US2617772A

US2617772A - Tack-fr ee alkaryl sulfonate

Info

Publication number: US2617772A
Authority: US
Publication date: 1952-11-11
Anticipated expiration: 1969-11-11

Description

Patented Nov. 11,1952

TACK-FR EE ALKARYL SULFONATE DETERGENT Vincent J. Keenan, Ardinore, Pa., assignor to The Atlantic Refining Company, Philadelphia, Pa.. a corporation of Pennsylvania N Drawing.

Application June 17, 1950,

Serial No. 168,833

12 Claims. (Cl. 252-461) This invention relates to a detergent composi tion containing a water-soluble alkyl substituted aryl sulfonate, and more particularly to a composition containing a Water-soluble alkyl-sub- V stituted aryl sulfonate which does not develop objectionable tacky, adhesive sensations when used in contact with the human skin.

Detergent compositions in the form of bars, creams, shampoos, and similar cosmetic products have been made heretofore in which watersoluble alkyl-substituted aryl sulfonates constituted the surface active agent. Since these sulfonates, which hereinafter will be termed alkyl aryl sulfonates, do not form insoluble compounds with the calcium or magnesium ions found in hard 'water, it was assumed that such compositions would prove especially'valuable in hard water areas where present fatty acid soap compositions precipitate insoluble soaps and exhibit poor detergent and lather properties. Cosmetic preparations containing an alkyl aryl sulfonate were found, however, to produce an ad hesive or tacky sensation on the skin. This propertyis objectionable, so much so, that in spite of the superior detergency, lather, and solubility properties of alkyl aryl sulfonate compositions as'compared with fatty acid soap compositions in hard water, the sulfonate compositions have gofdmet with public acceptance in the cosmetic e v r The exact reason for the development of this tackiness by alkyl aryl sulfonate-containing compositions has not been exactly determined. However, the alkyl aryl sulfonates are highly active surface-active agents and consequently, it ispossible that they remove most of the natural protective oils of the skin, with the result their strongly polar sulfonate radicals become attached to or at least closely associated with the proteins of the skin, and thereby produce the characteristic, highly objectionable tacky sensation. Whatever the theoretical explanation, this tack has prevented full commercial utilization of alkyl aryl sulfonates in cosmetic detergents and until the present invention, no solution had been found to this problem.

{ In addition, alkyl aryl sulfonate formulations are ,extremelydifficult to extrude into bar forms.

These formulations are much too hard and either "freeze in the extruder or discharge as lumps likeribbon. H a

i It is an object otthis invention to produce a detergent composition in the form of a solid bar, cream, or liquid which contains an alkyl aryl sulfonate as surface active agent, and which,

instead of in the form of a smooth, coherent, gelwhnused in contact .with thehuman skin, does not develop objectionable tacky sensations.

It is an additional object to provide a deter gentcomposition containing an "alkyl substituted aryl sulfonate which may be-easily and smoothly extruded into coherent gel-like ribbons for the production of bars.

The detergent compositions of the present in vention may be prepared by forming a primary aqueous dispersion of the alkylaryl sulfonate together with commercial lecithin in an amount of at least 20%, but less than 70% by weight, based on the weight of the dry sulfonate. The amount of water used to form the primary dispersion is not critical, but in generalmay range, for example, between 0.5and 5 volumes of-water per volume of dry ingredients, this range being preferred in order to form a fluid dispersion which does not contain a large excess of water, since the water must be removed by a subsequent drying operation. In order to improve the appearance or performance of the finished product, various agents such as fillers, abrasives, dyes, perfumes, emollient oils, glycerol, and waxes may be dispersed in the primary mixture to form a final dispersion which when drum or spray dried, will produce a product in the form of freelyflowing flakes, sheets, pellets, or-beads. In addition, such dried material may be molded'into smooth bars or plodded or milled and subsequently extruded, sliced, and molded into bars. The compositions produced as above described, in addition to their ease of extrusion to form bars.-

, are entirely free of the objection of causing a tacky sensation when u'sed in contact with the hydrogen atoms of the aromatic.

human skin, a It is known that in many cases, fatty acid soap products cause severe dermatic and allergic reactions due to the'fact that they hydrolyze in water togive an alkaline solution.- 'Ihecompositions of the present invention, however, en-' tirely avoid such objectionable reactions since: both the lecithin and alkyl aryl sulfonatesar'e:

v non-alkaline even in aqueous solutions.

The water-soluble alkyl aryl sulfonates' suit--; able for use in the present detergent composi-: tions are prepared by sulfonating a suitable alkyl aromatic and neutrallizing' the resultant alkylaryl. sulfonic acid with an alkaline compound.

The alkyl aromatics suitable for preparing the desired sulfonates'have an alkyl group containing from 8 to 15 carbon atoms. In addition to thelong chain alkyl group, short chainalkyh groups may maybe substituted for other nuclear Th oin-J pounds maybe prepared by a variety of methods, for example, by the alkylation of an aromatic hydrocarbon with albranched-chain olefin -hav-j ing from 8 'to 15 carbon atoms in the presence similar acid-type catalysts. The olefins may be obtained from the polymerization of propylene over phosphoric ,acid or similar catalyst or by the polymerization of butylenes, etc. The aromatic employed may be benzene, naphthalene, toluene, any one of the isomeric xylenes or mixtures of such isomers, ethyl benzene, propyl benzene, or similar lower aIkyL-aromatics.

Another method of preparation involves the reaction of an alcohol containing from 8 to 15 carbon atoms with an aromatichydrocarbon in the presence of such catalysts as H2SO4,:BF3, BF3H2SO4, BF3-H3PO4, or AlCla. The ,alcohols may be obtained by the reaction of aniolefin with carbon monoxide and hydrogen in the socalled x0 process, or by the oxidation .;of paraffinic hydrocarbons. The aromatic hydrocarbon-email .b enzene, naphthalene, .toluene.

yl benz ne, nropyl .b nzene,.ors imi1a1' lower elkv -zaromaties.

Athird methodoi-prepa ationof ,the alkyl aromatics employs :a chlorinated hydrocarbon havin g;f -rom r 8 to :carbon atoms reacted with the {a matic hydrocarbon {in the presence .of a Miedel-Crafts catalyst such as AlC13. .The 7 alkyl ha idemay be conveniently obtained by chlorinating-the z-proper petroleumiraction such as aizkerosene fraction. The-aromatics suitable in the previousmxamples are likewisesuitablein this method.

Typical -compoundswhich fallwithin this class are-.nonyl benzene, dodecyl benzene, pentadecyl benzene,,nonyl-toluene, dodecyl toluene, pentadecyl toluene, dodecyl ,Xy1ene,-andthe like. Obviously,-,alarge number of-simila-r-compounds might be .enumerated; however,.in theinterest of brevity eandnlarity, it.-is:sufficient to state that all compounds having an aromatic .nucleus with one side-chain containing from 8 170 15 carbon atoms and-including-also those compounds whereinetheraromatic nucleus has, in addition to the 8 -,to ;15 carbon ,atom side-chain, one or more short chain .alk-yl radicals up to -3 carbon atoms in:-length.

rflhe agentswhich may be employed in sulfonating the alkyl aromatics toproduce-the alkyl aryl sulfonic acid include sulfuric 'acid ranging in concentration from-about 98% to-100%,-fuming sulfuric acid containing 'up to free S03, chlorosulfonic acid, and similar reagents.

The alkylaryl sulfonicacid resulting from the sulfonatlonsterrmay-beneutralized with a variety of ;:alkalinecompounds, forexample, with an alkali or alkaline earth metal hydroxide or carbonate, with ,ammorula, or with various amines including primary; secondary, and tertiary alkyl amines, alkyl alkanol ,rami-nes, -alkanol amines, hetero cyclic amines; or other alkaline compoundswhich will produce "watersoluble su'lfonates. Specific examples of the :aminesi-nclude methyl amine, dimethylamine, -trimethylami-ne, ethanolamine, diethanolamine, diethyl ethanolami-ne, ethyl -diethanolamine, itriethanolamine, pyridine, methyl pyridine, randrsimilar compounds.

The water-soluble alkyl aryl sulfonate soap resultinafrom the neutralization step may be used :inthe zfinal composition either alone or in combination with various amounts of asimilar soap ,orysoaps prepared as above described.

=Thejlecithins whichwmay be used include'both the animal and vegetable types, all of which are structurally, esters of-glycerol and resemblea .fat, b ut-; difier .therefrom in that .at least one .f-atty acid, radiealis replaced by a complex amine-phos- 'Saponin The amine is a quaternary The phoric acid radical. ammonium compound known as choline.

,lecithins of the vegetable type are derived from :soy bean, corn, linseed, peanut, ,or other similar oils and are commercially available as dispersions -or solutions in from 30% to 40% of the oils. The

term lecithin, as used herein and in the of thele-eithinand 35% of the oil. Soya lecithin is especiallyuseful from the standpoint of availability and low cost.

The amount of lecithin employed varies with qthejintended use of the final detergent. However, 'in'general, the amount ranges between 20% to 7.0% "by .weight based on the dry sulfonate. Amounts less than 20% ;'fail to impart detackifyinsnroperties to the finished detergent, whereas amou ts greater than 70% interfere with :the detergenteand .lethering properties of the finished product. .It :has been vfound, in v.tact, hat ithe addition ,oiilecitliin toaalkyl aryl :sulfonate compositionsiails to improve detergentactiomlathering, or foamstability of-the: finished detergent. The only effect of the'lecithin, as has beenrstated, is to improve the :extrudability and eliminate tack. The-amountof sulfonate and'lecithin in the. finished detergentpreferably ranges between 5% and 65 %,-and 1%.to40%,,respectively. How'- ever, in all cases, including those'intermediate theabove limits, the amount of the lecithin by weight based upon the weight of :sulfonate must range between 20% and 70%. The remainder of the composition mayconsist of'fillers, dyes, per- 1 fumes,.emol1ien-t -oils,-and waxes, all of which-are inert with respect "to detergent action. Small amounts of short-chain sodium alkyl aryl sulfonates Such as sodium xylene ;-sulfonate, sodium isopropyl sulfon-ate, sodium isopropenyl sulfonate, and the like, may ,beadded ,to the composition forthe purpose of producing 'rapidsudsing .of the finished detergent, but this refinement is not necessary or critical.

As 'hereinbefore stated, the instant compositionsare-suitablefor both :solidand liquid formulations. In the two-tables immediately-following, typical formulations are shown giving desirable percentages of components, on the basis of the weight of the finished composition for a bar soap (Tablet) and a liquid soap (Table l1). These examples are not .totbeconstrueda's limiting-the invention, since, as is well known in the artofsoapmanufacture, many-modifications may be made by the additionof various inert materials, some of which have .been. enumeratedhereinbefore.

TABLE vI Bar soaps "Per cent Alkyl aryl sulfonate '15 to 50 Lecithin .3 to '25 Starch 0 to 50 China clay 'O'to 35 Talc .,0 to 35 Xylene sulfonate 0 to 0 Polyethylene glycol waxes 0to'l0 (2000-6000 mol. wt.) Natural waxes '(carnau'ba, cande'llila, bees, etc.)

In all cases, the .amountof lecithin ranges between l2)0% and 70% of the alkyl aryl sulfonate on tlry weight asis.

Liquid soaps Per cent 1 The upper limit given is true only for alkyl aryl sulfonates which are soluble to the extent, for example, the triethanolamine sulfonates; other "sulfonates such as alkali metal sulfonates are soluble in water in an amount only up toabout 30% by weight, which obviously would define the upper limit in those cases.

I In the case of the liquid soaps, as in all others, the weight of lecithin ranges between 20% to 70% by weight of the sulfonate. Where the sulfonate is present in amounts near the upper range of concentration it maybe impossible to have the lecithin present in amounts approaching 70% because of r'solubility limitations. Where, however, the amount of sulfonate is somewhat removed from the upper range, the amount of lecithin may be increased accordingly. By way of example, a composition might contain 40% sulfonate, 28% lecithin, and 32% water. Compositions haying amounts of sulfonate and lecithin near the upper limits of the above stated ranges for liquid soaps, may actually be cream or gel-like in form suitable for shampoos, whereas compositions containing amounts of sulfonate and lecithin nearer the lower limits will be true TABLE III 6 the weight of the dry salt cf'the alkylarylsulfonic acid. 1 p 2. A detergent composition comprising a watersoluble salt of an alkyl aryl sulfonic acid in which the alkyl radical contains from 8 to 15 carbon atomsand from to 70% of lecithin'by weight based on the weight of'the dry salt'of the alkyl aryl sulfonic acid. r

3. A detergent composition comprising the sodium salt of an alkyl aryl sulfonic acid in which the alkyl radical contains from 8 to 15"carbon -atomsand from-20% to 70% of lecithin by Weight:

based on the weight of the dry salt. r

4. A detergent composition comprising the triethanol amine salt of an alkyl aryl sulfonic acid in which the alkyl radical contains from 8 to 15 carbon atoms, and from 20% to 70% of lecithin by weight based on the weight of the dry salt.

5. A detergent composition comprising the sodium salt of nonyl benzene sulfonic acid and from 20% to 70% of lecithin by weight based on the weight of the dry salt. U

6. A detergent composition comprising the sodium salt of dodecyl benzene sulfonic acid and from 20% to 70% of lecithin by weight based on the weight of the dry salt.

7. A detergent composition comprising the sodium salt of pentadecyl benzene sulfonic acid and from 20% to 70% of lecithin by weight based on the weight of the dry salt.

8. A detergent composition comprising the magnesium salt of dodecyl benzene sulfonic acid and from 20% to 70% of lecithin by weight based on the Weight of the dry salt.

9. A detergent composition comprising a watersoluble salt of an alkyl aryl sulfonic acid in an amount ranging between 1 5% and 65% of the total weight of the detergent and lecithin in an amount ranging between 20% and 70% by weight based on the weight of the dry salt of the alkyl aryl sulfonic acid.

Composition (amounts in parts by Weight) Component sodium dodecyl benzene sulfona .4 100 100 150 100 50 25 130 sodium nonyl benzene sulionate 4. 75 magnesium dodecyl benzene sulfonate 150 75 25 triethanol amine salt of dodecyl benzene sulfonic acid soya lecithim; '50 70 50 5O corn lecithin i 40 linseed oil lecithin t 150 90 80 200 100 25 10 xylene sulionate 75 2O 5 25 20 polyethylene glycol wax (mol wt. about 6000) 30 10 30 15 10 carnauba wax. in 5 beeswax 5 10 8 10 In all of the above examples, the active deterr sulfonates, however, if desired, a'portion of the alkyl aryl sulfonate or sulfonates may be replaced with other known detergents such as alkyl sulfates, alkyl aryl sulfates, fatty acid soapsand similar compounds.

I claim:

1. A detergent composition comprising a watersoluble salt of an alkyl aryl sulfonic acid and 7 from 20% to 70% of lecithin by weight based on 10. A detergent composition comprising a gent component of such formulations is shown as water-soluble salt of an alkyl aryl s lf ni i an alkyl arylsulfonate or mixture of alkyl aryl in which the alkyl radicalcontains from 8 to 15 carbon atoms, said salt of the sulfonic acid being present in an amount ranging between 15% and 65% of the total weight of the detergent,

O and lecithin in an amount ranging between 20% carbon atoms, said salt being present in an amount ranging between 15% and 65% of the 1 total weight of the detergent, and lecithin in an amountranging between 20% and 70% by weight based on the weight of the dry salt.

VINCENT J. KEENAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,232,117 Kyrides Feb. 18, 1941 FOREIGN PATENTS Number Country Date 1 473,638 Great Britain Oct. 18, 1937

Claims

1. A DETERGENT COMPOSITION COMPRISING A WATERSOLUBLE SALT OF AN ALKYL ARYL SULFONIC ACID AND FROM 20% TO 70% OF LECITHIN BY WEIGHT BASED ON THE WEIGHT OF THE DRY SALT OF THE ALKYL ARYL SULFONIC ACID.