US2307047A

US2307047A - Thickening of solutions

Info

Publication number: US2307047A
Application number: US393845A
Authority: US
Inventors: Katzman Morris; Frank J Cahn
Original assignee: EMULSOL CORP
Current assignee: EMULSOL Corp
Priority date: 1941-05-16
Filing date: 1941-05-16
Publication date: 1943-01-05
Anticipated expiration: 1960-01-05

Description

tented .lan. fi i943 THICKENING F SOLUTIONS Morris Batman and Frank J. Calm, Chicago, BL,

assign-101's to The Emulsol ,Corporation, Chico, M1.

N0 Drawing. Application y 16, 19M,

Serial No. 393,845

16 'Elaims.

This invention relates to the thickening of detergent solutions and is particularly concerned with the thickening of shampoos comprising aqueous solutions of anionic interface modifying agents having good lathering and detergent properties.

In dealing with detergent solutions of interface modifying agents which are known to the prior art, it frequently becomes highly desirable to increase the thickness, consistency or viscosity of said solutions. As an example, preparations have been produced in accordance with prior art teachings wherein an interface modifying agent having sudsing and detergent powers is dissolved in a suitable solvent such as water or organic solvents such as alcohol or aqueous-organic solvents such as mixtures of water and alcohol. For meeting the demands of certain classes of trade, it is highly advisable to provide a product having a relatively heavy consistency or an enhanced thickness. While an increase in thickening may, in certain cases, be accomplished by increasing the concentration of the interface modifying agent in its solvent, this becomes impracticable in most cases since the interface modifying agents are frequently soluble to only a limited extent in the particular solvent preferred to be used. In addition, the increase in the concentration of the interface modifying agents, aside from other disadvantages emanating from such practice, is usually uneconomic since the degree of enhancement of thickness or increase in viscosity attainable by such method is insufficient to warrant the substantiall greater cost involved.

Solutions, for example, aqueous solutions, containing as high as or more, by weight, of some interface modifying agents are almost as limpid as water. When poured from a bottle and handled, there is a marked tendency for loss of solution by spilling.. It becomes highly advantageous in many instances to increase the thickness, consistency or viscosity of such and similar solutions to facilitate the handling thereof and minimize the loss during pouring and the like from bottles or similar containers or receptacles. Other advantages accrue from the present invention into which it is not necessary to go into detail.

It is, accordingly, an important object of the present invention to increase thickness or viscosity of solutions of interface modifying agents in a relatively simple and inexpensive manner.

A further object of the invention is to increase the thickness or viscosity of shampoos comprising aqueous solutions of interface modifying agents which have high sudsing and detergent properties.

Other objects and features of the invention will become apparent as the detailed description of the invention proceeds.

As a result of considerable research work, a

large class of thickening agents has been discovered of general utility for thickening solutions of interface modifiers, and of marked utility for thickening solutions, particularly aqueous solutions, of interface modifying agents having good sudsing and detergent properties. These thickeners may be characterized as certain partial esters of aliphatic polyhydric alcohols or allphatic polyhydroxy substances. Particularly useful are the caprylic acid mono-esters of diethylene glycol and triethylene glycol, and of unusual utility is the caprylic acid mono-ester of triethanolamine hydrochloride.

The aliphatic polyhydroxy substances whose partial esters comprise the thickening agents utilized in accordance with the present invention may be selected from a large group including, among those previously mentioned, glycerol; glycols such as ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol and the like; polyglycols such as diethylene glycol, triethylene glycol, and tetraethylene glycol; pentaerythritol; quercitol; di-hydroxy acetone; polyglycerols such as diglycerol, triglycerol, tetraglyceroi and the like including mixtures thereof; carbohydrates and sugars including mono-, diand polysaccharides such as dextrose, sucrose, xylose, arabinose, galactose, fructose, maltose, mannose, and the like; the natural and synthetic simple and complex glucosides; sugar alcohols such as arabitol, mannitol, mannitan, sorbitol, sorbitan, and dulcitol; and polyhydroxy-carboxylic acids such as tartaric acid, 'mucic acid, saccharic acid, gluconic acid, glucuronic acid, gulonic acid, mannom'c acid, trihydroxyglutaric acid, glycerlc acid, carboxylic oxidation products of polyglycerols, others of similar character, and hydroxyethyl and hydroxypropyl ether derivatives of the above, as, for example:

(For convenience, all hydroxyl groups are written facing one way.)

Still others are triethanolamlne, tripropanolamine, tri-isopropanolamine, tributanolamine, tripentanolamine, trihexanolamine, monoethanol dipropanolamine, diethanol mono-propanolamine, monoethanol monobutanolamine, diethanol monobutanolamine; l-amino-2,3 -propanediol; 2- amino-1,3-propanediol; 2-amino-2 methyl 1,3- propanediol; trimethylol-amino methane; Z-amino-Z-n-propyl-1,3-propanediol; 2-amino-2-3-isopropyl-1,3-propanediol; 2-amino-2-ethylol 1,3- propanediol; trimethylol amino methyl methane; alkylol polyamines such as alkylol derivatives of ethylene diamine, diethylene triamine, and triethylene tetra-amine as, for example, di (hydroxy-ethyl) ethylene diamine; polyhydroxy amino-carboxylic acids; hydroxy tertiary amines derived from other polyhydric alcohols, including glycols, sugars and sugar alcohols such as ethylene glycol, diethylene glycol, dextrose, sucrose, sorbitol, mannitol and dulcitol;

and the like. Polymerized hydroxy tertiary amines prepared, for example, by polymerizing triethanolamine or other hydromr tertiary amines such as those mentioned hereinabove, particularly in the presence of a catalyst such as sodium hydroxide or the like, may also be employed. The preparationof polymerized hydroxy tertiary amines is disclosed, for example, in United States Patent No. 2,178,173. Homologues substitution derivatives of theabove-mentioned hydroxy amines may also be utilized.

It will be understood that the aliyphatic polyhydrow substances may be utilized in pure, im-

or commercial form.

The aliphatic acids which are esterifled with the aliphatic polyhydroxy substances to form the thickening agents may be selected from a large group including straight chain and branched chain, saturated and unsaturated, carboxylic, aliphatic, cycloaliphatic, and fatty acids, including caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, sebacic acid, behenic acid, arachidic acid, lauric acid, myris'tic acid, mixtures of any two or more of the above mentioned acids or other acids; hydroxy and alpba-hydroxy higher carboxylic aliphatic and fatty acids such as alpha-hydroxy capric acid, alpha-hydroxy lauric acid, alpha-hydroxy myristic acid, alphahydroxy coconut oil mixed fatty acids, and the like. It will be understood that mixtures of any two or more of said acids may be employed if desired. The acids may be employed as such or in the form of their anhydrides, esters including mono-, di-, tri-glycerides and the like,,and acyl halides, or, in general, in the form of any of their acylating compounds. Of particular utility are the unsubstituted fatty acids containing from six to ten carbon atoms and their acyl halides.

The thickening agents should be soluble in the solutions of the interface modifying agents. In

molecule of the compounds themselves.

acorns"? As illustrative of thickeners falling within the scope of the invention may be mentioned, by way of example, in addition to those previously referred to, Z-ethyl hexoic acid mono-ester of triethanolamine hydrochloride; caproic acid monoester of tripropanolamine acetate; capric acid mono-ester of tributanolamine hydrochloride; enanthic acid mono-ester of diethylene glycol; pelargonic acid mono-ester of tetraethylene glycol, and the like.

It is convenient to prepare a solution of the thickener and add it in the desired amounts to the interface modifying agent solution although the manner of incorporation is optional and may be accomplished in various ways, as, for example, in certain cases, in situ during the preparation of the solution of the interface modifying agent. Since, in the main, aqueous solutions of interface modifiers are employed, the thickeners utilized in such solutions will be water-soluble. It will be understood that in all cases the thickener must be soluble in the solution of the interface modifier in which it is employed.

The anionic interface modifying agents whose solutions may be thickened by means of the compounds disclosed hereinabove are generally characterized by the presence of at least one higher molecular weight lipophile group containing preferably at least eight carbon atoms, preferably although not necessarily, aliphatic in character, and by the presence of at least one hydrophile or hydrophillic group. preferably in the form of an oxygenated sulphur, phosphorus or boron radical, particularly sulphur in the form of sulphate or sulphonic acid radicals, although, as will be seen, the hydrophillic group is not so limited. Preferabh', the lipophile and hydrophile groups are in a state of balance whereby the resulting compound has the property of reducing the spattering of margarine when used for frying. This concept of balance of lipophile and hydrophile groups is treated in considerable detail in the patent to Benjamin R. Harris, No. 1,917,250, isssued July 11, 1933, and need not here be elaborated upon further. While this "balance may be determined empirically by means of a margarine frying test, as described in said patent, those skilled in the art will, in most cases, readily be able to predict the existence of balance" from merely an inspection of the As a general rule, the hydrophile and lipophile groups should preferably be at the ends or extremities of the molecule as, for example, in the case of lauryl sodium sulphate wherein the lauryl group, or, in other words, the lipophile group, is present at one end of the molecule, and the sulphate or hydrophile group is present at the other end of the molecule.

As previously indicated, the invention is particularly useful with respect to the thickening of solutions of those interface modliying agents which have good sudsing, foaming and detergent properties. This aspect of the invention will become more apparent as the description proceeds.

It will be understood that the term lipophile group" includes groups having a definite alfinity for oils and fats and comprises, for example, alkyl, aralkyl, aryl, ether or ester groups containing "preferably at least eight carbon atoms. The lipophile group possesses predominantly'hydrocarbon characteristics and, in general, is derived from triglyceride fats and oils, waxes, mineral oils, other hydrocarbons. and the like.

asoaoer in contra-distinction thereto, the term hydrophile group or hydrophillic group" includes groups which possess an amnity for water and aqueous media. As examples of such groups may be mentioned the following: hydroxyl, hydroxylcarboxylic, sulphate, sulphonic, phosphate, pyrophosphate, tetraphosphate, borate, lower molecular weight sulpho-carboxylic acids such as sulphoacetates, sulphopropionates, sulphosuccinates, sulphoglutarates, and the like.

Among the interface modifying agents whose solutions may be thickened in accordance with the present invention are organic substances having balanced lipophile and hydrophile groups, the lipophile group containing at least eight carbon atoms and the hydrophile group comprising a radical selected from the class consisting of oxygenated sulphur, oxygenated phosphorus, and oxygenated boron inorganic acid radicals.

One sub-class thereof, several members ofwhlch have excellent sudsing, foaming, frothing, lathering, and detergent powers, comprises the higher molecular weight alcohol sulphates and sulphonates. The alcohols from which these sulphates and sulphonates may be prepared include the following: aliphatic straight chain and branched chain alcohols such as octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, oleyl alcohol, llnoleyl alcohol, stearyl alcohol, ricinoleyl alcohol, palmitoleyl alcohol, melissyl alcohol, ceryl alcohol, carnaubyl alcohol, myricyl acohol, branched chain octyl, decyl, dodecyl, tetradecyl, hexadecyl and octadecyl aliphatic alcohols as, for example, 2-ethyl hexanol-l, 2-n butyl octanol-l, Z-butyl tet'radecanol-Land, in general, the higher molecular weight saturated and unsaturated aliphatic straight chain and branched chain alcohols. Preferably, the alcohols which are utilized are those corresponding to the fatty acids occurring in triglyceride oils and fats of vegetable or animal origin, natural or hydrogenated, such as corn oil, cottonseed oil, sesame oil, coconutoil, palm kernel oil, sunflower seed oil, lard, tallow, soya bean oil and the like, those alcohols containing from 12 to 18 carbon atoms being preferred. Other alcohols which may be employed are the cycle-aliphatic or all-cyclic alcohols such as the sterols, as, for example, cholesterol, iso-cholesterol, phytosterol, sitosterol, hydroaromatic alcohols such as abietol, and such unsaturated alcohols as llnalol, citronellol, geraniol and the like. Also included within the class of alcohols which may be employed are such compounds as the hydroxy and alpha-hydroxy higher aliphatic and fatty acids as, for example, ricinoleic acid, alphahydroxy stearic acid, alpha-hydrow lauric acid, di-hydroiw stearic acid, i-hydroxystearic acid, alpha-hydroxy palmitic acid, and the like, as well as esters of hydroxy-fatty acids, such as ethyl rlcinoleate, castor oil, butyl alpha-hydroxystearate, cetyl hydroxystearate, and the like.

The term alcohols" as employed herein, is intended to include alcohols which may or may not contain other groups such as carboxylic, halogen, sulphonic, sulphate, or other radicals. The alcohols obtainable by substituting alkyl or acyl radicals, preferably of high molecular weight, in place of the hydrogen of one or more hydroxy groups of polyhydroxy substances or polyhydric alcohols, it being understood that at least one hydroxy group attached to the nucleus of the polyhydroxy substance or polyhydric alcohol remains, are also within the scope of the alcohols sulphates and sulphonates may be produced. As examples of such alcohols may be mentioned pan tially esterified or partially etherified sugars and sugar alcohols such as monolauric acid ester of sucrose, monostearic acid ester of dextrose, monopalmitic acid ester of mannitol, dicaproic acid ester of maltose, monooctyl ether of sorbitol, monolauryl ether of pentaerythritol, monolauric acid ester of pentaerythritol, and the like; the monoglycerides and diglycerides, preferably of the higher fatty acids, as, for example, monolaurln, monornyristin, monostearin, distearin, diolein, dicaproin, mono-lauryl ether of glycerol, di-cetyl ether of glycerol, monostearic acid ester of diethylene glycol, monolauric acid ester of ethylene glycol, and the like.

It is, of course, obvious that the alcohols from which the sulphates and sulphonates may be produced may be prepared in accordance with any desired method. For example, many of these alcohols may be prepared by the so-called Bouveault and Blank method or, alternatively, by the reduction or catalytic reduction with hydrogen of natural or hydrogenated animal or vegetable fats and oils, or mixtures thereof, in accordance with well known practices. Again the alcohols may be derived from synthetic processes such as by the oxidation of hydrocarbons or may be prepared by saponifieation of waxes and the like. Alternatively, they may be prepared by reduction of aldehydes or by the Grignard reaction.

It is likewise apparent that mixtures of the foregoing or other alcohols may be utilized in the preparation of the sulphates and sulphonates as, for example, the mixture of alcohols resulting from the hydrogenation of coconut oil or the free fatty acids of coconut oil. Lauryl alcohol comprises about 45% of the total alcohol mixture, the remaining alcohols running from Co to C13. Again, mixtures of alcohols such as are present in the socalled sperm oil alcohols, as well as those present in wool-fat, may equally efllcaciously be utilized. Indeed, these higher molecular weight alcohols are generally offered on the market in the form of mixture of different alcohols. If desired, for any specific purpose, special fractions which predominate in a certain particular higher molecular weight alcohol may be utilized or, if so desired, the products may be prepared from a single, substantially pure alcohol.

These sulphates and sulphonates, described hereinabove, may, in general, be represented by the formula wherein R represents the residue of a normal primary alcoholcontaining from 8 to 18 carbon atoms, Y represents a cation or the residue of a salt-forming compound such as sodium, triethfrom which the fitanolamlne or the like, and n is a small whole number, at least one.

The sulphates and sulphonates described are preferably utilized in the form of salts and, in

their preparation, the acid sulphuric ester or sulphonic acid may be neutralized, in whole or in part, with suitable anti-acid materials. In this connection, considerable latitude and modification may be exercised. In general, inorganic as well as organic anti-acid agents may be employed. Examples of such agents which may be used satisfactorily are bicarbonates of the alkali metals, potassium hydroxide, sodium oxide, sodium carbonate, ammonium hydroxide, ammonia gas, potassium stearate, sodium stearate, magnesium oxide, magnesium carbonate, organic anti-acid nitrogenous materials including amines and alkylolamines such as, for example, mono-, diand triethanolamine and mixtures thereof, propanolamines, butanolamines, polynitrogenous amines such as ethylene diamlne, ethylene triamine and the like, pyridine, piperidine, quaternary ammonium bases such as tetraethyl ammonium hydroxide, tetra-methyl ammonium hydroxide, and in general, primary, secondary and tertiary amines substituted or not with other radicals such as hydroxy groups, and the like. It will be understood that by the term cation, as used throughout the specification and claims, is meant hydrogen and such other element as are mentioned herein, and, in general. atoms or radicals which are regarded 'as bearing a positive charge or capable of replacing acidic hydrogen. The reaction products may be neutralized to methyl orange, litmus or phenolphthalein. As a general rule, if the salts of the reaction products are employed, it is preferred to use the sodium, potassium, ammonium, triethanolamine. quaternary ammonium, or other relatively highly soluble salts.

The sulphates and sulphonates disclosed hereinabove are described, among other places, in the following United States Patents 1,897,741; 1,968,793; 1,968,794; 1,968,796; 1,968,797; 2,006,309; 2,023,387; 2,028,091; 2,052,027, and 2,077,005.

Another sub-class of interface modifying agents whose solutions may be thickened are those compounds which correspond to the higher molecular weight alcohol sulphates and sulphonates described hereinabove but wherein the hydrophile group comprises oxygenated phosphorus instead of oxygenated sulphur. Among these compounds may be mentioned lauryl pyrophosphate, palmityl orthophosphate, sodium lauryl tetraphosphate, stearyl triethanolamine orthophosphate, oleyl monoethanolamine pyrophosphate, monolauric acid ester of diethylene glycol tetraphosphate, monoethanolamine salt, and the like. As in the case of the sulphates and sulphonates described previously, it is generally preferred to employ the oxygenated phosphorus derivatives in the form of their alkali, ammonium, or nitrogenous base or alkylolamine salts. These compounds are disclosed, among other places, in the following United States Patents 2,026,785; 2,052,029; 2,053,653; 2,128,946, and 2,177,650.

Again, in place of either the oxygenated phosphorus or oxygenated sulphur compounds, similar as well as corresponding oxygenated boron compounds may be employed. These include boric acid esters of higher molecular weight alcohols such as lauryl borate, cetyl borate, and boric acid esters of monoglycerides of higher fatty acids such as monostearin borate. For a more complete description of such or similar compounds, reference may be made to United States Patent No. 2,052,192.

Another class of interface modifying agents whose solutions may be thickened in accordance with the principles of the present invention are the lower molecular weight sulphocarboxylic acid esters of higher molecular weight alcohols such as those described hereinabove. Among these compoundsmay. e mentioned the monoethanolamine or triethanolamine salts or other highly soluble salts of octyl sulphoacetate, lauryl sulphoacetate, cetyl sulphoacetate, and the like. For a more complete description of such compounds, reference may be had to the following United States Patents Nos. 1,917,250; 2,166,141; 2,166,142; 2,166,143, and 2,185,455; and British Patent No. 377,249.

Another class of interface modifying agents whose solutions may be effectively thickened in accordance with the teachings of the present invention are the salts, such as the alkali metal salts, of the sulphoacetates of halogenated lauryl alcohol, as disclosed in the application of Benjamin R. Harris et al., Serial No. 308,578, filed December 11, 1939, now Patent No. 2,251,932, issued August 12, 1941. 7

Still another class of interface modifying agents whose solutions may be thickened in ac- -cordance with the teachings of the present invention are the compounds which correspond to the general formulae or the like, and w is a small whole number. As illustrative of these compounds may be mentioned the following:

1 7, W at These compounds and others of similar nature are disclosed in the following United States Patents 1,981,792; 1,931,540; 1,932,177, and 1,932,180.

It will be understood that the radical R in the above general formulae may be derived from higher aliphatic, fatty, cycloaliphatic, aromatic, and hydroaromatic acids such as the following: saturated and unsaturated higher molecular weight aliphatic acids such as the higher fatty acids containing at least eight carbon atoms and including caprylic acid, pelargonic acid, caprlc acid, melissic acid, stearic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid, lauric acid, myristic acid, palmitic acid, mixtures of any two or more of the above mentioned acids, or other acids, mixed higher fatty acids derived from animal or vegetable sources, for example, lard, coconut oil, sesame oil, corn oil, cottonseed oil, sardine oil, tallow, partially or completely hydrogenated animal and vegetable oils such as those mentioned; hydroxy and alpha-hydroxy higher aliphatic and fatty acids such as i-hydroxy stearic acid, dihydroxystearic acid, alphahydroxy stearic acid, alpha-hydroxy palmitic acid, alpha-hydroxy lauric acid, alpha-hydroxy coconut oil mixed fatty acids, and the like; aliphatic acids derived from various waxes such as beeswax, spermaceti, montan wax, and camauba wax and higher molecular, weight carboxylic acids derived, by oxidation and other methods, from petroleum; hydroaromatic acids such as abietic acid; aromatic acids such as naphthoic acid, hydroxy aromatic acids such as hydroxy naphthoic acids, and the like.

Another class of sulphur-containing interface modifying agents the thickening of whose solutions may be effected in accordance with the teachings of the present invention comprises those compounds which correspond, in general, to the formula Z--OX -S-X=-Y wherein X and X represent members selected from the class consisting of alkylene and substituted alkylene groups, Z represents a lipophillic group, and Y represents a hydrophillic group such as hydroxyl, sulphate, sulphonic, phosphate,

phosphonic, and the like. Illustrative of such compounds are the following:

oiwgenated phosphorus. Examples of such compounds are as follows:

may be thickened in accordance with the present invention are those disclosed in United States Patent No. 2,184,770. At least most of the compounds disclosed in said patent correspond to the following general formula:

wherein 0 at is an aliphatic acyl radical containing at least eight carbon atoms, alk is hydrocarbon, Y is a member selected from the group consisting of hydrogen, alkyl, cycloalkyl, alkoxyl, aralkyl, aryl,

and alkylol, Z. is a hydrocarbon residue, and X is a sulphonic group.

Additional groups of compounds which may be thickened by means of the process of the present invention include those which are disclosed in United States Patents Nos. 2,176,896; 2,178,139; 2,198,806; 2,236,528; 2,236,529, and in the following copending applications:

Morris Katzmanet a1 286, 776 July 27, 1939 Morris Katzman--." $6, uly 27,1939 Morris Katzman et a1... 291, 898 ug. 25, 1930 -Albert K. E stein at al 919 Sept. 28, 1939 Frank J. C natal Nov. 28,1939

Representative compounds disclosed in said pat- 5 ents and applications, whose salts, and especially whose organic nitrogenous base salts may be I thickened in accordance with the process of the It will, of course, be appreciated that the various thickening agents vary in their potency. Tha

p se invention, p se t o n amount to be employed will accordingly be determined not only by this fact but also will be a dependent upon the specific character and concentration of the interface modifying agent in (b) C"Hitl-C-NH-ClHl-O-fi-CE:- OIH.NE(CI IOH)x the solution thereof, and the particular results desired.

0 While, as stated and as is obvious, the amount O W of thickener which may be employed is variable i (c) CaHr-O- CuHn within relatively wide ranges of proportions, in

order to indicate the remarkable and unusual aspects of this phase of the invention, the following facts should be understood. Aqueous solutions it of the thickening agents, or substantially all of the same, which are disclosed herein, even in concentrations as high as 50% where they are solu- O ble to such an extent, are of a very limpid char- CnHarC-NH-CaHc-NH-C-CHz-CH-CO0K acter with viscosity practically identical with or OHBNHMIOH), as not much greater than that of ordinary water.

Nevertheless, the addition of relatively small proportions of such limpid solutions to interface modifying agent solutions results in an entirely unexpected increase in thickness and viscosity 2% of said latter solutions. That this happens in the face of and notwithstanding the mutual dilution which simultaneously occurs is all the more remarkable. The following table illustrates the nature of the results which have been '30 obtained:

Interface modifier solution Addition agent Result]! 2 g. caprylic acid Considerable in mono-eater of crease in vis- (i) 100 g. of a 17% aqumcua aolution oi monocthanolamine salt of triothanolocosity.

mine.

acidified with 1 g. tartaric acid. (2) 100 g. of a 17% aqueous aolution oi monoethanolsmins salt of 8 g. caprylic acid Do.

mono-ester of diothylene glycol.

(t) 100 g. of a 17% aqueous solution or! monocthanolsmine salt of 3 hg. 01f Z-ethIyJ Do.

exo e no C Hm-GO-CzHr-NHCHaBOaH mono-ester of triothanolamine.

acidified with 1.5 g. tartaric acid. (4) 100 g. of a 3102, aqueous aolution of tristhauolomins salt of lauryl sulphate acidified with 2. g. 4 g. caprylic acid Do.

tartaricaci mono-ester of triethanola- (5) cc. of a 10% aqueous solution of tristhauolaminc salt of lam'yi oulphoacotato 1.5 enanthio Substantial inaci monocster crews in viaoli til'iothylono coaity.

' i! 57 (6) 10 cc. of a aqueous aolution oi ixicthanolamino salt oi lauryl aulphtatc 1.8 g. pelargonic Appreciablc thiclracid mono-eater suing. Elf diethylono YOO (7) 10 cc. of a 25% aqueous solution of tricthanolamhio salt of lauryl sulphate E. mouocapry- Do.

(a) 10 cc. of a ii0% aqueous aolntion of iaopropylnaphthaleno sulphonaie, sodium salt 0.5 t. of hydro- Do.

chloride of caprylic acid mono-cater oi triothanolamine.

0 H o 0 It will be understood that, by the selection of (m c I certain thickeners and certain interface modi- W hers, and by varying the proportions or concen- CIHP'O C CHT-SOIH-HINC!-HOH trations thereof, the increase in thickness or viscosity can be readily controlled to any desired value. The thickening agent is utilized in proportions substantially less than the proportions of the interface modifying agent, in the usual case from 5% to 20% thereof. In general, it is preferred to increase the thickness or viscosity of the interface modifying agent solutions by at least several fold, preferably a minimum of fivefold and usually at least ten-foldto fifty-fold.

- thereto a substantially is it is preferred to carry out the invention with respect to the thickening of aqueous solutions of the interface modifying agents, it must not be inferred that the invention is so limited. Alcohols or other organic solvents may be employed, as well as aqueous-organic solvent mixtures, but for economic and other obvious reasons water is preferred.

The term solution" as employed herein and in the appended claims is employed in a broad sense to include not only true solutions but also colloidal dispersions.-

The term higher, as employed herein, is intended to mean not less than eight carbon atoms and, concomitantly, the term lower will be understood to mean less than eight carbon atoms, unless otherwise specifically stated.

The terms interface modifier and interface modifying agent, are employed interchangeably herein and are intended to embrace substances which comprise lipophile and hydrophilegroups and which are capable of reducing surface and interfacial tension, other than soaps or salts such as alkali metal salts of higher fatty acids.

While the thickening effect increases, in general, with increasing concentrations of interface modifying agents, it commences to become appreciable, in most cases, at concentrations of the order of magnitude of five to ten percent. The invention is, therefore, particularly applicable in connection with concentrations of interface modifiers of this order of magnitude and substantially beyond the above-mentioned range. Indeed, the invention is applicable to the treatment of solutions of interface modifiers of as high as or strength, or even higher.

What we claim as new and desire to coveriby Letters Patent of the United States is:

Lil

l. A method of thickening a solution of at least 5% of an anionic interface modifier having a lipophile group with at least eight carbon atoms and a hydrophile group, which comprises adding thereto a substantially lesser proportion of an aliphatic partial ester of an aliphatic polyhydroxy substance, which ester is soluble in said solution, sumcient to appreciably thicken the same.

2. A method of thickening a solution of at least 5% of an anionic interface modifier having a lipcphiie group with at least eight carbon atoms and a hydrophile group, which comprises adding lesser proportion of a fatty acid mono-ester of an aliphatic polyhydroxy substance, the fatty acid radical oi which contains from 6 to 10 carbon atoms, which ester is soluble in said solution, suflicient to appreciably thicken the same.

3. A'method of thickening a solution of at least 5% of an anionic interface modifier having a lipophile group with at least eight carbon atoms and a hydrophile group, which comprises adding thereto a substantially lesser proportion of a fatty acid mono-ester of an hydroxy-alkyl tertiary amine, which ester is soluble in said solution, sumcient toappreciably thicken the same.

i. A method of thickening a solution of at least 5% of an anionic interface modifier having a lipophile group with at-least eight carbon atoms and a hydrophile group, which comprises adding thereto a substantially lesser proportion of a caprylic acid mono-ester of triethanolamine, which ester is soluble in said solution, sufficient to appreciably thicken the same.

5. A method of thickening an aqueous solution of at least 5% of an anionic interface modifier with-at least eight carhaving a lipophile group bon atoms and a hydrophile group, which comprises adding thereto a proportion of a caprylic acid mono-ester of diethylene glycol, suificient to appreciably thicken the same.

6. A substantially clear solution of at least 5% of an alkyl sulphate having at least eight carbon atoms, containing a substantially lesser proporlion of an aliphatic partial ester of an aliphatic polyhydroxy substance, which ester is soluble in said solution, sufiicient to-appreciably thicken the same.

7. A substantially clear solutionof at least 5% of an organic nitrogenous base salt of a sulphuric acid ester of an aliphatic alcohol having from eight to eighteen .carbon atoms and containing a substantially lesser proportion of a fatty acid mono-ester of an aliphatic polyhydroxy substance, the fatty acid radical of which contains from 6 to 10 carbon atoms, which ester is soluble in said solution, sufilcient to appreciably thicken the same.

8. A substantially clear solution of at least 5% of an alkylolamine salt of a sulphuric acid ester of a straight chain aliphatic alcohol having from eight to eighteen carbon atoms and containing a small proportion of a caprylic acid mono-ester of diethylene glycol, which ester is soluble in said solution, sufli'cient to appreciably thicken the same.

9. A substantially clear aqueous solution of at least 5% of an alkylolamine salt of lauryl sulphate and containing a substantially lesser proportion of ,a caprylic acid mono-ester of triethanolamine, which ester is soluble in said solution, sufl'icient to appreciably thicken the same.

10. An aqueous solution of at least 5% of an alkylolamine salt of the sulphuric acid ester of a mixture of alcohols derived from cocoanut oil and comprising predominantly lauryl alcohol, and containing a substantially lesser proportion of a partial ester of a fatty acid with a watersoluble polyhydric alcohol, the fatty acid radical containing from 6 to 10 carbon atoms, which ester is soluble in said solution, suiflcient to appreciably thicken the same.

11. A solution'of at least 5% of an anionic interface modifying agent falling into the caten e-04pm wherein R is an aliphati hydrocarbon radical containing at least 7 carbon atoms and preferably between 11 and 17 carbon atoms, X is hydrogen, n is zero or one, Y is a lower molecular weight hydrocarbon radical, M is an oxygenated sulphur-containing inorganic acid radical, and w is a small whole number, and containing a small proportion of an aliphatic partial ester of an aliphatic polyhydroxy substance, which ester is soluble in said solution, sufllcient to appreciably thicken the same. 12. An aqueous solution interface modi formulae R-o -0 clms oz of at least 5% of an ying agent having the general wherein taining 12 to 18 carbon atoms, and Z is a cation, and containing a small proportion of a partial ester of an aliphatic polyhydroxy substance with a fatty acid containing from 6 to 10 carbon atoms, which ester is soluble in said solution, sufficient to appreciably thicken-the same.

13. An aqueous solution of at least of an alkylolamine salt of an anionic interface modifier having a iipophile group with at least eight carbon atoms and an oxygenated sulphur hydrophile group, said solution containing a substantially lesser proportion of a water-soluble monoester of a fatty acid with an aliphatic water-soluble polyhydroxy substance, which ester is soluble in said solution, sumcient to appreciably thicken the same.

14. An aqueous solution of at least 5% of a salt of a chemical compound corresponding to the general formula wherein R is an organic radical containing at least eight carbon atoms, all: and Z are each members'selected from the class consisting of hydrocarbon radicals and substitution products thereof, Y is a member selected from the group consisting of hydrogen, allryl and allrylol, m and w are whole numbers, and X is a sulphonic acid with an aliphatic polyhydroxy substance,

the fatty acid radical of which contains from 6 to 10 carbon atoms, which ester is soluble in said solution, suificient to appreciably thicken the same.

15. An aqueous solution of at least 5% of a monoethanolamine salt of the sulphoacetic acid amide of the lauric acid ester of monoethanolamine, and containing a small proportion of a fatty acid mono-ester with a glycol, the fatty acid radical of which contains from 6 to 10 carbon atoms, which ester is soluble in said solution, sufilcient to appreciably thicken the same.

16. An aqueous solution of at least 5% of a monoethanolamine salt of the sulphoacetic acid amide Of the lauric acid ester of monoethanolamine, and containing a small proportion of a caprylic acid mono-ester of triethanolamine, sumcient to appreciably thicken the same.

MORRIS KATZMAN. FRANK J. CAHN.