which is the actual mineral, has 2 Mohs hardness of about 3. It thus may be expected that the ~ynthetic Boehmite would not have a hardnes6 greater than the naturally occurring Boehmite. Corundum, on the other hand, appears to have a Mohs hardness of at lea6t 8 and perhaps higher. Thus, any abrasive action provided by colloidal aluminum oxides may be ~everely mitigated due to their relatlve ~oftness. An important aspect of the hydrated aluminas used herein is that they 6hould be chemically insoluble, i.e., ~hould not dissolve in acidic, basic or neutral media in order to have effective thicXening AS well ~s stability properties. ~:owever, colloi~al Eoehmite a!uminas will dissolve in highly basic media, e.g., 50% NaOH.
A further important point is that these ,~
colloidal alumina thickeners, in order to be useful as thickeners in the cleaners of this invention, must be initizlly dispersed in ~queous dispersion by means of strong acids. Preferable acids used to disperse these colloidal aluminas include, but are not limited to, acetic, nitric and hydrochloric acids. Sulfuric or phosphoric acids are not preferred.
Generally, a 1-50%, more preferably are about 5-40%, and most preferably about 10-35%
dispersion is made up, although in some instances, percentages of colloidal alumina are calculated for 100% (i.e., as if non-dispersed) active content. In practice, the colloidal alumina may be added to water sufficier.t to make up the desired percent dispersion and then the acid may be added thereto. Or, the acid may be first added to the water and then the colloidal alumina is dispersed in the dilute acid solution. In either case; a substantial amount of shearing (i.e., mixing in a mixing vat) is required to ¢btain the proper rheology.
Usually, a relatively small amount of concentrated acid is added. For instance, for a 25 wt.% dispersion material, 25% alumina monohydrate is combined with 1.75% concentrated (12M) hydrochloric acid ~nd then dispersed in 73.75% water. The colloidal alumina thickener itself is generally present in the cleaner in the ranse of about 1 to about 15% by weight based on the total weight of the cleaner, preferably about 1 to zbout 10%, more preferably about 1 to 6%, and most preferably, about 1 to about 5.5. Many useful formulations will contain from about 2.5 to about 5~ colloidal alumina according to the present invention.
Neutralization of the acidified dispersed colloid is necessary to obtain the desired, finished product rheology (i.e., it thickens). Thus, the acidified, diluted colloid is neutralized, preferably by sodium hydroxide te.g., a 50~ solution), although if the electrolyte/bu~fer is so~dium carbonate or sodium silicate, it may be possible to forego the sodium hydroxide as a ~eparate component. Secondly, since a halogen bleach may be added, if desired, to the cleaner~ of this invention, and such bleaches are unstable in the presence of acid, neutralization is ~lso desirable when a bleach is used.
With respect to thickening, it should be noted that while there are many types of inorganic and organic thickeners, not all will provide the proper type of plastic, flowable rheolosy desired in the present invention, particularly the preferred pourable consistency. Common clays, for instznce, those used in U.S. Patent 3,985,668 and ~.S. Patent 3,558,496, will likely lead to a false body rheology.
False body rheology pertains to liquids which, 2t rest, turn very viscous, i.e., form gels.
Problematic with such false body liquids i6 that they appear to tend to thicken very rapidly and harden or set up so that flowability is a problem. A
thixotropic rheology is also not particularly desirable in this invention since in the thixotropic ~tate, a liquid at rest also thickens dramatically, but, theoreticslly, ~hould flow upon shearing. If the thixotrope has a high yield stress value, as typically found in clay-thickened liquid media, the fluid at rest may not re-achieve flowability without shaking or agitation. As a matter of fact, if colloidal alumina alone is used to thicken the liqu-d cleaners of this invention, A thixotrope with high yield str2ss values appears to result. This type OL
product is less preferred, ar.d therefore, the surfactants included in the formulas of thi~
invention are crucial towards schieving a desire~
creamy, flowable, plastic rheology, particularly the preferred pourable consistency. Ordinarily, a 1 33~670 thixotrope will flow from a dispenser only upon Ehaking or 6queezing. ~n example of a typlcal thixotrope is catsup, which Ecmetl~es requires quite a bit of ~haking and pounding of ~he bottom of the bottle containing it to induce flow.
The type of rheology desired in this invention is a plastic, flowable rheology. This sort of rheology does not require shearing to promote fluidity. Thus, a product made in accordance with the present invention will not require, in its preferred form, sgueezing (assuming a deformable plastic squeeze bottle), 6haking or agitation to flow out of the container or dispenser, but will have a pourable consistency. In a non-preferred form, the cleaners of the present lnvention ~ay not be pourable from a particular container, but nevertheles6 are a ~moothly flowabie, plastic consistency and are not thixotropes.
Attaining this rheology in the cleaners of the presen. inventicn containing o~ganic solvents was ~sur~risir,g since it h2s b en thougr.~ that the combination of thickeners in cleane-s containing organic solvents would result in a different rheology. It was al~o surprising that cleansers such as in Choy et al. U.S. Patent 4,695,394, which are thickened and stabilized with colloidal alumina, would have such plastic rheology and also such abrasive-suspending stability so as to not become unstable when organic solvents were included in such compositions in accordance with the invention in ~o-pending application Serial No. 595,430 filed on March 31, 1989.
Moreover, nothing in the art had ever disclosed that fluent, solvent-containing household hard surface cleaners could be thickened with colloidal alumina to a flowable or plastic, preferably pourable, consistency.
lS Other Inqredients As mentioned above, the cleaners of the present invention can, when desired, contain a bleach. A source of bleach is selected from various halogen bleaches. ~or the purposes of the present invention, halogen bleaches are particularly favored.
As examples thereof, the bleach can be selected from the group consisting escentially of the al~al$ metal and alkaline earth salts of hypohalite, hypohalite addition products, haloamines, haloimines, haloimides and haloamides. These ~lso produce hypohalous bleaching species in situ with hypochlorites being a I :3 3 6 6 7 0 preferred form of bleach. Representative hypochlorite producing compounds include sodium, pota~ium, lithium and calcium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potas~ium 2nd sodium dichloroisocyanurate, trichloroisocyanuric acid, dichlorodimethyl hydantoin, chlorobromo dimethylhydantoin, N-chlorosulfam'de, and chloramine.
As noted above, a preferred bleach employed in the present invention is sodium hypochlorite having the chemical formula NaOCl, in an amount ranging from about 0.1% to about 5%, more preferably about 0.25% to 4% and most preferably 0.5S to 2.0%.
The purpose for the bleach is evident in forming an oxidizing cleaning agent which~is very effective against oxidizable stains such as organic stains.
A principal problem with the use of bleach in such composltions is its tendency to be unst2ble or to cause instability of other components, particularly cert2in surfact2nts if they are present in s~bst2nti21 ~mounts. In ~ny event, because of the usP of co710idal alu~inz ~s a thickener in the present invention together with a fatty acid s02p, 2 surfactant, and organic solvent together with only limited amounts of additional surfactant components, the bleach stability of the composition of the present invention ~expressed in half-life stability) i8 ~urprisingly good resulting in a product capable of maintaining excellent flow characteristics and bleach strength even after considerable periods of shelf life.
Abrasives may be added to the cleaners of the present invention to form scouring abrasive cleansers. The abrasives suitable for use and the useful amounts thereof are disclosed in copending application Serial No. 595,430 filed on March 31, 1989.
The cleaners of the present invention are particularly 6uited to inclusion of abrasives, because the colloidal alumina/surfactant/soap/organic ~olvent system of the present cleaners provide stable suspensions of abrasives therein to provide scouring cleansers. The clear,ers of the present invention may contain small ~mounts of fine or mild a~rasives to enhance cleaning efficacy for some applications, without producing a scouring action typical of many abrasive cleansers.
3 3 ~ 6 7 C
In addition to the components for the cleaning composition of the present invention as set forth above, further desirable ad~uncts may include bleach-stable dyes (for example, ~nthraquinone dyes~, pigments (for example, phthalocyanine, Tio2 and ultramarine blue), colorants and fragrances in relatively low amounts, for example, about 0.001~ to 5.0% by weight of the cleaner composition.
Water Water i6 the medium used as the medium in which the various components of the cleaner of the present invention are dissolved, dispersed or mixed.
Some of these components may be added to the cleaner in a water base, thus contributing to the total water present in the cleaner. While watPr and the miscellanecus minor ingredients or additives make up the remainder of t~.e composition, water is generally present in amounts ranging from about 10 to about 90 by weight of the cleaner.
Method of Pre~arinq As previously mentioned, the method of preparing the liouid cle2ner of this invention comprises combining:
(a) an initial portion of the total water with a colloidal alumina thickener;
~b) a final portion of the total water and a discrete amount of a neutralizing ~gent;
(c) optionally, a halogen bleach;
(d) a fatty acid Eoap;
(e) a Eurfactant (bleach ~table nonionic when a bleach is used);
(f) a buffer/electrolyte which interacts with the Eurfactant6 recited in 6teps (d) and (e) and the thickener recited in step (a) to result in a plastic rheology; and (g) an organic solvent.
As similarly described in U.S. Patent 4,657,692 at column 13, to produce the cleaner, alumina i6 charged into a vat or Euitable mixing vessel which has been provided with a 6uitable mixing mezns, 6uch as an impeller, which is in constant agitation with Euitable angular velocity.
The alumina is acidl'ied and diluted with about 50%
of the total water used. ~n alkyl benzene Eulfonate phase stabilizer can be optionally added at this point. A neutralizer, such as a 50% NaOH Eolution, can be added with the remainder of the water. Next, optional ingredients, such zs halogen bleach, 2brasives, dyes, fragrances, etc., czn be added, if desired. Thereafter, the anionic surfactants are added. When ~ilicate is used as the electrolyte/buffer, it is necessary to have a fatty acid soap as one of the anionic surfactants ~ince, as explained in U.S. Patent 4,695,394, the ~oap appears to surprisingly break up any network which could form between the silicate and the colloidal slumina.
Next, the bleach-stable nonionic surfactant is added, which is generally a trialkyl amine oxide (although a betaine or other surfactant would likely be suitable). At this point any alkyl benzené sulfonate is most preferably, although optionally, added. The electrolyte/buffer is then added and finally, the organic ~olvent i6 added. Alternatively, the organic solvent can be premixed with surfactants if desired.
Note that at virtually any step in this method, the optional minor ingredients, such ~s fragrance and pigments could be added. However, since fragrance is an organic component which m2y be more susceptible to oxidation by the h~logen ble2ch, ~t is prefer2ble to add it last when a bleach is present.
The invention is further illustrated by the e~bodiment ~et forth below:
1 33667~
EX~PLE
The following embodiment illustrates the thic~ened cleaner of the present invention containing surfactant, soap and an organic solvent, thickened with colloidal alumina.
Materi21 Wt.
Water 71.06 HCl (38%1 0.21 Disperall 4.50 Pigment 0.7s Ter~itol2 * 2.70 LAS 2.80 sAS4 2.65 Soap SolutionS 7.33 Sodium Chloride 2.00 Terpinolene6 * 3.00 Silicate ~U7 3.00 100. 00 1. Alumina (A1203.H20) from Condea Chemie.
2. Tergitol*TMN-6 from Union Carbide.
3. Biosoft L~S*40-S(40%) from Stepan Chemical Company.
4. Hostapur SAS*, secondary zlkane 6ulfonate from Hoechst A.G.
5. S02p solutior, prepared from 13.62 parts by weight laurlc zcid, 13.62 parts 50% NaOH and 72.75 parts water.
6. From SCM Arom2 znd Flavor Chemicals.
7. Sodium silicate RU from PQ Corporation.
~ *Trade Mark The above cleaner composition has a viscosity of l,720 cps (Brookfield RVT, ~pindle No.
4, 5 rpm, room temperature). It also exhibits the properties of being Emoothly flowable and pourab'e at room temperature, thus making it particularly us~ful as a thicXened aqueous cleaner.
The present invention also contemplates methods for forming cleaners including compositions such as those described above and illustrated by the various examples. Generally, such a method comprises the steps of combining the various components to form the cleaner composition.
The present invention also contemplates methods for cleaning hard surf2ces or removing 50il in z manner believed obvious from the preceding description. However, to assure a complete understanding of the invention, 6uch a method is carried out by contacting the surface, stain or 50il with a composition according to the present nvention. Thereafter, the composition Logether with the suspended staln is pre e-ably removed from the surface by rinsing.
Accordingly, there has been disclosed above a number of embodiments and examples for a thickened aqueous cleaner particularly characterized by a ~moothly flowable cr plastic consistency while demonstrating the ability to resist syneresis. W~ile preferred embodiments and examples of the invention have been illustrated and described above, it is to be understood that these embodiments are capable of further variation and modification; therefore, the present invention i6 not to be limited to precise details of the embodiments set forth above but is to be taken with ~uch changes and variations as fall within the purview of the following claims.
~ *Trade Mark The above cleaner composition has a viscosity of l,720 cps (Brookfield RVT, ~pindle No.
4, 5 rpm, room temperature). It also exhibits the properties of being Emoothly flowable and pourab'e at room temperature, thus making it particularly us~ful as a thicXened aqueous cleaner.
The present invention also contemplates methods for forming cleaners including compositions such as those described above and illustrated by the various examples. Generally, such a method comprises the steps of combining the various components to form the cleaner composition.
The present invention also contemplates methods for cleaning hard surf2ces or removing 50il in z manner believed obvious from the preceding description. However, to assure a complete understanding of the invention, 6uch a method is carried out by contacting the surface, stain or 50il with a composition according to the present nvention. Thereafter, the composition Logether with the suspended staln is pre e-ably removed from the surface by rinsing.
Accordingly, there has been disclosed above a number of embodiments and examples for a thickened aqueous cleaner particularly characterized by a ~moothly flowable cr plastic consistency while demonstrating the ability to resist syneresis. W~ile preferred embodiments and examples of the invention have been illustrated and described above, it is to be understood that these embodiments are capable of further variation and modification; therefore, the present invention i6 not to be limited to precise details of the embodiments set forth above but is to be taken with ~uch changes and variations as fall within the purview of the following claims.
Claims (12)
1. A thickened aqueous hard surface cleaner characterized by being smoothly flowable or plastic, comprising:
(a) at least one of an anionic, nonionic, amphoteric or zwitterionic surfactant being present in at least a cleaning-effective amount;
(b) an electrolyte/buffer forming about 0.1 to about 10% by weight of the cleaner;
(c) a fatty acid soap being present from an effective amount to about 5% by weight of the cleaner;
(d) an organic solvent present from cleaning-effective amount to about 10% by weight of the cleaner; and (e) a colloidal alumina thickener having an average particle size, in dispersion, of no more than about one micron, the colloidal alumina thickener forming from about 1 to about 15% by weight of the cleaner.
(a) at least one of an anionic, nonionic, amphoteric or zwitterionic surfactant being present in at least a cleaning-effective amount;
(b) an electrolyte/buffer forming about 0.1 to about 10% by weight of the cleaner;
(c) a fatty acid soap being present from an effective amount to about 5% by weight of the cleaner;
(d) an organic solvent present from cleaning-effective amount to about 10% by weight of the cleaner; and (e) a colloidal alumina thickener having an average particle size, in dispersion, of no more than about one micron, the colloidal alumina thickener forming from about 1 to about 15% by weight of the cleaner.
2. The cleaner of claim 1 wherein the colloidal alumina thickener has a maximum particle size in dispersion of not more than about 0.1 micron.
3. The cleaner of claim 1 wherein the surfactant comprises an anionic surfactant.
4. The cleaner of claim 1 wherein the fatty acid soap is an alkali metal fatty acid soap.
5. The cleaner of claim 4 wherein the anionic surfactant is monovalent.
6. The cleaner of claim 1 wherein the hydrocarbon solvent is at least one of d-limonene, terpinolene, pine oil, a glycol ether, an alcohol or a mixture thereof.
7. The cleaner of claim 1 wherein the fatty acid soap comprises from about 0.1 to about 4%
by weight of the cleanser.
by weight of the cleanser.
8. The cleaner of claim 1 wherein the hydrocarbon solvent comprises from about 0.1 to about 7% of the cleanser.
9. The cleaner of Claim 1 further comprising hypochlorite bleach.
10. The cleanser of Claim 1 characterized by being pourable.
11. A method for preparing a thickened aqueous hard surface cleaner characterized by being smoothly flowable or plastic, comprising the step of combining:
(a) at least one of an anionic, nonionic, amphoteric or zwitterionic surfactant being present in at least a cleaning-effective amount;
(b) an electrolyte/buffer forming about 0.1 to about 10% by weight of the cleaner;
(c) a fatty acid soap being present from an effective amount to about 5% by weight of the cleaner;
(d) an organic solvent present from cleaning-effective amount to about 10% by weight of the cleaner; and (e) a colloidal alumina thickener having an average particle size, in dispersion, of no more than about one micron, the colloidal alumina thickener forming from about 1 to about 15% by weight of the cleaner.
(a) at least one of an anionic, nonionic, amphoteric or zwitterionic surfactant being present in at least a cleaning-effective amount;
(b) an electrolyte/buffer forming about 0.1 to about 10% by weight of the cleaner;
(c) a fatty acid soap being present from an effective amount to about 5% by weight of the cleaner;
(d) an organic solvent present from cleaning-effective amount to about 10% by weight of the cleaner; and (e) a colloidal alumina thickener having an average particle size, in dispersion, of no more than about one micron, the colloidal alumina thickener forming from about 1 to about 15% by weight of the cleaner.
12. A method for cleaning a surface with a thickened aqueous cleaner characterized by having a smoothly flowable or plastic consistency comprising contacting the surface having a stain thereon with a thickened aqueous cleaner comprising:
(a) at least one of an anionic, nonionic, amphoteric or zwitterionic surfactant being present in at least a cleaning-effective amount;
(b) an electrolyte/buffer forming about 0.1 to about 10% by weight of the cleaner;
(c) a fatty acid soap being present from an effective amount to about 5% by weight of the cleaner;
(d) an organic solvent present from cleaning-effective amount to about 10% by weight of the cleaner; and (e) a colloidal alumina thickener having an average particle size, in dispersion, of no more than about one micron, the colloidal alumina thickener forming from about 1 to about 15% by weight of the cleaner.
(a) at least one of an anionic, nonionic, amphoteric or zwitterionic surfactant being present in at least a cleaning-effective amount;
(b) an electrolyte/buffer forming about 0.1 to about 10% by weight of the cleaner;
(c) a fatty acid soap being present from an effective amount to about 5% by weight of the cleaner;
(d) an organic solvent present from cleaning-effective amount to about 10% by weight of the cleaner; and (e) a colloidal alumina thickener having an average particle size, in dispersion, of no more than about one micron, the colloidal alumina thickener forming from about 1 to about 15% by weight of the cleaner.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US17660388A | 1988-04-01 | 1988-04-01 | |
| US176,603 | 1988-04-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1336670C true CA1336670C (en) | 1995-08-15 |
Family
ID=22645049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000595432A Expired - Lifetime CA1336670C (en) | 1988-04-01 | 1989-03-31 | Thickened pourable aqueous cleaner |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5376297A (en) |
| EP (1) | EP0336652B1 (en) |
| JP (1) | JP2784028B2 (en) |
| AT (1) | ATE116357T1 (en) |
| AU (1) | AU626836B2 (en) |
| CA (1) | CA1336670C (en) |
| DE (1) | DE68920182T2 (en) |
| ES (1) | ES2065372T3 (en) |
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| US5731276A (en) * | 1996-07-30 | 1998-03-24 | The Clorox Company | Thickened aqueous cleaning composition and methods of preparation thereof and cleaning therewith |
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| EP2366769B1 (en) * | 2010-03-05 | 2013-05-08 | Ivoclar Vivadent AG | Use of a Composition containing cleaning particles |
| US20150060322A1 (en) * | 2013-08-27 | 2015-03-05 | The Dial Corporation | Cleaning product exhibiting increased stability with crystalline particles |
| EP3040408A1 (en) | 2014-12-31 | 2016-07-06 | Hayata Kimya Sanayi Anonim Sirketi | Aqueous liquid cleaning compositions comprising bleaching agent and abrasive particles |
| US10119099B2 (en) | 2017-01-10 | 2018-11-06 | Envirox, L.L.C. | Peroxide based multi-purpose cleaner, degreaser, sanitizer/virucide and associated solutions and methods for preparing the same |
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| US4005029A (en) * | 1973-08-01 | 1977-01-25 | The Procter & Gamble Company | Laundering adjunct |
| DE2362114C2 (en) * | 1973-12-14 | 1984-07-05 | Henkel KGaA, 4000 Düsseldorf | Liquid foam-regulated detergent and cleaning agent |
| IE38738B1 (en) * | 1974-01-07 | 1978-05-24 | Unilever Ltd | Pourable liquid compositions |
| US4051056A (en) * | 1974-09-09 | 1977-09-27 | The Procter & Gamble Company | Abrasive scouring compositions |
| US4049467A (en) * | 1976-04-23 | 1977-09-20 | Lever Brothers Company | Method and compositions for removal of hard surface manganese ion-derived discolorations |
| US4116851A (en) * | 1977-06-20 | 1978-09-26 | The Procter & Gamble Company | Thickened bleach compositions for treating hard-to-remove soils |
| US4158553A (en) * | 1978-01-16 | 1979-06-19 | S. C. Johnson & Son, Inc. | Non-scratching liquid scouring cleanser using abrasives with a Mohs hardness of greater than 3 |
| US4235732A (en) * | 1978-02-08 | 1980-11-25 | The Procter & Gamble Company | Liquid bleaching compositions |
| US4352678A (en) * | 1978-10-02 | 1982-10-05 | Lever Brothers Company | Thickened abrasive bleaching compositions |
| US4240919A (en) * | 1978-11-29 | 1980-12-23 | S. C. Johnson & Son, Inc. | Thixotropic abrasive liquid scouring composition |
| US4248728A (en) * | 1979-02-28 | 1981-02-03 | Chemed Corporation | Liquid scouring cleanser |
| US4457856A (en) * | 1980-01-07 | 1984-07-03 | The Procter & Gamble Company | Liquid detergent composition contains abrasive particles, anionic and nonionic surfactants |
| CA1160134A (en) * | 1980-01-07 | 1984-01-10 | Sharon J. Mitchell | Abrasive-containing liquid detergent composition |
| US4287079A (en) * | 1980-06-02 | 1981-09-01 | Purex Corporation | Liquid cleanser formula |
| US4455250A (en) * | 1981-01-12 | 1984-06-19 | American Cyanamid Company | Stable liquid hard surface cleanser composition containing DGH and a quaternary germicide |
| US4414128A (en) * | 1981-06-08 | 1983-11-08 | The Procter & Gamble Company | Liquid detergent compositions |
| US4396525A (en) * | 1981-09-14 | 1983-08-02 | Lever Brothers Company | Phosphate free liquid scouring composition |
| EP0126545B1 (en) * | 1983-04-19 | 1987-08-19 | The Procter & Gamble Company | Liquid scouring cleansers containing solvent system |
| EP0137616B1 (en) * | 1983-08-11 | 1988-01-27 | The Procter & Gamble Company | Liquid detergents with solvent |
| US4507219A (en) * | 1983-08-12 | 1985-03-26 | The Proctor & Gamble Company | Stable liquid detergent compositions |
| US4533487A (en) * | 1983-08-15 | 1985-08-06 | Pitre-Jones | Process for producing blended d-Limonene and uses of the blended product |
| US4508634A (en) * | 1983-11-15 | 1985-04-02 | Minnesota Mining And Manufacturing Company | Aqueous skin cleaner composition comprising propylene carbonate |
| JPS60108499A (en) * | 1983-11-18 | 1985-06-13 | ライオン株式会社 | Abrasive-containing liquid detergent composition |
| US4599186A (en) * | 1984-04-20 | 1986-07-08 | The Clorox Company | Thickened aqueous abrasive scouring cleanser |
| US4695394A (en) | 1984-04-20 | 1987-09-22 | The Clorox Company | Thickened aqueous cleanser |
| US4657692A (en) * | 1984-04-20 | 1987-04-14 | The Clorox Company | Thickened aqueous abrasive scouring cleanser |
| US4576738A (en) * | 1984-12-21 | 1986-03-18 | Colgate-Palmolive Company | Hard surface cleaning compositions containing pianane |
| GB8519699D0 (en) * | 1985-08-06 | 1985-09-11 | Procter & Gamble | Scouring compositions |
| EP0216416A3 (en) * | 1985-09-24 | 1988-06-01 | The Procter & Gamble Company | Improved viscous phase stable liquid scouring cleansers containing solvent |
| US4788005A (en) * | 1987-05-15 | 1988-11-29 | The Clorox Company | Thickened aqueous abrasive cleanser exhibiting no syneresis |
| US4970016A (en) * | 1987-09-29 | 1990-11-13 | Colgate-Palmolive Co. | Thixotropic aqueous liquid automatic dishwashing detergent composition |
| US5089161A (en) * | 1987-09-29 | 1992-02-18 | Colgate-Palmolive Co. | Thixotropic aqueous liquid automatic dishwashing detergent composition |
| US4968445A (en) * | 1987-09-29 | 1990-11-06 | Colgate-Palmolive Co. | Thixotropic aqueous liquid automatic dishwashing detergent composition |
| US4842757A (en) * | 1988-01-21 | 1989-06-27 | The Clorox Company | Thickened liquid, improved stability abrasive cleanser |
| US5298181A (en) * | 1988-04-01 | 1994-03-29 | The Clorox Company | Thickened pourable aqueous abrasive cleanser |
| US5279755A (en) * | 1991-09-16 | 1994-01-18 | The Clorox Company | Thickening aqueous abrasive cleaner with improved colloidal stability |
-
1989
- 1989-03-13 AU AU31268/89A patent/AU626836B2/en not_active Ceased
- 1989-03-20 JP JP1066477A patent/JP2784028B2/en not_active Expired - Lifetime
- 1989-03-30 EP EP89303176A patent/EP0336652B1/en not_active Expired - Lifetime
- 1989-03-30 ES ES89303176T patent/ES2065372T3/en not_active Expired - Lifetime
- 1989-03-30 DE DE68920182T patent/DE68920182T2/en not_active Expired - Fee Related
- 1989-03-30 AT AT89303176T patent/ATE116357T1/en not_active IP Right Cessation
- 1989-03-31 CA CA000595432A patent/CA1336670C/en not_active Expired - Lifetime
-
1993
- 1993-02-22 US US08/021,645 patent/US5376297A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| ATE116357T1 (en) | 1995-01-15 |
| JP2784028B2 (en) | 1998-08-06 |
| US5376297A (en) | 1994-12-27 |
| JPH01292099A (en) | 1989-11-24 |
| EP0336652B1 (en) | 1994-12-28 |
| EP0336652A2 (en) | 1989-10-11 |
| DE68920182D1 (en) | 1995-02-09 |
| ES2065372T3 (en) | 1995-02-16 |
| EP0336652A3 (en) | 1990-04-04 |
| DE68920182T2 (en) | 1995-05-11 |
| AU3126889A (en) | 1989-10-05 |
| AU626836B2 (en) | 1992-08-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |