US 3728265 A
Description (OCR text may contain errors)
3,728,265 HIGH-FOAMING LIQUID DETERGENT COMPOSITIONS John Anthony Celia, Lake Forest, and Thomas Oliver York, Chicago, Ill., and William Howard Schmrtt, Branford, Conn., assignors to Alberto-Culver Company, Melrose Park, Ill. No Drawing. Continuation-impart of abandoned appl cation Ser. No. 9,976, 1970. This application 6 1971 Ser. No.2 ,8 Dec 1 Int. Cl. Clld 17/00 US. Cl. 252-90 9 Claims ABSTRACT OF THE DISCLOSURE High-foaming liquid detergent compositions, adapted to be packaged in conventional non-pressunzed contamers as, for example, glass bottles and metal or plastiocontainers, comprising substantially anhydrous compositions containing a compressible water-insoluble gas, particularly in the form of an aliphatic hydrocarbon or halogenated hydrocarbon, dissolved in an organic solvent, such as propylene glycol, which organic solvent is also watersoluble, and certain other agents to complete the l1qu1d detergent compositions for their intended uses, such as hair shampoos. When said compositions are wetted or admixed with Water, said dissolved compressible gas is displaced from said organic solvent and is released to form extremely profuse or large amounts of foams or suds.
This application is a continuation-in-part of application Ser. No. 9,976, filed Feb. 9, 1970, now abandoned.
This invention relates to novel high-foaming liquid detergent compositions which, upon contact or admlxing with Water, form extraordinary amounts of foams or suds. They contain, as one ingredient thereof, a compressible water-insoluble gas but, nevertheless, they can be packaged in conventional non-pressurized containers such as glass bottles or metal or plastic containers.
The liquid detergent compositions of this invention are substantially anhydrous or essentially non-aqueous compositions which, when brought into contact with Water, as in connection with the shampooing of hair, evolve a gas which, in turn, in combination with the detergent formulation, causes a mechanical action leading to exceedingly large amounts of foams or suds.
The liquid detergent compositions of the present invention are radically different from those of previously known and marketed types and operate on an entirely unrelated principle of gas fogmation and evolution. In broad terms, the liquid detergent compositions of this invention comprise (a) a substantially water-insoluble compressible gas, (b) a Water-soluble solvent for said compressible gas which lowers the vapor pressure of the resultant solution to a point at which said solvent solution of said compressible gas can be maintained at ambient temperatures in conventional non-pressurized containers, (c) a watersoluble anionic detergent, particularly a sulfated or sulfonated synthetic detergent, and (d) an alkanolamide, with or without certain supplemental ingredients. While the proportions of the aforesaid ingredients are variable, they will usually be utilized in approximate proportions, in terms of percent 'by Weight of the finished liquid de tergent compositions, as follows in relation of the (a) to (d), inclusive, ingredients referred to above:
(a) 10 to 25 (b) 10 to 25 (c) 30 to 45 (d) to 25 3,728,265 Patented Apr. 17, 1973 The liquid detergent compositions of the present invention, although including a solution of a water-insoluble compressible gas in a solvent, are handled and packaged as ordinary uncompressed liquids at normal storage temperatures, as pointed out above, and may simply be poured from the containers thereof into contact with water. They are particularly useful as hair shampoos but they are also useful for other detergent purposes as, for instance, rug shampoos.
Any volatile organic material which exists as a gas at use temperature, particularly at body temperatures (and ambient or atmospheric pressure), and which exists as a liquid at the same temperatures under superatmospheric pressures, and is soluble in the organic chemical compound (or mixtures thereof) utilized as a solvent, and is substantially insoluble in water, can be used as the gasproducing agent. Especially suitable are the C -C aliphatic hydrocarbons, namely, liquefied propane, n-butane, isobutane, isobutylene, n-pentane, isopentane, n-hexane, and hexene-Z; and halogenated aliphatic hydrocarbons which contain from 1 to 2 carbon atoms and include, by Way of example, vinyl chloride, ethyl chloride, chloroform, trichloroethylene, methylene chloride, dichlorodifluoromethane, monochlorodifiuoromethane, dichlorotetrafluoroethane, trichlorofluoromethane, trichlorofiuoroethane, difiuoroethane, difiuoromonochloroethane, trichlorotrilluoroeth'ane, and mixtures of 'two or more thereof, most desirably the saturated hydrocarbons and halogenated saturated aliphatic hydrocarbons. Especially satisfactory are dichlorotetrafluoroethane, trichlorofluoromethane and isopentane but, because of flammability considerations, the last-mentioned is less desirable. The boiling points of said aliphatic hydrocarbons and halogenated aliphatic hydrocarbons should fall within the range of about -30 to about 60 C. at atmospheric pressure, preferably about 3 C. to about 37 C. The proportions thereof in the liquid detergent compositions of the present invention will, in general, range from about 5 to about 25%, by weight, preferably about 10 to about 15 to 20%. The vapor pressure of the finished liquid detergent compositions is, in general, in the range of from about 0 to 10 p.s.i.g. at 25 C. and not greater than about 15 p.s.i.g. at 50 C.
The organic solvent or solvents for the compressed gas are limited only by a solubility for the compressed gas, the resultant vapor pressure of the solution, and the fact that the compositions comprise high-foaming liquid detergent compositions. Said organic solvent must be watersoluble, may be normally liquid, semi-solid or solid but will usually be a liquid at room temperature. Among such organic solvents are, for instance, propylene glycol, monobutyl ether of diethylene glycol (butyl Cellosolve), and polyethylene glycol 400. Still others which can be used are water-soluble polyethylene glycols such as those having molecular Weights of about 200, 300, 600, 1000 and higher. Various aliphatic polyhydric alcohols such as glycerol, monoalkylene and polyoxyalkylene glycols in which the alkylene groups contain from 2 to 4 carbon atoms, such as ethylene glycol, 1,3-butylene glycol, hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and higher polyoxyethylene glycols can also be used. Still other organic solvents which can be used are, for instance, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, tort-butyl alcohol, dioxane, dimethyl ether, Cellosolve acetate, acetone, methyl ethyl ketone, methyl acetate and acetonitrile. Particularly advantageous are propylene glycol, butyl Cellosolve and polyethylene glycol 400. Others of the ingredients forming a part of the liquid detergent compositions of the present invention, such as the water-soluble anionic detergents and the non ionic detergents, may contribute to solubilizing the waterinsoluble compressible gas.
The water-soluble anionic detergent can be selected from among many. Particularly useful are water-soluble salts of alkylaryl sulfonic acids, such as alkanolamine salts, preferably diethanolamine or triethanolamine or isopropanolamine salts of C C linear alkylbenzene sulfonic acids such as the aforesaid salts of linear dodecylbenzene sulfonic acid, tridecylbenzene sulfonic acid and pentadecylbenzene sulfonic acid. Others of such anionic synthetic detergents are, most desirably, water-soluble salts of sulfated and sulfonated detergents having an aliphatic chain of 8 to 22. carbon atoms, or water-soluble salts of organic sulfonic acids, alkyl sulfuric acids and sulfuric acid esters of aliphatic polyhydric alcohols incompletely esterified with a fatty acid of higher molecular weight, as shown, for instance, in US. Pats. Nos. 2,383,737 and Re. No. 23,840, illustrative examples of which are the sodium, diethanolamine and triethanolamine salts of the sulfuric acid ester of lauryl or dodecyl alcohol and of the sulfuric acid ester of lauric acid monoglyceride.
The alkanolamides which are employed are well known and are shown in many patents as, for instance, in the aforementioned U.S. Pats. Nos. 2,383,737 and Re. No. 23,840. Particularly desirable are diethanolamides of lauric acid or myristic acid or coconut oil mixed fatty acids, fractions rich in lauric and/or myristic acid, for instance a fraction containing about 65% lauric acid and about 35% myristic acid, in which the mol ratio of the diethanolamine to lauric acid or myristic acid or coconut oil mixed fatty acids or said fractions is about 1:1. Others of the alkanolamides which are particularly satisfactory for use in the production of the liquid detergent compositions of the present invention are the oleic acid amide of monoisopropanolamine and the C -C fatty acid amides of diethanolamine in which the mole ratio of the diethanolamine to said fatty acids is about 2:1. Further examples of alkanolamines whose alkanolamides of C -C fatty acids can be used are n-propanolamine, glycerol monoand di-amines and aminoethylethanolamine; and such hydroxyalkyl alkylene polyamines as hydroxyethyl ethylenediamine and hydroxyethyl diethylenetriamine. The alkanolamides must be essentially soluble in the mixture comprising the remainder of the ingredients of the liquid detergent compositions of the present invention.
Nonionic surfactants are optionally used in the liquid detergent compositions of this invention and they comprise water-soluble polyoxyethylene adducts or condensates of (i) long chain (C -C preferably C -C aliphatic alcohols, which may be fatty alcohols or branched alcohols such as the oxo alcohols, or (ii) alkyl phenols in which there may be 1 or 2 alkyl groups and in which said alkyl groups contain from to 12 carbon atoms, there being from about 4 or 5 mols up to about 30 mols, preferably from about 6 to mols, of ethylene oxide per mol of the long chain aliphatic alcohol or alkyl phenol in said adducts or condensates. Illustrative examples of said nonionic surfactants are the aforesaid ethylene oxide adducts of such fatty alcohols as octyl alcohol, nonyl alco hol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, oleyl alcohol and octadecyl alcohol; the aforesaid ethylene oxide adducts of such aliphatic branched chain alcohols as iso-octyl alcohol, tridecyl oxo alcohol and pentadecyl oxo alcohol; and the aforesaid ethylene oxide adducts of such (T -C monoand di-alkyl phenols as amyl phenol, diamyl phenol, octyl phenol, dioctyl phenol, nonyl phenol, dinonyl phenol, decyl phenol, didecyl phenol, dodecylphenol and didodecyl phenol. Where employed, they are generally utilized in amounts up to about 30% by weight of the finished liquid detergent compositions.
Still others of such water-soluble nonionic surfactants are the polyoxyethylene adducts or condensates with polyoxypropylene glycols of 1200 molecular weight or higher. They are sold under the designation Pluronics and their preparation is shown, for instance, in US. Pats. Nos. 2,674,619 and 2,677,700. Various of the aforesaid and other similar nonionic surfactants are disclosed in many patents among which may be mentioned, by way of example, US. Pats. Nos. 2,855,367 and 2,867,585.
It will be understood, in the case of each of the ingredients described above, that compatible mixtures of two or more of each of them can be used, if desired, and that commercial sources of said ingredients are very satisfactory in the production of the liquid detergent compositions of the present invention.
In those instances in which the substantially waterinsoluble compressible gas contains halogen, as in the case, for instance, of trichlorofluoromethane, precipitates on occasion form on standing of the liquid detergent compositions over a period of time. While such precipitates do not have any significant adverse effect on the foaming properties of the liquid detergent compositions, it is distinctly preferred to avoid their formation for reasons of esthetics in packaging and otherwise. It has been found that good inhibition of such formation of precipitates is effected by the inclusion in the compositions of small proportions of water-soluble organic acids such as malic acid, citric acid, tartaric acid, gluconic acid, and the like. Generally, about 1% of such acids, based upon the weight of the finished liquid detergent composition, is sufficient, but the quantity may be somewhat less or somewhat more and it will ordinarily be unnecessary to exceed amounts of the order of about 2%.
It will also be understood that various supplemental ingredients can be added to the liquid detergent compositions of the present invention such as perfumes, dyes, germicidal agents and the like which, when employed, will usually be added in small proportions.
The following examples are illustrative of liquid detergent compositions made in accordance with this invention. It will be understood that numerous other liquid detergent compositions can readily be made in the light of the guiding principles and teachings of the present invention disclosed above. The examples given are, therefore, by way of illustration and not by way of limitation. All parts listed are in terms of weight.
EXAMPLE 1 Dodecylbenzene sulfonate (triethanolamine salt) 34.5 Laurie acid diethanolamide (mol ratio of diethanolamine to lauric acid is 1:1) 8.62 Octylphenoxypolyethoxyethanol (Polytergent) 26.88 Propylene glycol 9 Malic acid 1 Trichlorofluoromethane 20 EXAMPLE 2 Lauryl sodium sulfate 27 Cg-Clo fatty acid diethanolamide (mol ratio of diethanolamine to fatty acid is 2:1) 6.75 Ethoxylated Gig-C1 fatty alcohol (10 mol adduct) 20.25 Polyethyleneglycol 400 25 Isopentane 19 EXAMPLE 3 Diethanolamine salt of tridecyl benzene sulfonic acid 30 Diethyleneglycol monobutyl ether l8 Citric acid 1 Dichlorotetrafluoroethane 18 EXAMPLE 4 Dodecylbenzene sulfonate (triethanolamine salt) 35 Laurie diethanolamide (1:1) Octylphenoxypolyethoxyethanol (Polytergent) 28 Polyethyleneglycol 400 11 Gluconic acid 1 Trichlorofluoromethane 15 EXAMPLE 5 Dodeeylbenzene sulfonate (triethanolamine salt) 39.3 Laurie acid diethanolamide (mol ratio of diethanolamine to lauric acid is 1:1) 9.8 Laurie acid diethanolamide (mol ratio of diethanolamine to lauric acid is 2:1) 9.8 Propylene glycol Trichlorofluoromethane 20 Color and perfume as desired.
The ingredients may be mixed in any suitable order. Thus, for instance, in Example 1, the dodecylbenzene sulfonate (triethanolamine salt), the lauric acid diethanolamide and the octylphenoxypolyethoxyethanol initially may be mixed together, with slight heating, if desirable to aid in obtaining homogeneity, the propylene glycol containing previously dissolved malic acid is mixed in, the mixture is cooled to about 15 C. or below, and then the trichlorofluoromethane is incorporated. Alternatively, the trichlorofluoromethane can be dissolved in a mixture of the propylene glycol and the octylphenoxyethoxyethanol and then each of the remaining ingredients is blended into the mixture. tWhere perfumes or the like are added, it is desirable to add them in at or near the end of the mixing procedure.
We are aware that it has heretofore been disclosed to prepare foam-producing liquid detergent compositions, which are adapted to be packaged in non-pressure containers, such as collapsible or squeezable metallic tubes, plastic containers, and the like and which, when spread out in a thin layer, foam spontaneously. Such compositions, which are disclosed in US. Pat. No. 2,995,521, comprise a mixture of (a) at least one substance of the class of C to C saturated aliphatic hydrocarbons and various Freons, which may be jellified with aluminum octoate, and (b) a mixture of a plurality of ingredients including substantial proportions of water, the water constituting, in certain of the formulations, in ex cess of 60% of the finished composition (see, for instance, Example 11 of said patent). The gas is suspended in a metastable state in the examples as described in the above patent, and the release of the gas is effected by the spreading out of the compositions in a thin layer. The liquid detergent compositions of our invention are sharply distinguishable therefrom in a number of particulars in that, for instance, our liquid detergent compositions are essentially non-aqueous or anhydrous or substantially anhydrous, being devoid of water or containing at the most not more than 3 or 4% of water and, better still, less than about 1% water. The compositions are radically different from anything disclosed or suggested in said patent, and the gas-producing agent or agents are in solution in an organic solvent and are displaced or released from solution when contacted with water and issue as a gas at the ambient temperatures conventionally encountered in the environment of their use.
We are aware that it has been suggested to prepare foam-producing compositions for dispensing from aerosol containers, as disclosed, for instance, in US. Pat. Nos. 3,055,834 and 3,131,153, the compositions of said latter patent containing (a) an alcohol or dialkyl ketone, (b) glycerol or an alkylene glycol such as polyoxyethylene glycol 200, 400, 600, etc., (c) a surface active agent, and (d) a propellant in the form of a liquefied normally gaseous aliphatic hydrocarbon or halogenated aliphatic hydrocarbon such as butanes or pentanes or dichlorodifluoromethane or dichlorotetrafluoroethane. Such foamproducing compositions are suggested for use as preelectrie shave lotions, after-shave lotions, astringents, colognes, sun tan lotion, hair-coloring tints, hair dressings, paint removers, etc. The said compositions are dispensed by means of conventional aerosol propellants and contained in conventional aerosol packaging. Again, our liquid detergent compositions and their manner of use and the basis upon which foaming is achieved are sharply distinguishable from the disclosures and teachings in said patents in that a requirement of the latter is the dispensing from aerosol or pressure containers. Our liquid detergent compositions, in sharp contrast, not only are packaged in ordinary or conventional non-pressurized containers, such as glass, metal or plastic containers as, for instance, rigid non-pressure containers, but, indeed, if simply placed as such, and Without more, in an aerosol container, would not be dispensable therefrom. Furthermore, they differ radically in composition from anything disclosed or suggested in said patents.
What is claimed is:
1. A high-foaming essentially non-aqueous liquid detergent composition packaged in a non-pressurized container, the vapor pressure of said composition being in the range of from 0 to 10 p.s.i.g. at 25 C. and not greater than 15 p.s.i.g. at 50 =C., and consisting essentially of the following ingredients in approximately the following proportions in percentages by weight of said composition:
Percent (a) A substantially water-insoluble compressible gas 10-25 (h) A water-soluble organic solvent for said compressible gas which lowers the vapor pressure of the resultant solution to permit packaging of the liquid detergent composition in non-pressurized containers and maintaining said composition at ambient temperatures 10-25 (c) A water-soluble anionic detergent 30-45 ((1) A C -C fatty acid alkanolamide 5-25 said composition, when admixed with water, producing a profuse foam.
2. A composition according to claim 1 in which the (a) ingredient comprises a member selected from the group of trichlorofiuoromethane and dichlorotetrafiuoroethane.
3. A composition according to claim 2 in which the (b) ingredient comprises a member selected from the group of propylene glycol, polyethylene glycol 400 and the monobutyl ether of diethylene glycol.
4. A composition according to claim 3 in which the (c) ingredient comprises a member selected from the group of diethanolamine and triethanolamine salts of dodecylbenzene sulfonic scid, and sodium, diethanolamine and triethanolamine salts of the sulfuric acid ester of dodecyl alcohol.
5. A composition according to claim 4 in which the (d) ingredient comprises a member of the group of lauric acid and myristic acid diethanolamides in which the mol ratio of the diethanolamine to said acid is in the range of about 1:1 to 2:1, and (I -C fatty acid amides of diethanolamine in which the mol ratio of the diethanolamine to said fatty acid is about 2:1.
6. A composition according to claim 5 including up to 30% by weight of a member of the group of 4 to 30 mol ethylene oxide adducts of (i) long chain C -C aliphatic alcohols, (ii) Cg-Czg monoand di-alkyl phenols, and (iii) polyoxypropylene glycols.
7. A composition according to claim 1 in which the following ingredients are present in approximately the following proportions:
(a) Trichlorofluoromethane 20 (b) Propylene glycol 20 (c) Diethanolamine or triethanolarnine salt of dodecylbenzene sulfonic acid 40 (d) Lauric acid diethanolamide (mol ratio of diethanolamine to lauric acid about 1:1) 10 Laurie acid diethanolamide (mol ratio of diethanolamine to lauric acid about 2:1) l0 8. A composition according to claim 1 including up to about 2% of at least one organic acid selected from the group consisting of malic acid, citric acid, tartaric acid and gluconic acid.
9. A composition according to claim 6 including up to about 2% of at least one organic acid selected from the group consisting of malic acid, citric acid, tartaric acid and gluconic acid.
References Cited UNITED STATES PATENTS 3,541,581 11/1970 Monson 252-90 2,995,521 8/1961 Bluard 252305 3,055,834 9/1962 Charle 252-90 3,131,153 4/1964 Klausner 252-305 FOREIGN PATENTS 838,913 6/1960 Great Britain 25290 LEON D. ROSDOL, Primary Examiner W. E. SCHULZ, Assistant Examiner US. Cl. X.R.
252-307, DIG 13; 424--70