|Publication number||US3723330 A|
|Publication date||Mar 27, 1973|
|Filing date||Oct 5, 1970|
|Priority date||Oct 5, 1970|
|Publication number||US 3723330 A, US 3723330A, US-A-3723330, US3723330 A, US3723330A|
|Original Assignee||Tri D Corp|
|Export Citation||BiBTeX, EndNote, RefMan|
|Referenced by (21), Classifications (11)|
|External Links: USPTO, USPTO Assignment, Espacenet|
United States Patent 3,723,330 DETERGENT COMPOSITIUN Bob W. Shellin, Avon, Conn. Tri-D Corporation, 7 Johnson Ave., Plainville, Conn. 06062) No Drawing. Filed Oct. 5, 1970, Ser. No. 78,260 Int. Cl. C11d 3/18 US. Cl. 252-153 Claims ABSTRACT OF THE DISCLOSURE A new general purpose aqueous alkaline detergent composition particularly effective against unctuous soil consists essentially of a homogeneous dispersion of soap or synthetic detergent, a volatile alkaline detergent builder, water and volatile water-insoluble organic solvents of the halogenated hydrocarbon and dialkyl ether types. The composition preferably is formulated as a concentrated emulsion and at the time of use is diluted with Water to obtain a working concentration.
BACKGROUND AND SUMMARY OF THE INVENTION The present invention relates to general purpose liquid cleaning compositions. More particularly, it is directed to a new and improved aqueous detergent composition exhibiting an exceptional effectiveness on unctuous or oilbase soils and dirts.
As is well known, a great many different compositions including plain Water, soaps, detergents and various types of chemicals including acidic and alkaline materials, have been suggested as general purpose cleaning compositions. Each type of cleaner desirably loosens and disperses the soil, either physically or by chemical reaction, so that the soil can be solubilized and removed from the article being cleaned. Unfortunately, many of the previously suggested detergent compositions are effective for cleaning only certain types of soil and are completely ineffective against other materials, and even have a deleterious effect on the surfaces to be cleaned.
A common failing of many detergent cleaning compositions results from the fact that while apparently loosening and dispersing the soil, they fail to pick up and retain the soil and it is redeposited as the cleaning composition is removed from the surface being cleaned. Emulsified oils, such as pine oil cleaners and oil soaps, have been particularly eifective against unctuous soils since they attack the oily base of the soil. However, generally speaking, the emulsified oil cleaners have the disadvantageous tendency of leaving behind some of the cleaning constituents upon which their effectiveness is based. In fact, this occurs not only after wiping off the cleaner but even after fully rinsing the articles to which these cleaners are applied.
It had been suggested that aqueous detergent compositions of high strength or industrial strength would overcome these difiiculties. However, when the compositions were strengthened to the necessary degree, they adversely affected the surfaces being cleaned, that is, they tended to cut into the paint or other finish on the surface. Additionally, such compositions are so strong that the user frequently is required to wear rubber gloves or use other protective means to avoid the harsh dermatological effects produced by such strengthened compositions.
Accordingly, it is an object of the present invention to provide a new, improved and efiicient alkaline cleaning composition of the general purpose liquid type which is particularly effective for removing greases, oils, wax, fats, foods and similar oil-base soils, yet upon application is sufliciently mild so as not to damage painted or varnished surfaces or the like or have a harsh dermatological effect on the user. Included among the salient objects of this invention is the provision for a detergent cleaning composition which can be used without damage to plastics, fabric, walls, appliances, woodwork, machinery, furniture or light fixtures, that is, a composition for effective and efiicient general purpose cleaning in homes, ofiices, machine shops or other locations where oil-base soils tend to collect.
Another object of the present invention is to provide a new and improved detergent cleaning composition of increased cleaning ability that is safe to substantially all types of surfaces yet exhibits a controlled short duration period of high cleaning activity once applied to a surface to be cleaned. This rapid, high efliciency cleaning action is coupled with an ability to attract and retain the loosened and dispersed soil within the cleaning composition for easy removal thereof without redeposit on the surface being cleaned, yet is sufficiently mild after the controlled period to permit prolonged contact with the skin of the normal user without adverse effect.
Another object of the present invention is to provide a cleaning composition of the type described which is adapted for spray application, does not require rinsing of the treated surface and can be readily and completely removed by wiping. Included in this object is the provision for a cleaning composition of the type described which contains volatile and flammable organic components, yet is nonfiammable and nontoxic under normal use conditions.
Other objects will be in part obvious and in part pointed out in more detail hereinafter.
A better understanding of the objects, advantages, features, properties and relationships of the invention will be obtained from the following detailed description which is indicative of the various ways in which the principles of the invention are employed.
DESCRIPTION OF A PREFERRED EMBODIMENT The new general purpose cleaning composition of the present invention is an aqueous alkaline detergent composition consisting essentially of a homogeneous mixture of a soap or synthetic detergent, an alkaline detergent builder, volatile water-insoluble organic solvents of the halogenated hydrocarbon and dialkyl ether types and water. The composition preferably is formulated as a concentrated emulsion and at the time of use is diluted with water in a Water to concentrate ratio of about 15:1 to obtain a working concentration. Despite the high volatility of the organic solvents and particularly the flammability of the ether component, the cleaning composition is relatively stable in a spray applicator prior to application, is nonflammable and will not support combustion.
As will be appreciated, the amounts of the different constituents may vary within certain broad limits without deleteriously aflfecting the beneficial effects and desirable properties of the composition. For example, the general concentration limits for the cleaning composition in its emulsified condition are shown in Table I. Of course, it is necessary to maintain certain relationhips between the components, as described in greater detail hereinafter. A specific example of a preferred composition ratio is also set forth in Table I.
The soap or synthetic detergent used in the composition of the present invention is preferably a water-soluble material capable of acting as a dispersing and emulsifying agent for the organic solvent components and may be any suitable commercially available soap or synthetic detergent. These include the alkaline metal salts of fatty acids or long chain alkyl aromatic sulfonates used alone or as mixtures. It is, of course, easier to employ commercially available mixtures in which it is believed the alkyl portion of the fatty acid soap or synthetic detergent generally has a carbon chain of about to 24 carbon atoms. Typical of the soaps that may be used in the composition of the present invention are the alkaline metal salts, such as the sodium salts, of oleic, lauric, palmitic, stearic, linolenic, linoleic and capric acids and mixtures thereof. The preferred synthetic organic detergents are anionic agents such as the sulfated and sulfonated detergents. These include the alkyl aromatic sulfonates such as sodium dodecyl benzene sulfonate. These higher alkyl aryl sulfonates may contain, for example, about 35 to 65 parts by weight of sodium sulfate and 65 to 35 parts by weight of the water-soluble salt of a monoalkyl aromatic hydrocarbon sulfonic acid wherein the alkyl group has about 9 to 16 carbon atoms. Part of the sodium sulfate may be replaced by other salts such as magnesium sulfate, sodium carbonate, tetrasodium pyrophosphate, borax or the like. Detergents used in the composition of the present invention with repeatedly good success include the commercially available detergents sold under the trade designations Orvis," Tide, Cheer and the like, whose primary constituent is believed to be an alkyl aryl sulfonate.
Water-soluble nonionic and anionic wetting agents, such as glycols and glycol ethers, may be present in the synthetic organic detergent formulation together with the alkylated aromatic sulfonates. For example, the detergent may contain as much as about percent by weight of a surface active wetting agent such as diglycol laurate, sorbitan monolaurate, polyoxypropylene, glycol-ethylene oxide polymers, polyalkylene glycol esters, oxyethylated fatty acid partial esters of polyhydric alcohols, ethylene oxide-fatty alcohol condensates, alkyl aryl polyglycol ethers such as nonyl phenol-ethylene oxide condensate or the condensation product of a long chain mercaptan and ethylene oxide. Other ingredients such as abrasives, antiseptics, germicides, perfumes, dyes and other adulterants may also be incorporated without adversely altering the physical properties of the resultant composition.
Although various conventional detergent builders may be present in the detergent utilized, it is preferred in accordance with the present invention to incorporate additional alkaline detergent builders and more specifically those alkaline detergents builders which exhibit a high vapor pressure or contain volatile constituents capable of rapid release upon application of the cleaning formulation to the surface being cleaned. In accordance with the present invention, the preferred material for use as a detergent builder is concentrated ammonium hydroxide which, of course, is diluted during the formulating process.
The amount of volatile detergent builder will vary substantially as indicated in the generalized formulation set forth hereinbefore in Table I. However, it is necessary that the requisite alkalinity of the cleaning concentrate be maintained. In this connection a concentrate pH in the range of about 913 may be used while a pH of 10-12 is preferred with lower pHs being acceptable so long as the composition maintains an alkaline condition. Although buffers may be added they generally are not required since it is preferred that the detergent builder remain active only for the short period required for etfective cleaning, that is, within a few minutes after application to the surface being cleaned, after which time it preferably should evaporate, volatilize or decompose.
As indicated hereinbefore, the cleaning composition of th p s n i ent on contains Water-insolubl g nic solvents of the halogenated hydrocarbon and lower alkyl ether type as additional volatile components thereof. These materials are selected not only for their ability to cut into and solubilize oil-base soils but also for their volatility characteristics. It is an important feature of the present invention that the volatile organic solvents exhibit little or no solubility in water and have a vapor pressure of at least about 30 mm. Hg at room temperature. Thus, as a rule, the relatively insoluble organic solvents have a boiling point about or below C.
The amounts of the respective organic solvents may vary but the halogenated hydrocarbon should always be present in amounts greater than the lower alkyl ethers. In fact, the amount of halogenated hydrocarbon will substantially exceed the amount of lower alkyl ether in the cleaning formulation by a factor varying from 2x to 20X. Generally, the weight ratio of halogenated hydrocarbon to alkyl ether will vary from about 2:1 to about 15:1 with the preferred ratio of relative amounts being within the range of 3:1 to 5:1.
The halogenated hydrocarbon solvents exhibiting the requisite volatility and chemical stability are the polyhalogenated lower alkyl materials of relatively low boiling point, i.e., those having a boiling point below 100 C. They are substantially insoluble in water and have alkyl groups of about 1 to 5 carbon atoms. Typical of such materials are 1,1-dichloro ethane, 1,2-dichloro ethane, dichloro methane, dibromo methane, 1,1-dichloro ethylene, 1,2-dichloro ethylene, 1,1-dichloro propane, 1,2-dichloro propane, 2,2-dichloro propane, 1,1-dichloro propylene-1, 1,2-dichloro propylene-1, 1,2-dichloro propylene-2, chloroform, 1,1,1-trichloro ethane, trichloroethylene and carbon tetrachloride.
The lower alkyl ethers utilized in accordance with the resent invention also exhibit volatility characteristics similar to the halogenated hydrocarbons. They are lower dialkyl ethers containing a single ether linkage and having alkyl groups containing from about 1 to 4 carbon atoms. They are only slightly soluble in water, have boiling points below 100 C., and should be distinguished from those water-soluble ethers containing multiple ether linkages or free hydroxyl groups, such as the soluble glycol ethers which are used as wetting agents to assist the detergent action of the synthetic detergent materials. Thus, materials such as diethyl ether, dipropyl ether, diisopropyl ether, methpropyl ether, ethylpropyl ether, methybutyl ether, ethylbutyl ether, diallyl ether, allylethyl ether, allylpropyl ether and allylisopropyl ether are generally employed.
The ether component should at all times be present in amounts substantially less than the amount of the detergent utilized in the cleaning composition. In fact, in the preferred formulations, the combined amounts of organic solvent are only about one half that of the detergent. Although the detergent-ether ratio may vary from about 2:1 to about 35:1, the preferred ratio is generally in the range of about 8:1 to 10:1.
The relative amounts of the detergent and halogenated hydrocarbon on the other hand, may vary substantially. Thus the detergent-halogenated hydrocarbon ratio may range from about 1:2 to about 9:1, although it is generally preferred that the detergent be present in greater amount than the halogenated hydrocarbon. In practice it has been found that a ratio of approximately 2:1 to 4:1 gives good results.
The cleaning composition is a homogeneous mixture and preferably takes the form of a stable emulsion of the insoluble organic phase within the aqueous matrix. In accordance with a preferred method of formulation, the detergent and water are intimately mixed to form a viscous pasty liquid having a smooth fiowable consistency. It will, of course, be appreciated that this detergent premix will function both as a dispersant and emulsifier for the organic solvents subsequently added thereto. However, supplemental emulsifying agents may be used, if
needed. Although the detergent builder can be added separately to the pasty detergent blend, it is generally preferred that it be premixed with the halogenated hydrocarbon and that the admixture of the builder and halogenated hydrocarbon be slowly added to the smooth detergent paste with constant agitation so as to fully and completely blend it into the detergent paste. Subsequently, the insoluble lower alkyl ether is intermixed to provide the desired stable emulsion. It will, of course, be appreciated that each stage of the mixing process should be substantially complete before progressing with the addition of subsequent materials.
The resultant cleaner concentrate is a product of slight viscosity and is readily adapted to dilution with water prior to use. Generally the concentrate has an alkaline pH on the order of about 12.5 so that after dilution with water in a ratio of about 15:1, it results in a general purpose composition having a pH of about 11.0. This alkaline solution is extremely effective against unctuous or oil-base soils with the emulsified organic solvents being capable of rapidly effecting release of the soil and permitting the detergent to immediately attract and sequester the soil within the emulsion and prevent redeposit thereof on the surface being cleaned.
Although the exact mechanism of the cleaning emulsion of the present invention is not fully understood, it is believed that the rapid volatilization or evaporation of the organic solvents and detergent builder provides microvoids within the emulsion which are quickly and rapidly filled by the soil released from the surface being cleaned. The soil is drawn into these microvoids and securely held within the stable dispersion to prevent its redeposition on the surface being cleaned. In this way, all the dirt is carried with the emulsion as the emulsion is wiped from the surface or otherwise removed to provide a highly eifective cleaning operation. Additionally, the rapid release of ammonia upon application of the emulsion quickly lowers the pH of the cleaning composition and avoids harsh dermatological effects upon contact with the skin of the user. Although this modus operandi is believed to be an accurate explanation, it will, of course, be appreciated that the cleaning operation of the composition should not be restricted to any one particular theory.
While the laundry industry has developed standard testing procedures for determining the cleaning ability of various detergent compositions on textile materials and the like, no such standard test has been found for general purpose cleaning formulations intended for use on solid surfaces, such as walls, woodwork, furniture and the like. Therefore, a testing procedure was developed to determine the elfectiveness of the composition of the present invention, particularly on oil-base soils. This procedure utilizes as a standard soil a dispersion of finely divided graphite and grease coated on a solid, slightly irregular yet non-absorbent surface such as a sheet of textured plastic, e.g., the material sold under the trade name Formica.
The standard soil is prepared by applying a substantially uniform coating of colloidal graphite to the textured surface from a pressurized spray can or the like. The graphite coating is preferably permitted to dry and a thin coating of grease is applied to and admixed with the graphite. The particular colloidal graphite found to give good results is an isopropyl alcohol suspension of graphite sold under the trade designation DAG 154 grade by Acheson Colloids Company. A general purpose lubricating grease is employed as the grease component of the soil. In practice, automotive greases such as the grease sold by Mobil Oil Company under the trade designation Mobilux Grease No. 2, have been found most suitable since they readily provide an acceptable seal for the graphite coating.
Using the graphite-grease test soil, it is possible to evaluate the cleaning power of the present inventions cleaning composition in comparison with commercially available general purpose cleaners. In particular, it is possible to determine the ability of the respective cleaning compositions to not only wet the surface being cleaned, but also to attack and cut into the unctuous soil, to lift it from the surface to be cleaned, and to retain or fix the soil within the cleaning composition for ready removal.
The following specific examples are given in order that the effectiveness of the present invention may be more fully understood. These examples are set forth for the purpose of illustration only and are not intended in any way to limit the practice of this invention. Unless otherwise specified all parts are given by weight.
EXAMPLE 1 A mixing container of appropriate size was charged with 50 pounds of synthetic organic detergent sold under the trade designation Orvis and 12.5 gallons of water and the contents were mixed until a smooth pasty consistency resulted.
In a separate container about 1.5 gallons of chloroform (technical grade) was admixed with an equal amount of concentrated ammonium hydroxide. The resultant mixture was then slowly added to the paste with constant agitation. After the addition was complete, the agitation was continued for 2-5 minutes to assure thorough mixing. About 0.75 gallon of isopropyl ether was then slowly added to the admixture with agitation to produce a stable emulsion of the cleaner concentrate.
The resultant concentrate was diluted with about 15 parts of water for each part of concentrate to produce a cleaning composition, designated Composition 69 in Table II. This composition was then subjected to comparative testing with four commercially available general purpose cleaners. In order to compensate for variations unavoidably occurring in the test soil samples. Composition 69 was tested in side-by-side relationship with each commercial cleaner on separate graphite-grease test soil samples. The results are set forth in Table II.
As indicated by the test results set forth in Table II, the composition of the present invention performed comparably or better than commercially available general purpose cleaners. In fact, under actual working conditions on a machine shop wall, it outperformed all other cleaners in its abiilty to thoroughly remove all soil.
TAB LE II Cleaner performance Soil fixing 4 Oil Soil Standard Shop Cleaner Wetting 1 cutting 1 lifting 3 soil wall 5 Composition 69.-. Wets Yes 6O 6 5 Commercial F do No 60 5 4 Composition 69 do Yes 5 5 Commercial S do No 80 5 3 Composition 69 rdo. Yes 5 5 Commercial A. Partial Yes 70 5 4 Wets. Composition 69.-. Wets Yes 5 6 Commercial W do No 80 4 3 1 The cleaning compositions were sprayed on a soil sample held in a vertical position and a visual determination was made of the cleaners ability to wet. the soil.
9 The test sample from the wetting test was observed for evidence of gravity streaking immediately after spraying.
3 The percentage of clean area within the area wiped after a clean clcth makes one pass through the soil.
4 A visual evaluation of the cleaners ability to remov all the dirt, using a scale 1 to 5 with 5 indicating total soil removal.
5 The wall of a machine shop was used as the test soil to which the cleaning compositions were applied.
EXAMPLES 2 THROUGH 19 Six cleaning composition concentrates within the teachings of the present invention were prepared in accordance with the procedure of Example 1. The amounts of the respective components are set forth in Table III.
TABLE III Concentrated Orvis ammonium Isoprop detergent Water Chloroiorm hydroxide ether Example N0. Gms. Percent Gms. Percent Gms. Percent Gms. Percent Gms. Percent TABLE IV Fixing onpmcnmphmir-wuhmp Comparably good results were obtained from the additional formulations set forth in Table V.
ether, while in Example 23, 23 grams of ammonium hydroxide was used together with 90 grams of isopropyl ether. Side by side comparative tests on a single graphite soil sample gave the following results:
TABLE VII Example Lifting Fixing No. ability ability Due to some stratification of both cleaning compositions, it was necessary to shake the compositions prior to application to the test soil.
EXAMPLE 24 The cleaning formulation of Example 1, namely, Composition 69, was tested in comparison with a similar emulsified composition, Composition X, containing a glycol ether and mixed cresols. The formulation for Composition X is as follows:
TABLE V Example Nos.
Orvis" 27.3 27.7 Tide Cheer Ivory Flakes" Chlorol'orrn Carbon tetrachlorid Trichlorocthylene Dichloroethylenc Ammonium hydroxide (c0110.) lsopropyl ether t Dipropyl ether 2.4 2.4 Diethyl etl1cr 2.4 2.3 2.4 Water 51.0 55.4 54.2 55.4 54.6 54.2 54.6 54.6 54.6 522 54.2 54.6
EXAMPLES 20 AND 21 TABLE VIII Two separate cleaning formulations were prepared 50 Component: Peroent according to the procedure of Example 1 from 100 grams Detergent 9 .prvi detergent, 200 grams of water, it) grams of Mixed cresols boiling between C. and isopropyl ether and diifering amounts of chloroform and C. and having a spgcific gravity of 1040 to concentrated ammonium hydroxide. In Example 20, 180 L050 25 grams of chloroform was used together with 23 grams of Trichloro ethylene 11 concentrated m n m hydroxide vyh in E mp 2 methylene glycol monoethyl ether 30 36 grams of chloroform was used in combination with sulfurized terpanes (30% sulfur) 1 38 grams of concentrated ammonium hydroxide. Side by Water 25 side comparative test results are reported in Table VI.
Comparative test data on graphite-grease soil samples is TABLE VI set forth in Table D(.
Example Lifting Fixing TABLE IX No. ability ability 20 90 5 Ci iii-2 L tlt eaner 8. 21 s5 4 W a 1 y Composition 69- 6O 5 gomposittion 22%...- (530 1 n 0 EXAMPLES 22 AND 23 03533531169 50 5 Two separate cleaning compositions were prepared ac- 70 As can be seen from Table IX the composition of the cording to the procedure of Example 1 from 100 grams of detergent, 200 grams of water, 36 grams of chloroform and differing amounts of ammonium hydroxide and iso propyl ether. In Example 22, 230 grams of ammonium hydroxide was used together with 9.6 grams of isopropyl specific disclosure can be made without departing from the teachings of the present invention.
1. A general purpose liquid cleaning composition particularly effective for removing grease, oil and similar unctuous soils without adversely affecting the finish of the surface being cleaned comprising a stable emulsion of a water insoluble organic phase in an aqueous mixture of a dispersing agent, the organic phase constituting up to about 45 percent by weight of the composition and the water constituting at least about 55 percent by weight of the composition, said organic phase including a volatile halogenated hydrocarbon of l to carbon atoms and a volatile lower dialkyl ether having a single ether linkage and alkyl groups of 1 to 5 carbon atoms, said halogenated hydrocarbon and lower dialkyl ether being substantially insoluble in water and having vapor pressures of at least 30 mm. Hg when applied to the surface being cleaned and boiling points below about 100 C., the weight ratio of dispersing agent to ether being at least 2:1 and the amount by weight of ether being less than the amount by weight of said halogenated hydrocarbon, said aqueous mixture having a pH up to about 12.
2. The composition of claim 1 wherein the dispersing agent is a water-soluble detergent.
3. The composition of claim 2 wherein the weight ratio of detergent to halogenated hydrocarbon varies from 1:2 to 9:1 and the weight ratio of halogenated hydrocarbon to ether varies from 2:1 to 15:1.
4. The composition of claim 1 including an alkaline detergent builder in an amount sufficient to impart to the composition a pH of at least about 9.
5. The composition of claim 1 wherein the aqueous mixture is in the form of a concentrate containing about 5 to 55 percent by weight dispersing agent, about 5 to 35 percent by weight halogenated hydrocarbon and about 1 to 10 percent by weight ether.
6. The composition of claim 1 wherein the halogenated hydrocarbon contains at least two halogen atoms and the composition has a pH of about 10-12.
7. The composition of claim 1 wherein the ether is diisopropyl ether. 7
8. The composition of claim 1 wherein the halogenated hydrocarbon is selected from the group consisting of chloroform and dichloroethylene.
9. The composition of claim 1 wherein the aqueous mixture includes about 0.5 to 10 percent by weight of concentrated ammonium hydroxide.
10. The composition of claim 1 wherein the mixture contains about up to 10 percent by weight of a detergent alkaline builder, at least 5 percent by Weight of a detergent as the dispersing agent, at least 5 percent by weight of the halogenated hydrocarbon and up to about 10 percent by weight of the dialkyl ether.
References Cited UNITED STATES PATENTS 491,413 2/1893 Ehrnan 252139 X 3,336,232 8/1967 Bauer et al. 252-l53 2,548,766 4/1951 Baum et a1. 2521l8 8,546,124 12/1970 Fleischer 282-l53 2,753,939 7/4956 Carpenter et a1. 282-470 X 3,094,469 6/1963 Strauss et al 134-4O X MAYER WEIN'BLATT, Primary Examiner US. Cl. X.R.
13439, 252DIG. 8, DIG. 10, 111, 139,
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US3887497 *||Mar 15, 1973||Jun 3, 1975||Ulvild George B||Liquid cleansing composition and method of producing|
|US3950185 *||May 7, 1974||Apr 13, 1976||Nichiban Co., Ltd.||Film removing compositions|
|US4302365 *||Feb 11, 1980||Nov 24, 1981||American Grease Stick Company||Engine degreaser composition|
|US4592856 *||Nov 2, 1984||Jun 3, 1986||Shin-Etsu Chemical Co., Ltd.||Liquid detergent composition|
|US4652389 *||Dec 14, 1984||Mar 24, 1987||The Clorox Company||Carpet cleaner|
|US4780100 *||Nov 26, 1986||Oct 25, 1988||The Clorox Company||Fabric cleaner|
|US5075026 *||May 21, 1986||Dec 24, 1991||Colgate-Palmolive Company||Microemulsion all purpose liquid cleaning composition|
|US5700331 *||Jun 14, 1996||Dec 23, 1997||Colgate-Palmolive Co.||Thickened cleaning composition|
|US5703028 *||Jun 14, 1996||Dec 30, 1997||Colgate-Palmolive Co||Liquid crystal detergent compositions based on anionic sulfonate-ether sulfate mixtures|
|US5719114 *||Jun 28, 1996||Feb 17, 1998||Colgate Palmolive Company||Cleaning composition in various liquid forms comprising acaricidal agents|
|US5723431 *||Apr 26, 1996||Mar 3, 1998||Colgate-Palmolive Co.||Liquid crystal compositions|
|US5759290 *||Jun 13, 1996||Jun 2, 1998||Colgate Palmolive Company||Liquid crystal compositions|
|US5763386 *||Jun 20, 1996||Jun 9, 1998||Colgate Palmolive Company||Microemulsion all purpose liquid cleaning compositions comprising ethoxylated polyhydric alcohols with at least partial esters thereof, and optional dralkyl sulfosuccinate|
|US5811383 *||Jan 27, 1997||Sep 22, 1998||The Dow Chemical Company||High water content, low viscosity, oil continuous microemulsions and emulsions, and their use in cleaning applications|
|US6159925 *||Apr 6, 2000||Dec 12, 2000||Colgate-Palmolive Co.||Acidic liquid crystal compositions|
|US6194371||May 1, 1998||Feb 27, 2001||Ecolab Inc.||Stable alkaline emulsion cleaners|
|US8785366||May 26, 2009||Jul 22, 2014||Colgate-Palmolive Company||Liquid cleaning compositions and methods|
|EP0187004A2 *||Dec 13, 1985||Jul 9, 1986||The Clorox Company||Fabric cleaner|
|EP0187004A3 *||Dec 13, 1985||Aug 9, 1989||The Clorox Company||Fabric cleaner|
|WO1994023012A1 *||Mar 31, 1994||Oct 13, 1994||The Dow Chemical Company||Microemulsion and emulsion cleaning compositions|
|WO1998004761A1 *||Jul 24, 1997||Feb 5, 1998||The Dow Chemical Company||High water content, low viscosity, oil continuous microemulsions and emulsions, and their use in cleaning applications|
|U.S. Classification||510/365, 134/39, 510/432, 510/417, 134/40, 510/506, 510/435|
|International Classification||C11D3/43, C11D17/00|