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US5998355 - US005998355A United States Patent[19[11 Patent...

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Unformatted text preview: US005998355A United States Patent [19] [11] Patent Number: 5,998,355 Brumbaugh [45] Date of Patent: Dec. 7, 1999 [54] LIQUID DISHWASHING DETERGENT 4,954,292 9/1990 Hull et al. . 5,389,282 2/1995 Saijo et al. ......................... 252/174.17 [75] Inventor: Ernest H. Brumbaugh, Rockford, 5,403,509 4/1995 Pujol etal. ........................ 252/174.22 Mich. 5,425,891 6/1995 Pujol et al. . 5,599,785 2/1997 Mondin et al. ......................... 510/417 [73] Assignee: Amway Corporation, Ada, Mich 5,653,970 8/1997 Vermeer ............................... 424/7024 FOREIGN PATENT DOCUMENTS [21] Appl' No“ 08/976’900 W0 95/23204 8/1995 WIPO . [22] Filed: Nov. 24, 1997 OTHER PUBLICATIONS Related US. Application Data International Cosmetic Ingredient Dictionary, Seventh Edi- tion, vol. 1, 1997. [63] Continuation of application No. 08/559,552, NOV. 16, 1995. . . 5 Primary Exammer—Yogendra Gupta [51] Int. Cl. ................................. C11D 1/12; C11D 1/83 Assistant Examiner—Gregory E. Webb [52] US. Cl. .......................... 510/424; 510/235; 510/427; Attorney, Agent) or Firm—Brinks Hofer Gilson & Lione; G. 510/434 Peter Nichols [58] Field of Search ..................................... 510/235, 236, 510/237, 424, 437, 503, 505, 427, 434 [57] ABSTRACT _ Liquid dishwashing detergent compositions are prepared [56] References Clted that exhibit increased Viscosity, better dissolution rate and US. PATENT DOCUMENTS surprisingly improved cleaning performance in hard water, . comprising from about 1% to about 90% of an anionic 3,427,248 2/1969 Lambertti et al. ...................... 252/117 surfactant and from about 1% to about 30% of a solvent 492069070 6/1980 Jones; hydrotrope selected from the group consisting of alkoxy- :jiégjggg) 1313:: Eggéiaét a1 lated glycerides, alkoxylated glycerines, esters of alkoxy- 4,483,780 11/1984 Llenado ' ' lated glycerines, alkoxylated fatty acids, esters of glycerin, 4,492,646 1/1985 Welch . . polyglycerol esters and combinations thereof. 4,743,394 5/1988 Kaufmann et al. . 4,780,249 10/1988 Pittz et al. .............................. 252/547 22 Claims, N0 Drawings 5,998,355 1 LIQUID DISHWASHING DETERGENT This application is a continuation of application Ser. No. 08/559,552, filed Nov. 16, 1995. BACKGROUND OF THE INVENTION This invention relates to light duty dishwashing detergents, and in particular, to light duty dishwashing detergent compositions that contain a fatty acid or glycerine derivative as a hydrotrope. The term “dishes” as used in the following description indicates utensils that maybe required to be washed free from food particles and other food residues, greases, proteins, starches, gums, dyes, oil, and burnt organic resi- dues. Light duty liquid detergents, such as are suitable for use in the washing of dishes, are well known and have met with a high degree of consumer acceptance because of their good washing and foaming properties and convenient form for use. Many current dishwashing formulations contain anionic surfactants that may gel unless prevented by various sol- vents or hydrotropes. Hydrotropes are viscosity controlling agents, gel suppressants, stability agents and dispersability aids. Commonly used hydrotropes include alcohols and alcohol derivatives including glycols and alkoxylated alco- hols. Aperceived problem with alcohols and glycols is that the amount required to achieve formulation stability may be enough to reduce overall levels of viscosity of the compo- sition to an extent that consumers may believe they are not receiving an optimum dishwashing formulation. High levels-of alcohol can also effect the perception of the fra- grance used in the composition and affect consumer percep- tion of the product. In addition, both alcohols and glycols can produce less than optimum dissolution rates. Moreover, alcohols are flammable and thus present hazardous condi- tions. Alcohols can also contribute to the drying of a user’s hands. The present invention solves these problems by replacing the commonly used hydrotropes in whole or in part with a hydrotrope selected from the group consisting of alkoxy- lated glycerides, alkoxylated glycerines, esters of alkoxy- lated glycerin, alkoxylated fatty acids, esters of glycerin and polyglycerol esters and combinations thereof. The hydrotrope of the present invention provides opti- mum viscosity and composition stability compared to the current formulae in industry. Surprisingly, it has also been found that the hydrotrope of the present invention improves the cleaning performance of the detergent composition in hard water, increases the dissolution rate and increase the mildness of the detergent composition. SUMMARY OF THE INVENTION The present invention relates to a dishwashing detergent composition having from about 1 to about 90% of an anionic surfactant and further employing from about 1% to about 30% of a solvent hydrotrope selected from the group con- sisting of alkoxylated glycerides, alkoxylated glycerines, esters of alkoxylated glycerines, alkoxylated fatty acids, esters of glycerin, polyglycerol esters and combinations thereof. In a preferred embodiment, the anionic surfactant con- tains at least one sulfur group. The dishwashing detergent may also contain from about 1% to about 40% of a surfac- tant component selected from the group consisting of non- 10 15 20 25 30 35 40 45 50 55 60 65 2 ionic surfactants, amphoteric surfactants and combinations thereof. Known adjuvants and additives such as perfumes, fragrances, and the like may also be present at nominal levels with an aggregate of less than about 10% by weight of the composition. Water may comprise the balance. Unexpectedly, it has been found that dishwashing- detergents that incorporate the hydrotrope of the present invention exhibit optimum viscosity and formula stability, improved dispersability and improved cleansing perfor- mance in hard water compared to commonly used detergent compositions containing only alcohol or alcohol derivatives as the hydrotrope. It is noted that, unless otherwise stated, all percentages given in this specification and the appended claims refer to percentages by weight. It is also noted that the hardness values, as used in this specification and the appended claims, is intended to refer to hardness expressed as calcium carbonate. These and other objects, advantages, and features of the present invention will be better understood upon review of the following detailed description of the preferred embodi- ments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The liquid dishwashing detergent composition of the present invention includes an anionic surfactant and a sol- vent hydrotrope selected from the group consisting of alkoxylated glycerines, alkoxylated glycerides, esters of alkoxylated glycerin, esters of glycerin, alkoxylated fatty acids, polyglycerol esters and combinations thereof. Anionic surfactants useful in a detergent formulation of the present invention include but are not limited to those that are listed in McCutcheon’s Emulsifiers & Detergents, Annual 1992; and in US. Pat. No. 5,298,195 assigned to the same assignee of the present invention, both references are incorporated herein by reference. Anionic surfactants particularly useful in the present invention include those containing at least one sulfur group. Thus, for example, the anionic surfactant useful in the present invention include sulfated and sulfonated anionic surfactants. Useful sulfated anionic surfactants include but are not limited to primary and secondary alkyl sulfates, primary and secondary sulfates of ethoxylated alcohols, and sulfates of fatty esters. Useful sulfonated anionic surfactants include but are not limited to sulfonates of alkylbenzene, sulfonates of dodecyl benzene, sulfonates of tridecylbenzene, primary and secondary alkyl sulfonates, alpha olefin sulfonates, sulfonates of naphthalene and alkyl naphthalene, and sulfonates of petroleum. Other useful anionic surfactants containing a sulfur group include but are not limited to sarcosinates, sulfosuccinamates, sulfosucci- nates and taurates. In addition, anionic surfactants with a carboxyl group are also useful in the present invention. Anionic surfactants with a carboxyl group include salts of fatty acids, commonly referred to as soaps, and carboxylated alcohol ethoxylates, commonly referred to as carboxylates. Particular examples of these anionic surfactants include but are not limited to those that can be found in McCutcheon’s. The particularly preferred anionic surfactants of the present invention include ether sulfates. Ether sulfates include, for example, the alkyl ether sulfates such as poly- oxyethylene alkyl ether sulfates and tridecyl ether sulfates, alkyl ether sulfates derived from natural alcohol such as sodium lauryl alcohol polyglycol ether sulfates and fatty alcohol ether sulfates, alkyl ether sulfates derived from 5,998,355 3 synthetic alcohol, and ether sulfates derived from aliphatic carboxylic acids such as sodium lauryl ether sulfates, sodium myristyl ether sulfates, polyoxyethylene lauryl ether sulfates, triethanolamine lauryl ether sulfates, and ammo- nium lauryl ether sulfates. The amount of anionic surfactant present in a detergent composition in accordance to the present invention ranges from about 1% to about 90%, preferably from about 5% to about 70%, with from about 15% to about 50% being particularly preferred. The hydrotrope of the present invention includes alkoxy- lated glycerines such as ethoxylated glycerines and alkoxy- lated glycerides such as ethoxylated glycerides. Ethoxylated glycerines and ethoxylated glycerides are preferred because they are biodegradable. The ethoxylated glycerines useful in the present invention have the following general structure: (I) T HZC—O(— CHZCH—O—) [H R HZC—O(—CH2CH—O—)mH R HZC—O(—CHZCH—O—)nH «1” a :a a :a 3 wherein: m , n are each a number from 0 to about 20, with l+m+n=from about 2 to about 60, preferably from about 10 to about 45, and R represents H, CH3, or Csz- The ethoxylated glycerines of Formula (I) can be prepared according to conventional methods, for example, by the reaction of glycerine and ethylene oxide in the presence of an alkaline catalyst such as KOH or NaOH. Examples of the preparation of ethoxylated glycerine can be found in US. Pat. No. 5,425,891 to Pujol et al., which is incorporated herein by reference. The ethoxylated glycerides useful in the present invention are the ethoxylated mono- and diglycerides and can be prepared according to conventional methods, for example, by reaction of ethylene oxide with mono- or diglyceride fats. The ethoxylated glycerides useful in the present invention have the following general structure: (11) H2C—R1 HC—R2 R3 HZC—O— (CHZCH— O)—H wherein: R1 and R2 are each 0 R3 CnC—O— or —(CH2CH—O)I—H,R3=H,CH3, or C2H5> and “l” is a number from about 1 to about 60 and “n” is a number from about 6 to about 24. Examples of ethoxylated glycerides useful in the present invention include but are not necessarily limited to ethoxy- lated monoglycerides, and ethoxylated diglycerides. A par- ticularly preferred ethoxylated glyceride is an ethoxylated monoglyceride. The hydrotrope of the present invention further includes esters of alkoxylated glycerines. The esters of alkoxylated 10 15 20 25 30 35 40 45 50 55 60 65 4 glycerines useful in the present invention can be prepared according to conventional methods, for example, by alkoly- sis of an alkoxlyated glycerine by an acid chloride. Particu- lar examples of esters of alkoxylated glycerines useful in the present invention include but are not limited to those that can be found in McCutcheon’s. The hydrotrope of the present invention additionally includes alkoxylated fatty acids. The alkoxylated fatty acids useful in the present invention can be prepared according to conventional methods, for example, by reacting a fatty acid with ethylene oxide in the presence of an alkaline catalyst such as KOH or NaOH. Useful alkoxylated fatty acids of the present invention include but are not limited to polyethylene glycol esters of fatty acids, polyoxyethylene esters of fatty acids, carboxylic acid polyglycol esters, fatty acid polyglycol esters and polypropylene glycol esters of fatty acids. Particular examples of alkoxylated fatty acids include but are not limited to those that can be found in McCutcheon’s. The hydrotrope of the present invention further includes esters of glycerin. The esters of glycerin useful in the present invention can be prepared according to conventional meth- ods such as alkolysis of glycerin with an acid chloride. Particular examples of esters of glycerin useful in the present invention include but are not limited to those that can be found in McCutcheon’s. The hydrotrope of the present invention also includes polyglycerol esters. The esters of polyglycerol useful in the present invention can be prepared according to conventional methods. Polyglycerol can be prepared by dehydration of glycerin using alkaline catalysts such as sodium hydroxide. The polyglycerol is then further esterified with a fatty acid to form a polyglycerol ester. Particular examples of polyg- lycerol esters useful in the present invention include but are not limited to those that can be found in McCutcheon’s. The amount of solvent hydrotrope present in the detergent composition in accordance to the present invention ranges from about 1% to about 30%, preferably from about 2% to about 20%. More preferably, the solvent hydrotrope is present at about 3% to about 10%, with from about 4% to about 8% particularly preferred. The solvent hydrotrope in accordance to the present invention may contain combinations of the above-described components as well as individual compounds. The detergent composition of the present invention may also include other surfactants such as nonionic and ampho- teric surfactants. Nonionic surfactants useful in the present invention include but are not limited to alkanolamides, amine oxides, alkoxylated alcohols and phenols, block polymers, alkoxylated amines, alkyl polysaccharides, glucosamides, sugar esters and combinations thereof. Par- ticular examples of nonionic surfactants include but are not limited to those that can be found in McCutcheon’s and US. Pat. No. 5,298,195. Amphoteric surfactants include mono- and diacetates, betaines, glycinates, imidazolines and their derivatives, isethionates, mono- and diproprionates, hydroxy sultaines, and taurates. Particular examples of amphoteric surfactants include but are not limited to those that can be found in McCutcheon’s. The amount these surfactant components present in the detergent composition ranges from about 1% to about 40%, preferably from about 15% to about 40%. Moreover, the present invention may contain optional ingredients such as alkalinity sources, acidifying agents, pH buffering agents; and pH control agents. Examples of acidi- fying agents include but are not limited to citric acid, acetic acid, benzoic acid, phenol and palmitic acid. Examples of 5,998,355 5 pH control agents include but are not limited to alkali metal carbonates and bicarbonates, monoethanolamine, triethanolamine, tris hydroxy methylamine, ammonium hydroxide, alkaline metal earths, and alkali metal hydrox- 6 The dishwashing detergent in the following examples contain common composition (Composition A): COMPO- SITION A ides. The mono-, di-, and triethanolamines are preferred and 5 can be added up to a level of about 5%. COMPOSITIONA Builders may also be added, although they have limited — value in dishwashing compositions. Either inorganic or Component Weight % organic builders may be used alone or in combination with themselves. Examples of such builders include but are not 10 (53113131; iii; limited to alkali metal carbonates, phosphates, CAPAO 4:5 polyphosphates, and silicates. Citric Acid 09 Sequestrants can also be incorporated into the composi- tions. Examples of sequestrants include but are not limited to the alkali metal polycarboxylates, such as sodium and i5 potassium citrate, sodium and potassium tartrate, citric acid, sodium and potassium ethylenediaminetetraacetate EDTA , . . . triacetates, sodium and potassium nitrilotriacetates( (NTAg, A comparative detergent formulation (Formulation X) and mixtures thereof. Up to about 5% of sequestrants can be was prepared by adding the followmg composition 0f com- used. 20 mon hydrotropes (Composition B) to Composition A: In addition, the detergent compositions of the present invention can contain, if desired, other optional ingredients COMPOSITION B including any of the usual adjuvants, diluents, and additives — such as perfumes, enzymes, dyes, anti-tarnishing agents, Component Weight % antimicrobial agents, abrasives, hand softening agents such 25 as aloe vera gel, water soluble salts of alkaline earth metals PNrsribfiesilrfzgant C with 7 moles E0 3 5 such as magnesium sulfate, and the like, provided that they 11’ I do not detract from the advantageous properties of the compositions in accordance to the present invention. The compositions can contain up to about 10% of these 30 o tional in redients. . . . pIt is undgrstood that the amount of water comprising the The VISCOSHy 0f Formulation X’ as measured by ASTM balance of the detergent composition of the present inven- MéthOd number D1200’ #4 Ford Cup, IS 60 seconds centi- tion can be varied depending upon the desired concentration pOISe' of the final product. 35 The following examples are given to illustrate the com- positions of the invention. Example 1 EXAMPLES In the examples the abbreviations used have the following 40 meanings: . . . . Detergent formulations containing a hydrotrope in accor- dance to the present invention and Composition A were Abbreviation Description evaluated for formulation clarity, viscosity and dissolution CDEA Coconut diethanolamide 45 rate as compared to Formulation X. CAPAO Cocamidopropyl amine oxide SLES Sodium lauryl ethoxy sulfate Table 1 summarizes the results. TABLE 1 Weight Percent Formulation Viscosity3 Formulation Solvent/Hydrotrope Used1 Clarity2 (centipoise) Dissolution Rate4 1 PEG-4 Laurate 5 separated 2 PEG-4 Laurate 2.5 + 2.5 clear 70 & Propylene Glycol 3 PEG-8 Laurate 5 clear 67 > Formulation X 4 PEG-9 Laurate 5 clear 69 > Formulation X 5 Glycereth-7 Trioctanoate 5 separated 6 Glycereth-7 Trioctanoate + 2.5 + 2.5 clear 49 Propylene Glycol 7 Glycereth-26 Trioctanoate 5 clear 63 >> Formulation X 8 Glycereth-26 Trioctanoate 3 clear 65 >> Formulation X 9 Glycereth-26 Trioctanoate 1 clear 93 10 Glycereth-26 Trioctanoate + 1 + 1 clear 62 i Formulation X Hexylene Glycol 5,998,355 7 TABLE 1-continued Weight Percent Formulation Formulation Solvent/Hydrotroae Used1 Clarity2 11 Glycerol Tri(2-et1yl 5 separated hexanoate) 12 Glycerol Tri(2-et1yl 2.5 + 2.5 c ear hexanoate) + Propylene Glycol 13 PEG-18 Glycery 5 c ear Oleate/Laurate 14 Polyglyceryl-4 Isostearate 5 separated 15 Polyglyceryl-4 Isostearate + 2.5 + 2.5 c ear Propylene Glyco 16 Polyglyceryl-3 Oleate 5 separated 17 Polyglyceryl-3 Oleate + 2.5 + 2.5 c ear Propylene Glyco 18 PEG-3 Glyceryl Laurate 5 c ear 19 PEG-20 Glycery Laurate 5 c ear 20 PEG-7 Glyceryl Cocoate 5 c ear 21 PEG-7 Glyceryl Cocoate 3 c ear 22 PEG-7 Glyceryl Cocoate 1 c ear 23 Glycereth-26 3 c ear 24 Glycereth-26 1 c ear 25 Glycereth-26 + Propylene 1 + 1 c ear Glycol 1Amount of hydrotrope used, in weight percent. 2Formulation resulted in clear solution, or separated solution. 3Measured with ASTM D1200 4As compared with Formulation X Of the formulations tested, those containing the hydro- tropes ethoxylated glycerin, esters of ethoxylated glycerin, ethoxylated fatty acids and ethoxylated monoglycerides show acceptable formula stability and dispersability. Deter- gent formulations containing glycerin esters and polyglyc- erol esters show acceptable formula stability and dispers- ability when the hydrotropes ar...
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