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Publication numberUS3055836 A
Publication typeGrant
Publication dateSep 25, 1962
Filing dateDec 24, 1957
Priority dateDec 24, 1957
Publication numberUS 3055836 A, US 3055836A, US-A-3055836, US3055836 A, US3055836A
InventorsJoseph N Masci, Normand A Poirier
Original AssigneeJohnson & Johnson
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Detergent composition
US 3055836 A
Images(6)
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Description  (OCR text may contain errors)

res Fer 3,055,836 Patented Sept. 25, 1952 This invention relates to the art of detergent compositions and, more particularly, to those which are mild enough to be useful in contact with human skin.

Most detergents have intrinsic irritation properties, and these materials irritate sensitive membranes even when neutralized.

A shampoo detergent, for example, should possess good foaming action, detergency without excessive degreasing of the skin, absence of irritation to delicate membranes and skin, good rinsing qualities, and absence of acidity or alkalinity.

Although various preparations on the market today possess many of the above desired properties, very few neutral compositions which are otherwise desirable are good foamers,. and they are therefore undersirable as an ingredient in shampoo formulations.

A further characteristic of a desirable hair shampoo is good foaming action in the presence of grease and oils that arise naturally or from numerous hair preparations commercially available.

We have discovered that shampoos can be formulated in accordance with the teaching of this invention which possess extremely good foaming properties as well as the other properties indicated above, and with very low tendency to cause stinging when in contact with human skin.

It is therefore an object of this invention to produce new and improved detergent compositions.

It is another object to produce detergents possessing extremely good foaming properties, low stinging and the other desirable properties of detergents.

It is a more specific object to produce new and improved shampoos embodying my new detergent compositions.

It is a still further object to produce hair shampoos which have good foaming action in the presence of grease.

As a consequence of the remarkable properties of some of these compositions with regard to low sting and low incidence of irritation to sensitive tissues, such compositions may serve as wound detergents, skin cleansers, douches, toilet bars and the like.

It is likewise true that use of such detergent compositions where low eye stingis immaterial leads to a broad scope of the compositions herein disclosed.

For example, those nonionic detergents of a given class (sub-group (b) below) show maximum detergency where the number of units of ethylene oxide is about /3 the number of carbon atoms in the hydrophobic base. These facts are well known in the art where the hydrophobic base is a fatty acid (cf. A. T. Ballun et al., J. Am. Oil Chemists Soc., 31, 20 1954), a fatty alcohol (cf. J. V. Karabinos et al., I. Am. Oil Chemists Soc., 31, 419, 1954), or a mercaptan (cf. I. L. Eaton et al., Soap and Chem. Spec. 33, 49 (1957),

Accordingly, nonionic surfactans suitable for use in the broader phase of this invention are water soluble polyoxyethylenated derivatives of a hydrophobic base, said derivatives being members of the group consisting of:

(a) 9-18 carbon atom fatty acid monoesters of aliphatic polyhydric alcohols, which polyhydric alcohols contain at least 3 hydroxyls, reacted with at least 10 moles of ethylene oxide,

(b) A member of the group consisting of the reaction products of 9-18 carbon atom alcohols, acids, and mercaptans with at least as many ethylene oxide units as the number of carbon atoms in the hydrophobic base, and

(c) A member of the group consisting of the reaction products of 12-24 carbon atom alkyl phenols and alkyl cyclohexanols with at least as many ethylene oxide units as the number of carbon atoms in the hydrophobic base.

Unfortunately, nonionic surfactants having the lower ethylene oxide contents (i.e., maximum detergency range as discussed above) are in most cases highly irritating to the eyes, and are therefore unsuitable for use as shampoos in formulations according to the teaching of this invention. However, where eye irritation is unimportant, useful detergents are obtained by formulation of these particular nonionic surfactants with amphoteric-anionic surfactant combinations herein disclosed, especially where a high foaming, neutral cleaning composition is desired.

Although the products of this invention are all high foaming compositions exhibiting foam synergism, and excellent foam and detergency even in the presence of grease, there is disclosed herein a rigid test to distinguish between those compositions which serve better as general purpose detergents and those which make excellent shampoos and allied pharmaceutical preparations because of their mildness and non-irritating qualities.

This test, which is a modification of a test disclosed in the literature (J. H. Draize et al., Toilet Goods Assoc. #17, May 1952, #1, Proc. Sci. Sect), and constitutes a more exacting test before such a shampoo can be classified as mild and especially safe for use on young children, is as follows:

A 0.1 ml. sample of the neutral composition under test is dropped into one eye of each of three rabbits. A 0.1 ml. sample of a suitable control is dropped into the other eye of each of the same three rabbits. Daily administration of the same quantity of each of the samples is continued for 5 consecutive days. Observations are recorded after one hour, 24 hours, 72 hours and 7 days. The extremes of the results either show substantially no change or only a slight irritation (foreign body effect) in the appearance of the rabbits eyes, or severe irritation or complete corneal opacity, as the case may be.

Examples 1, 6, 9 and 10 were tested by this procedure. Indeed, the total concentration of surfactants in each case was 25%, but the results showed that each composition is in the low irritation extreme of the test.

The impact of these surprising results becomes more apparent when recourse to the prior art (e.g., Relation of Surface Active Properties to Irritation of the Rabbit Eye, L. W. Hazleton, Proc. Sci. Sect, The Toilet Goods Assoc., pp. 5-9, No. 17, May 1952) reveals the damage to rabbit eyes caused by an anionic surfactant alone. Furthermore, we have found that representative anionic surface active agents, one of which is used in preparing Example 6, become severe irritants when tested in rabbits eyes by the method described above, even at lower concentrations (5-6.2%

We have found further a distinguishing characteristic separating those detergent compositions which make excellent shampoos from those general purpose types in that those nonionic surface active agents of the classes cited above, but having a cloud point of at least C. (when determined at 2% concentration in distilled water), are found to be the most suitable nonionic surfactants to be used in our novel compositions as mild, non-irritating shampoos.

In order that such a cloud point he observed with the given classes of nonionic surfactants, it is required that 3 a relatively high ethylene oxide to hydrophobic base ratio (higher than the requirements for maximum detergency) be present, resulting in an over-all effect in our novel compositions of increased mildness while retaining synergistic foaming action, excellent detergency, and high foaming power in the presence of grease.

Examples 10, 16, 17 and 18, where the nonionic is t-dodecyl mercaptan reacted with 30, 9-10, 15 and 20 moles of ethylene oxide, respectively, illustrate the requirements for preferred, mild, non-irritating shampoo compositions where a graded series of ethylene oxide content in a particular hydrophobic base is used.

Only Example 10, where t-dodecyl mercaptan is reacted with about 30 moles of ethylene oxide, satisfactorily passes the rabbit eye test described above, and is therefore the most suitable for use as a shampoo.

Of special interest is the fact that Examples 10, 16, 17 and 18 all demonstrate detergent compositions of nearly equivalent performance with respect to foam synergism and high foam in the presence of grease, whereas only one of these compositions (Example satisfies the requirements of one of the preferred embodiments of this invention, namely a mild, non-irritating shampoo.

Accordingly, this invention not only teaches a method of making synergistic high foaming detergent compositions, but it also describes the requirements for making safe, mild, non-irritating shampoos, wherein the nonionic surfactant component must have an ethylene oxide content high enough to cause its cloud point to be safely above 100 C. at 2% concentration in distilled water. This observation is readily apparent from the cloud points observed with the nonionics just described.

Moles of Ethylene Oxide Reacted Clogd Point Example with one mole of (unt-dodecyl mercorrected) eaptan Consequently, with this particular mercaptan hydrophobic base, the ethylene oxide content of polyoxyethylenated t-dodecyl mercaptan must lie above 20 units for the nonionic component to be satisfactory in a mild shampoo composition, since 30 units is satisfactory and 20 units gives opacity in the rabbit eye.

Accordingly, nonionic surfactants suitable for use in the shampoos of this invention are water soluble polyoxyethylenated derivatives of a hydrophobic base, said derivatives being members of the group consisting of:

With the above and other objects in view, which will be apparent as the description proceeds, we have set forth our invention herein, and have illustrated it in the following examples which are set forth by way of illustration and not as a limitation. Parts are by Weight unless indicated otherwise.

EXAMPLE 1 52.1 parts (0.2 mole) of N-lauroyl-N-(2-hydroxyethyl) ethylenediamine are dispersed in 180 parts of warm Water (70-80 C.). Hydrochloric acid is added to give pH 8.5, at which point the aqueous slurry becomes less viscous. 77 parts of aqueous solution containing 31 parts of sodium chloracetate is added with stirring over 21 period of 2 hours, While maintaining the temperature at 70 C. 46 parts of 25% sodium hydroxide solution is added over a period of 1 hour and the mixture stirred an additional 3 hours at 70 C.

The resulting amphoteric product, weighing 358 parts, is a sparkling clear solution of pH 9. This aqueous solution contains 56.31 parts of N-lauroyl-N-sodium carboxymethyl-N-(Z-hydroxyethyl) ethylenediamine:

and 10.38 parts of unreacted N-lauroyl-N-(2-hydroxyethyl) ethylenediamine:

H O Hz;-ii1iT-0H2oH21 I oH,0H2oH 6.5 parts of the above solution (containing .0036 mole of amino group) is mixed with 3.2 parts of an aqueous solution containing 1.6 parts (.0036 mole) of tridecyloxydiethyleneoxyethyl sulfate sodium salt,

The latter is purified prior to use by extraction with petroleum ether in the presence of an equal weight of isopropanol to remove unsulfated alcohols. The mixture is stirred and heated on a steam bath for 30 minutes. The resulting solution of the amphoteric-anionic combination weighed 9.3 parts, had a pH of 8.7 and contained approximately 31.8% of the sulfate ester salts of the above amphoteric and aminoamide structures.

1.38 parts of this solution, containing 0.438 part surface active materials, is mixed with 0.56 part of the reaction product of 1 mole of sorbitan monolaurate and 20 moles of ethylene oxide. The solution is neutralized to pH 7 with hydrochloric acid. The polyoxyethylene derivative of sorbitan monolaurate has a cloud point above C. at 2% concentration in distilled water.

The above solution was found to give excellent lather when used as a shampoo in hard or distilled water or in the presence of grease.

EXAMPLE 2 The procedure of Example 1 is repeated, except that 4 parts by weight of the active amphoteric surface active solution is mixed with 1 part by weight of the reaction product of 1 mole of sorbitan monolaurate and 20 moles of ethylene oxide. The resulting solution, neutralized to pH 7 with hydrochloric acid, gives copious foam when used as a shampoo in hard or distilled water or in the presence of grease.

EXAMPLE 3 The procedure of Example 1 is repeated, except that 5.66 parts by weight of the active amphoteric surface active solution is mixed with 9.38 parts by Weight of the reaction product of 1 mole of sorbitan monolaurate and 20 moles of ethylene oxide. The resulting solution, neutralized to pH 7 with hydrochloric acid, is an unusually good foaming and cleansing composition when used as a shampoo in hard water, distilled water, or in the presence of grease.

EXAMPLE 4 1410 parts (0.8 mole of amino group) of an amphoteric surface active solution, prepared by the procedure of Example 1, is mixed with 320 parts of an aqueous solution containing 86.8 parts (0.2 mole) of tridecyloxydiethyleneoxyethyl sulfate sodium salt by brief warming on the steam bath with mild agitation. The resulting product weighed 1730 parts and contained about 21.7% surface active materials. 92.15 parts of this solution, containing 20 parts of surface active materials, is mixed with 7.5 parts of the reaction product of 1 mole of sorbitan monolaurate and 20 moles of ethylene oxide. The resulting solution, neutralized to pH 7 with hydrochloric acid, was found to have good detergent properties and good foaming action when used as a shampoo in the presence of distilled water, hard water, or grease.

EXAMPLE 5 Example 4 is repeated, except that 25.91 parts of the solution, containing 5.63 parts of the amphoteric-anionic surface active materials, is mixed with 9.38 parts of the reaction product of 1 mole of sorbitan monolaurate and 20 moles of ethylene oxide. The product was similar in performance to that of Example 4.

EXAMPLE 6 493 parts (0.276 mole of amino group) of an ampheteric surface active solution, prepared by the procedure of Example 1, is mixed with 437 parts of an aqueous solution containing 129.5 parts (0.276 mole) of sodium dodecyloxytriethyleneoxyethyl sulfate,

and heated in an open vessel with stirring on the steam bath for one hour. The product weighed 878 parts and consisted of approximately 25.5% surface active materials. 43.14 parts of this solution, containing 11 parts of surface active material, was mixed with 14 parts of the reaction product of 1 mole of sorbitan monolaurate and 20 moles of ethylene oxide. The product, neutralized to pH 7 with hydrochloric acid, was found to have excellent detergent properties and strong foaming action when used as a shampoo in the presence of hard water, distilled Water, or grease.

EXAMPLE 7 159' parts (0.089 mole of amino group) of the amphoteric surface active solution used in Example 6 is agitated at room temperature with 198.5 parts of an aqueous solution containing 50.4 parts (0.089 mole) of sodium tridecyloxypentaethyleneoxyethyl sulfate,

The product weighed 357 parts and contained approximately 22.6% surface active materials. 48.67 parts of this solution was mixed with 14 parts of the reaction product of 1 mole of sorbitan monolaurate and 20 moles of ethylene oxide. The product, neutralized to pH 7 with hydrochloric acid, was similar in performance to that of Example 6.

EXAMPLE 8 Example 7 was repeated, except that 53.1 parts of solution containin the 22.6% surface active materials was mixed with 6 parts of the reaction product of 1 mole of sorbitan monolaurate and 20 moles of ethylene oxide. The product, neutralized to pH 7 with hydrochloric acid, was better in performance than that of Example 7.

EXAMPLE 9 Example 1 was repeated by mixing 893 parts (0.5 mole of amino group) of the amphoteric surface active solution with 800 parts of an aqueous solution containing 217 parts (0.5 mole) of sodium tridecyloxydiethyleneoxyethyl sulfate. The product weighed 1693 parts and contained approximately 22.9% surface active materials. 48.03 parts of this solution was mixed with 14 parts of the reaction product of nonylphenol and 30 moles of ethylene oxide. The polyoxyethylene derivative of nonylphenol has a cloud point above 100 C. at 2% concentration in distilled water.

The solution was neutralized to pH 7 with hydrochloric acid and made up to 100 parts with distilled water. The final solution was a sparkling, clear, amber-colored liq- 6 old, which gave copious foam when used as a shampoo, and foamed especially well in the presence of grease.

EXAMPLE 10 Example 1 was repeated except that 17.29 parts of the amphoteric anionic combination was mixed with 7.00 parts of the reaction product of t-dodecylmercaptan and 29.8 moles of ethylene oxide. The product was neutralized to pH 7 with hydrochloric acid and made up to 50 parts with distilled water. The solution was found :to have excellent detergent properties and exceptionally strong foaming action when used as a shampoo in the presence of hard water, distilled water, or grease.

EXAMPLE 1 1 100.1 parts (containing 0.0508 mole of amino group) of a surface active amphoteric solution containing N- myristoyl-N-(2-hydroxyethyl) ethylenediamine and sodium chloroacetate is mixed with 81.3 parts of an aqueous solution containing 22.0 parts (0.0508 mole) of sodium tridecyloxydiethyleneoxyethyl sulfate. The mixture is warmed on the steam bath with stirring for ten minutes to give an amber-colored, homogeneous liquid Weighting 180.0 parts and containing about 22.8% surface active materials.

24.12 parts of this solution, containing 5.5 parts surface active materials, is mixed with 7 parts of the reaction product of sorbitan monolaurate and 20 moles of ethylene oxide. The solution is neutralized to pH 7 with hydrochloric acid and made up to 50 parts with water. The solution showed good foaming action and detergency when used as a shampoo in the presence of hard or distilled water or in the presence of grease.

EXAMPLE 12 200.0 parts (0.1203 mole of amino group) of an amphoteric surface active solution containing sodium N caproyl-N-carboxymethyl-N-(2-hydroxyethyl) ethylenediamine (prepared by the procedure of Example 1 from N-caproyl-N'-(Z-hydroxyethyl) ethylenediamine and sodium chloracetate) is mixed with 192.7 parts containing 5.23 parts (0.1203 mole) of sodium tridecyl oxydiethyleneoxyethyl sulfate by vigorous shaking at room temperature. The clear amber-colored product weighed 392.7 parts and contained about 23.0% surface active materials. 47.83 parts of the above solution, containing 11 parts of amphoteric surface active material, is mixed with 14 parts of the reaction product of sorbitan monolaurate and 20 moles of ethylene oxide. The re sulting solution is neutralized to pH 7 with hydrochloric acid, and made up to parts with distilled water. The above solution was found to give excellent lather when used as a shampoo in hard or distilled water or in the presence of grease.

Although the above examples are limited to ampholytes in which the alkyl radical is undecyl (C H nonyl (C d-I and tridecyl (C H it will be obvious that other aliphatic acids, such as those whose alkyl radical is C to C may be used, and the tridecyloxydiethyleneoxyethyl sulfate, tridecyloxypentaethyleneoxyethyl sulfate, and dodecyloxytriethyleneoxyethyl sulfate ester salts of these ampholytes will make useful products having similar properties to those set forth in the specific examples. Similarly, the alkylene group between the two nitrogen atoms may be C H or C H instead of C H with similar results.

In other words, although the above examples are limited to the use of a reaction product of aminoethylethanolamine and the fatty acid, as materials used for making the starting material, it will be obvious that other alkyl enediamines, such as ethylenediamine, may be used with similar results.

Likewise, the number of ethyleneoxy groups in the sulfate esters may vary from 2 to 6, with similar results.

M is an alkali metal (sodium or potassium), triethanol ammonium, a mixture of an alkali metal with hydrogen,

or a mixture of triethanol ammonium with hydrogen, depending on the pH.

Similarly, although the above shampoo examples are limited to the polyoxyethylene derivative of sorbitan monolaurate containing moles of ethylene oxide, the 30 mole ethylene oxide ether of nonylphenol, and the 29.8 ethylene oxide thioether of t-dodecylmercaptan, it will be obvious that other nonionics which pass the modified Draize test described above may be substituted for the nonionics of Examples 1-12. This would include, for example, the product of Example 13 when the nonionic is the reaction product of 1 mole of lauryl alcohol and 30 moles of ethylene oxide, or the reaction product of 1 mole of lauric acid and 30 moles of ethylene oxide. When this is done, using similar proportions, useful shampoos are produced which have high foam and low stinging properties.

The following examples (Examples 13 to 18) illustrate embodiments of this invention which, although possessing more stinging qualities than the shampoos of Examples 1-12, are useful as detergents, such as wound cleansers, skin cleansers, and allied pharmaceutical preparations.

EXAMPLE 13 The procedure of Example 1 is repeated, except that an equal weight of the reaction product of 1 mole of lauryl alcohol and 23 moles of ethylene oxide is substituted for the reaction product of 1 mole of sorbitan monolaurate and 20 moles of ethylene oxide. The polyoxyethylene derivative of lauryl alcohol has a cloud point above 100 C. at 2% concentration in distilled water.

The product was found to give excellent lather when used for cleansing skin in hard or distilled water or in the presence of grease.

EXAMPLE 14 500 parts (0.285 mole of amino group) of an amphoteric surface active solution, containing about 0.269 mole of N-lauroyl-N'-sodium carboxymethyl-N-(Z-hydroxyethyl) ethylenediamine, is mixed with 456 parts of an aqueous solution containing 124 parts (0.285 mole) of tridecyldiethyleneoxyethyl sulfate sodium salt. The product weighs 956 parts and contains approximately 23.2% surface active materials. 47.41 parts of this solution, containing 11 parts surface active materials, is mixed with 14 parts of the reaction product of one mole of tridecyl alcohol and 9.8 moles of ethylene oxide. The solution is neutralized to pH 7 with hydrochloric acid and made up to 100 parts with distilled water. The polyoxyethylenated tridecyl alcohol has a cloud point of 67 C. at 2% concentration in distilled water.

The above solution was found to give excellent lather when used for cleansing skin in hard or distilled water or in the presence of grease.

EXAMPLE 15 Example 14 is repeated, except that an equal Weight of the reaction product of one mole of lauric acid and 9.1 moles of ethylene oxide is substituted for the reaction product of one mole of tridecyl alcohol and 9.8 moles of ethylene oxide. The polyoxyethylenated lauric acid has a cloud point of 3840 C. at 2% concentration in distilled water.

The product is similar in performance, and is useful for the same purpose as Example 14.

EXAMPLE 16 Example 10 was repeated, except that the nonionic surfactant used was the reaction product of t-dodecylmercaptan and 9-10 moles of ethylene oxide. This material had a cloud point of about 55 C., when determined at 2% concentration in distilled water. The product was neutralized to pH 7 with hydrochloric acid and made up to 50 parts with distilled water. The solution was found to have excellent detergent properties and exceptionally strong foaming action when used for cleansing skin in the presence of hard water, distilled water or grease, but was quite irritating when it came in contact with the eyes.

EXAMPLE 17 Example 10 was repeated, except that the nonionic surfactant used was the reaction product of t-dodecylmercaptan and 15.4 moles of ethylene oxide. This material had a cloud point of about 88 C., when determined at 2% concentration in distilled water. The product was neutralized to pH 7 with hydrochloric acid and made up to parts with distilled water. The solution was found to have excellent detergent properties and exceptionally strong foaming action when used for cleansing skin in the presence of hard water, distilled water or grease, but was quite irritating when it came in contact with the eyes.

EXAMPLE 18 Example 10 was repeated except that the nonionic surfactant used was the reaction product of t-dodecylmercaptan and 19.85 moles of ethylene oxide. This material had a cloud point of about 102 C., when determined at 2% concentration in distilled water, where the solution was a superheated refluxing liquid. The product was neutralized to pH 7 with hydrochloric acid and made up to 50 parts with distilled water. The solution was found to have excellent detergent properties and exceptionally strong foaming action when used for cleansing skin in the presence of hard water, distilled water or grease, but was quite irritating when it came in contact with the eyes.

For the purpose of further illustrating this invention, We have set forth the results of foam tests by the Ross- Miles method in the following table, in which percent active signifies percent by weight of the indicated ingredient. The Amphoteric Ingredient column and Amphoteric-Nonionic column include not only the indicated surfactant but also anionic surfactant. The anionic is combined with the amphoteric in salt form. It signifies that the foam tests were carried out in distilled water containing 300 ppm. calcium chloride. All solutions were adjusted to pH 7, but it has been found that there is no substantial difference in foam when measured at pH 6.6 or pH 7.4. Not all compositions which show synergism will show it at exactly the same concentration. In the use of a shampoo best cleaning is generally obtained in the concentration range of 1 to 10%. However, good foaming is desirable even at lesser concentrations.

Table I mm. of Foam by Ross-Miles Method Water Used Example No. in Cone, Combination Foam Percent Amphoteric- Nonionic of Amphot,- Test Active Anionic Ingred. Anionic- Ingred. Nonionic Ingredient h 5 167 179 200 h 5 128 179 190 h 5 128 179 207 h. 5 45 179 208 h 5 45 179 214 h 5 184 179 214 h 7.5 189 167 202 h 5 210 179 21 1 h 5 147 204 h 5 167 159 205 h 5 160 179 203 h 5 179 204 h 5 167 150 195 h 5 102 183 187 h 5 102 98 134 h 5 140 175 18G h 5 128 210 h 5 167 159 205 For each example, a foam test in the presence of grease by the standard Ross-Miles method was conducted as follows:

(1) Lanolin, anhydrous, cosmetic grade is mixed with dioxane (technical grade) in the proportion of 2.5 grams lanolin and 100 grams of dioxane. The lanolin is first mixed with 25 cc. of dioxane. This mixture is heated over a steam bath to 45 C. in order to dissolve the lanolin in the dioxane. The remainder of the dioxane is then added and mixed. This lanolindioxane solution, which is stored in an amber bottle, should be prepared fresh on the day that the tests are run.

(2) The shampoo to be tested is diluted by adding 376 cc. of distilled Water to 4 grams of the shampoo, and then adding 20 cc. of the lanolin-dioxane solution described in (1) above while mixing. Heat is produced when the lanolin-dioxane solution is added to the slution of shampoo in water and care must be taken in adjusting the temperature of this solution to 2425 C. Both of these intermediate solutions should therefore be adjusted to 23 C. before mixing. The cooling of the lanolin-dioxane solution should be gradual in order to avoid precipitation of the lanolin. This will produce a final solution with a temperature of 2 25 C.

(3) The final solution of shampoo, water, dioxane and lanolin described in (2) is then run in the Ross-Miles foam column in the usual way. All tests are conducted in duplicate, and the average of the two results is taken.

For purposes of comparison of the surfactant combinations in the grease foam test, a solution containing 0.05 of sodium lauryl sulfate (commercially available, Duponol C, E. I du Pont de Nemours & Co., Inc., Wilmington 98, Delaware) is found to be a suitable standard. Accordingly, Table II records the grease foam height as the percent of the foam of a 0.05% active sodium lauryl sulfate solution, which has an average foam height of about 128 mm. in a typical test.

The concentration of each formulation is adjusted to 25%. Accordingly, 1% of the formulation would be a 0.25% solution of the active ingredients.

Table II GREASE FOAM Grease Foam Expressed as Percent of That Obtained v With 0.05%

Sodium Laurvl Sulfate Cone. Percent Example N o. Formulation HHHHHHHHHHHHHHHHb- H It is apparent that many widely different embodiments of this invention may be made without departing from the spirit and scope thereof; and, therefore, it is not intended to be limited except as indicated in the appended claims.

member of the group consisting of alkali metals, triethanol ammonium, mixtures of an alkali metal with hydrogen, and mixtures of triet-hanol ammonium with hydrogen, and (II) a water soluble nonionic surfactant comprising a polyoxyethylenated derivative of a hydrophobic base, said derivative being a member of the group consisting-of:

(a) 9-18 carbon atom fatty acid monoesters of aliphatic polyhydric alcohols, which polyhydric alcohols contain at least 3 hydroxyls, reacted with 10 to 20 moles of ethylene oxide,

(b) a member of the group consisting of the reaction product of 9-18 carbon atom alcohols, acids, and mercaptans with at least two-thirds as many ethylene oxide units as the number of carbon atoms in the hydrophobic base, but not exceeding 30 ethylene oxide units, and

(c) a member of the group consisting of the reaction products of 12-24 carbon atom alkyl phenols and alkyl cyclohexanols with at least as many ethylene oxide units as the number of carbon atoms in the hydrophobic base, but not exceeding 30 ethylene oxide units, the ratio of (II) to (I) being from 5.2-1 to 0.375-1.

2. The detergent composition of claim 1, in which R is C11H23, R0 is CHzCHg, R1 is C13H27: n iS 3 and M is sodium.

3. The detergent composition of claim 1, in which R iS C11H23, R0 iS CHZCHZ, R1 is C12H25, n iS 4 and M is sodium.

4. The detergent composition of claim 1, in which the nonionic surfactant is a reaction product of 1 mole of lauric acid and at least 9 moles of ethylene oxide;

5. The detergent composition of claim 1, in which the nonionic surfactant is a reaction product of 1 mole of tridecyl alcohol and at least 10 moles of ethylene oxide.

6. A substantially neutral shampoo consisting essen tially of (I) where R is a 913 carbon alkyl radical, R is an alkylene group of 24 carbon atoms, R is a member of the group consisting of C I-I and C H n is 2-6, and M is a member of the group consisting of alkali metals, triethanol ammonium, mixtures of an alkali metal with hydrogen, and mixtures of triethanol ammonium with hydrogen, and (II) a water soluble nonionic surfactant comprising a polyox-yethylenated derivative of a hydrophobic base, said derivative being a member of the group consisting of:

'(a) 918 carbon atom fatty acid mouoesters of aliphatic polyhydric alcohols, which polyhydric alcohols contain at least 3 hydroxyls, reacted with about 20 moles of ethylene oxide,

(b) a member of the group consisting of the reaction products of 9-l8 carbon atom alcohols, acids, and mercaptans with about 30 moles of ethylene oxide, and

'(c) a member of the group consisting of the reaction products of 12-24 carbon atom alkyl phenols and alkyl cyclohexailols with about 30 moles of ethylene oxide, the ratio of (II) to (I) being from 52-1 to 0375-1.

7. The shampoo composition of claim 6, in which R is CuHzg, R0 is CHZCHZ, R1 is C13H27, n is 3 M is sodium.

8. The shampoo composition of claim 6, in which R is C11H23, R0 IS CHZCHZ, R1 is CHI-I25, n iS 4 M is sodium.

9. The shampoo composition of claim 6, in which the nonionic surfactant is a reaction product of 1 mole of sorbita-n monolaur-ate and at least 20 moles of ethylene oxide.

10. The shampoo composition of claim 6, in which the nonionic surfactant is a reaction product of 1 mole of lauryl alcohol and at least 30 moles of ethylene oxide.

11. The shampoo composition of claim 6, in which the nonionic surfactant is a reaction product of 1 mole of nonylphenol and at least 30 moles of ethylene oxide.

12. The shampoo composition of claim 6, in which the nonionic surfactant is a reaction product of 1 mole of t-dodecylmercaptan and at least 30 moles of ethylene oxide.

13. The shampoo composition of claim 6, in which the nonionic surfactant is a reaction product of 1 mole of lauric acid and at least 30 moles of ethylene oxide.

14. The method of making a substantially neutral detergent composition which comprises reacting N-lauroyl- N-(2-hydroxyethyl) ethylenediamine with an aqueous alkaline solution of sodium chloracetate, adding aqueous sodium hydroxide solution and heating again until a sparkling clear solution of about pH 9 is obtained, heating the resulting product with an aqueous solution of where R is a member of the group consisting of C13H27 and C H n is 2-6, and M is a member of the group consisting of alkali metals, triethanol ammonium, mixtures of an alkali metal with hydrogen, and mixtures of triethanol ammonium with hydrogen, mixing the resulting product of pH about 8.7 with a Water soluble nonionic surfactant comprising a polyoxyethylenated derivative of a hydrophobic base, said derivative being a member of the group consisting of:

(a) 9-18 carbon atom fatty acid monoesters of aliphatic polyhydric alcohols, which polyhydric alcohols contain at least 3 hydroxyls, reacted with 10 to 20 moles of ethylene oxide, and

(b) a member of the group consisting of the reaction products of 9-18 carbon atom alcohols, acids, and mercaptans with at least as many ethylene oxide units as the number of carbon atoms in the hydrophobic base, but not exceeding 30 ethylene oxide units, and

(c) a member of the group consisting of the reaction products of 12-24 carbon atom alkyl phenols and alkyl cyclohexanols with at least as many ethylene oxide units as the number of carbon atoms in the hydrophobic base, but not exceeding 30 ethylene oxide units, the ratio of the nonionic surfactant to the other product being from 5.2-1 to 0.375-1,

and neutralizing the resulting product with hydrochloric acid.

15. The method of claim 14, in which R is C H n is 3 and M is sodium.

16. The method of claim 14, in which R is C I-I n is 4 and M is sodium.

17. The method of claim 14, in which the nonionic surfactant is the reaction product of 1 mole of lauric acid and at least 9 moles of ethylene oxide.

18. The method of claim 14, in which the nonionic surfactant is the reaction product of 1 mole of tridecyl alcohol and at least 10 moles of ethylene oxide.

19. The method of making a substantially neutral shampoo which comprises reacting N-lauroyl-N-(2-hydroxyethyl) ethylenediamine with an aqueous alkaline solution of sodium chloracetate, adding aqueous sodium hydroxide solution and heating again until a sparkling 123 clear solution of about pH 9 is obtained, heating the resulting product with an aqueous solution of where R is a member of the group consisting of C H and C H n is 2-6, and M is a member of the group consisting of alkali metals, triethanol ammonium, mixtures of an alkali metal with hydrogen, and mixtures of triethanol ammonium with hydrogen, mixing the resulting product of pH about 8.7 with a water soluble nonionic surfactant comprising a polyoxyethylenated derivative of a hydrophobic base, said derivative being a member of the group consisting of:

(a) 9-18 carbon atom fatty acid monoesters of aliphatic polyhydric alcohols, which polyhydric alcohols contain at least 3 hydroxyls, reacted with about 20 moles of ethylene oxide, and

(b) a member of the group consisting of the reaction products of 9-18 carbon atom alcohols, acids, and mercaptans with about 30 moles of ethylene oxide, and

(c) a member of the group consisting of the reaction products of 12-24 carbon atom alkyl phenols and alkyl cyclohexanols with about 30 moles of ethylene oxide, the ratio of the nonionic surfactant to the other product being from 52-1 to 0.375-1,

and neutralizing the resulting product with hydrochloric acid.

20. The method of claim 19 for making a shampoo, in which R is C13H27, n is 3 and M is sodium.

21. The method of claim 19 for making a shampoo, in which R is C H n is 4 and M is sodium.

22. The method of claim 19 for making a shampoo, in which the nonionic surfactant is the reaction product of 1 mole of sorbitan monolaurate and at least 20 moles of ethylene oxide.

23. The method of claim 19 for making a shampoo, in which the nonionic surfactant is the reaction product of 1 mole of lauryl alcohol and at least 30 moles of ethylene oxide.

24. The method of claim 19 for making a shampoo, in which the nonionic surfactant is the reaction product of 1 mole of nonylphenol and at least 30 moles of ethylene oxide.

25. The method of claim 19 for making a shampoo, in which the nonionic surfactant is the reaction product of 1 mole of t-dodecylmercaptan and at least 30 moles of ethylene oxide.

26. The method of claim 19 for making a shampoo, in which the nonionic surfactant is the reaction product of 1 mole of lauric acid and at least 30 moles of ethylene oxide.

References Cited in the file of this patent UNITED STATES PATENTS Isbell Nov. 25, 1952 Mannheimer Feb. 12, 1957 OTHER REFERENCES

Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3341460 *Oct 21, 1965Sep 12, 1967Colgate Palmolive CoShampoo composition
US3424849 *Jul 13, 1965Jan 28, 1969Procter & GambleBath oil composition containing octyl dodecanoate
US3928251 *Dec 11, 1972Dec 23, 1975Procter & GambleMild shampoo compositions
US3950417 *Feb 28, 1975Apr 13, 1976Johnson & JohnsonA betaine amphoteric surfactant, anionic surfactants, nonionic surfactants
US4138371 *Aug 8, 1977Feb 6, 1979Gaf CorporationWashing method using amphoteric surface active agents
US4177171 *Nov 3, 1975Dec 4, 1979Johnson & JohnsonShampoo
US4233192 *Nov 30, 1978Nov 11, 1980Johnson & JohnsonFoaming, non-irritating; for personal care
US4726915 *Mar 10, 1986Feb 23, 1988Johnson & Johnson Baby Products CompanyMixture of sulfated polyoxyalkylene anionic surfactant with amphoteric surfactant
US4759875 *Jan 14, 1986Jul 26, 1988S. C. Johnson & Son, Inc.Oxo-derived mild surfactant blends
US4876034 *Oct 29, 1987Oct 24, 1989Kao CorporationSecondary amidoamino acid based detergent composition
US4885112 *Nov 10, 1987Dec 5, 1989Kao CorporationSurface active secondary amidoamino acid or salt compounds
US8227393Dec 21, 2010Jul 24, 2012Johnson & Johnson Consumer Companies, Inc.Compositions comprising a polyglyceryl nonionic surfactant and a zwitterionic surfactant
DE3208311A1 *Mar 8, 1982Dec 30, 1982Johnson & Johnson Baby ProdAmphoter-fettsaeure-komplex und detergenshaltige gemische
EP0269939A2 *Nov 16, 1987Jun 8, 1988Kao CorporationDetergent composition
EP0269940A2 *Nov 16, 1987Jun 8, 1988Kao CorporationSurface active agent and process for preparing the same
Classifications
U.S. Classification510/126, 510/127, 510/506, 510/159, 510/424, 510/490
International ClassificationC11D1/88
Cooperative ClassificationA61K2800/596, C11D1/88, A61K8/466, A61K8/39, A61Q5/02
European ClassificationC11D1/88, A61Q5/02, A61K8/46F, A61K8/39