CA1077849A - Betaine with anionic and nonionic surfactant in non-irritating detergent - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
High lathering detergent compositions having excellent foam stability and low ocular irritation com-prise a member selected from the group consisting of surfactant alkylbetaines, alkylamidobetaines, alkylsulfobetaines, and alkylamidosulfobetaines; an anionic surfactant; and a water-soluble, polyoxy-ethylene derivative of a hydrophobic base as the nonionic surfactant in a weight ratio of about 1:1:3, respectively.

Description

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-: Back~round of the Invention . _ ~
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The present ~nvention relates to detergent compositions ~nd shampoos, and more particularly to thoæe deterge~t compositions and shampoos which have r~latlvely low ocular irrltatlon and yet have large ~oam volume and improved ~oam stability.
.', Detergent compo61tions, like most type~ o~
liquid cleaning agentsl generally compri~e a mixture o~
one or more ~ur~actantC as the active lngredlentl per-~.
~umes, coloring agents, thi~keners, etc. The sur~actantæ
h~ve two portions :1) hydrophoblc hydrocarbon chain miscible with organic material~ and 2) a h~drophilic end-group mi~cible with water. When such a ~ur~actant cont~ct~
a particle o~ ~oil, the hydrocarbon chain~ mix there-with and the hydrophilic end-gro~p~ are presented to the aqueous solution. Thls process of emulsification allows the soil, which otherwise would resist removal by the water~ to be cleaned from the body thereby, The ;` surfactants may be classi~ied as anionic, cationic, nonionic, or amphoterlc, depending upon the character ,: . .
o~ the end-groups.

It is desirable that deter~e~t compo3itions . .
have high ~o~m volume and foam ~tabllity, particularly i~ they are used as shampoos. The amount of foam or lather produced by a shampoo has a direct bearing on the perceived ef~lciency with which lt clean~ the halr. The ~ ~tability of that foam indicate~ how long lt will keep -~ khe hair lathered, Generally ~peaking, the larger the :.

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volume of ~oam produced and the more stable the ~oam, the more e~ficient the perceived cleaning action of the shampoo.

A ~urther desirable property ~or a shampoo, e~pecially one deeigned for use by ch~ldren, is ~hat it .
have l~w ocular irritation, Because a shampoo may accidentally contact the ocular mucosa during use, especially use by children, one which causes relatively little irritation is both desirable and useful. Such non-irrltating shampoo~ are known, ~ee for example Ma8ci, et al., United State~ Patent No. 3,055,836 but these generally have poor ~oam stab1llty, Surfactant betaines are generally known as amphoteric sur~actants use~ul in detergent compositions.
: See, ~or example, Unit ed States Patent No. 3,280,179, . 15 which teQche~ that high-lat~ering detergent Compo~itionB
may be pre~ared by replaclng some or all o~ the anionic or cationic surfactant in conventional shampoo ~ormulat~ons by the acyclic sulfobetain~ disclosed therein or by i~corporating the latter ~nto conventivnal soaps, But ~0 while these CompOBit~onS have large foam volume and foam stability, they are ~evere ocular irritants and hence are unsuitable for use by children or others who desire a .:. - . .
non-irritating shampoo, Although a low-irritation3 hlgh ~oam shampoo comprising a betaine and other amphoteric . ~5 3ur~actants ha~ suppo~edly been suggested by Ceccarelli and Proserplo [Riv, Ital, Es~enze, 59(9):573-577 (1971)], . applican~l ~ollowing of thi~ teachlng ylelded a shampoo which i8 a ~evere ocular irritant, ~hlle appllcants recognize~ that the u~e o~ ~ur~actant betaine~ ln ' .,.:
- _2_ ; ~.
8gL~
~ .

detergent composit~ons i8 taught by the~e publication~, there iB no suggestion o~ the formul~tions o~ the pre-sent invention, which comb-lne high foam and good ~oam st~bility with low ocular irritation.

, .:~ Summary o~ the Invention ` 5 Now it ha~ been discovered that a detergent ` compo~i~ion compri~lng a sur~a~tant betaine (as de~lned below), an ~nionic sur~actant, and a water soluble 3 poly-oxyethylene derivative of a hydrophobic ba6e as the . n~nionlc ~urfactant i~ relatively non~irritating to the ~10 eye whlle providing high foam volume and improved foam stablllty.

As u6ed herein, the term "sur~actant be~aine"
meanB compound~ having the ~ormula:
i,,,, _ ~
. - . , 11 ¦4 Rl2 ~ - - C - N - (CH2)m ~ . ~3 : n ., (I~
Wherein~ Rl is a member selected from the group consi~t-,15 ing of COO~ and Cl-CH2S03-, OH
-~ R2 is loweralkyl;
... .
:~ R3 is loweralkyl, R4 is a member selected ~rom the group con~isting o~
.j20 hydrogen and loweralkyl;
R5 is higher alkyl;
Y is loweralkyl, preferably methyl, m i~ an integer from 2 to 7; and n i~ the integer 1 or 0.

778~
i The term .~"alkali metal" i~ generlc to lithium, ~odium, and potassium The term ~alkaline earth metal" i8 generic to beryllium, magne~ium, calcium, strontium, and barium"
The term "loweralkyl" means stralght or branch chained, saturated, aliphatic hydrocarbon radlcal~ and substituted hydroc~rbon radicals having ~rom one to about three carbon atoms ~uch as, for example, methyl, ethyl, propyl, i~opropyl3 hydroxypropyl, hydroxyethyl, and the like. The term "higher alkyl" means straight or branch chained ~aturated and un~aturated aliphatic hydrocarbon radicalæ having from :. about eight to about twenty carbon atoms 8uch a~, for example, lauryl, cetyl, stearyl, oleyl, and the llke. It should be under~tood that the term "higheralkyl" lncludes . mlxture~ of a hlgh molecular weight alkyl radical~ which ; 15 may conta~n one or more intermediate linkage~ such a~
. ether or polyether l~nkages or non-functional substitutents such as hydroxyl or halogen radicals which do not affect the hydrophobic character of the radical.

.~ Example~ of surfac~ant betaines of formula (I) wherein n is zero which are use~ul herein include the alkylbetaines such as cocodimethylcarboxymethylbetaine, lauryldimethylcarboxymethylbetaine~ lauryldimethyl_ . ~,. . .
alpha-carboxyethylbetalne, cetyldimethylcarboxymethyl-m betaine, lauryl-bi~-(2-hydroxyethyl)carboxymethylbeta~ne, `~ 25 `stearyl-bis-(2-hydroxypropyl)carboxymethylbetaine, oleyldimethyl-.~amma-carboxypropylbetaine, lauryl-bi~-(2-hydroxypropyl)alpha-carboxyethylebetaine, etc.
The sulfobetaine~ may be repre~ented by cocodimethyl-ulfopropylbetaine, ~-tearyldlmethyl~ulfopropylbetaine, _L~_ ~L~7~
',~
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lauryl-bls-(2-hydroxyethyl)sulfopropylbetaine, and the like.

~ Sur~actant amido betaines and amidosulfo bet~ines - use~ul in the present invention are exemplified by com-pound~ of formula (I) wherein n is one but otherwise corresponding to the above examples. Examples of sur-factant betalnes of ~ormula (I) wherèln n i8 one which are u~eful herein include the amidocarboxybetaines, such a~ cocoamidodimethylc~rboxymethylbetaine, laurylamido-dlmethylc~rboxymethylbetaine, cetylamidodimethylcarboxy-methylbetaine, laurylamldo-bi~-(2-hydroxyethyl)-carboxymethyl-beta~ne, etc. The amidosul~obetaines may be repres~nted - by cocoamidodimethyls~lfopropylbetalne, stearylamidodi-methyl~ulfopropylbetaine~ laurylamido-bis-(2-hydroxy-ethyl)-~ul~opropylbetaine, and the like.
~ , The preferred betaine ln the present invention ls ~ member selected from the group consistlng of sur-factant amidocarboxybetaine6 and amidosul~obetaine6.
More preferred betaines are the sur~actant amidocarboxy-betaines~ particularly stripp0d cocoamidodimethylcarboxy-methylbetaine, sold by Goldschmidt Co. under the trade Tegobetaine C. m iæ most preferred betaine ha~ the ~ormula: 1l ICH3 R5-C-NH-(CH2 ) 3 7 2 CH

wherein ~5 i~ a mixture of C8 ko C18 alkyl radlcal~
~5 derived ~rom single distilled strlpped coconut oil, the ma~ority o~ ~aid alkyl radical~ being C12.

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It i~ envisioned that any an~onic aur~actant : may be used in the detergent compo~ltion of the inven-tion such as 3 for example, an alkyl sulfate of formula R-CH2-OS03X, an alkylether sulfate of formula R(OCH2CH2) OS03X, an alkylmonoglyceryl ether sulfonate of formula R-OCH2 T-CH2-S03X, an alkyl monoglycerlde sulfate o~
OH
~ormula RCOOCH2CI-CH20S03X , an alkyl monogl~ceride OH
sul~onate of formula RCOOCH2CH-CH2SO3X3 ~n alkyl sulfonate OH
of ~ormula RSO X, an alkylaryl ~ul~onate of formula R~ r~--~

03X, an alkyl ~ulfo~uccinate of formula R-CH2-0-C-CH -CH2-C-OX, ,......................................................................... .

~ an 81kyl ~arco~inste of formul R-C-~ -CH -COOX, an .~15 acyl isethlonate of formula R C-O-CH2CH2S03X, an alkyl O CH
. methyl t~urideo~ ~ormula R-C-N - CH2-CH2S03X, a fatty O R O
acid protein condensate of formula RC-(NH-CH-C-NH-CH)r-COOX, an alcohol ether carboxylate of formula R(CH2CH20) -COOX, and the like, wherein R i~ higheralkyl havlng ~rorn 8 to 18 carbon atom~, R and ~ are member~ each ~elected from the group con~i~ting o~ hydrogen, loweralky~ hydroxy-loweralkyl, thloloweralkyl, carbox~lower-alkyl, aminolower-alkyl, benzyl, and p-hydroxybenzyl; X is a member ~elected `` -6-. .

7~ 9 from the group con~isting o~ alkal-L metal ion~ alkaline :~ earth metal ions~ ~mmonium ion~, and ammonium ion~ sub-~tltuted wlth ~rom one to three loweralkyls; p is an integer ~rom about 2 to about 6; q is an integer ~rom 2 ; to about 6 and r i~ an integer ~rom 2 to 10.

The pre~erred type of anionic sur~actant is an ~lkyl ether ~ulfate, more preferably ~odium tridecylalcohol ether ~ulfate in whlch q i8 ~bout 4.4, known as tridecyl alcohol ether (4,4) sul~ate, .10 me nonionic ~urfactant of the invention i8 a - water-~oluble polyoxyethylene derivatlve o~ a hydrophobic base, ~ald derivative being a member of .the group consist-ng o~:
(aj The reaction products o~ 9-20 carbon atom ~atty ac~d ~onoesteræ of aliphatic polyhydr~c alcohols, which polyhydric alcohols contain at lea~t 3 hydroxyls, with at le~t 10 moles of ethylene oxide, (b) The reaction producta of 9-20 carbon atom alcohols, acids and m~rcaptans. wlth at lea~t 2/3 a~ many ethylene oxide units a~ the number o~ carbon atoms in the hydro~hobic ~aæe, (c) The reaction product~ of 12-24 carbon atom alkylphenol~ and ~lkylcylohexanols wlth at lea~t a~ many ethylene oxide ~nit~ aæ the number o~ carbon atom~ in the hydrophobic ba~e, and (d) Block copolymers of propylene uxide and ethylene oxide havlng the ~ormula:
(CH2CH2)a(CI C~I20)b(CH2CH2o)cH

, 7t7~

Whereln a i~ an integer greater than ~even~ b iB an inte~er ~rom about five to about twenty, and c i~ an lnteger, all such that (a plus c) is at lea~t equal to b and i~ pre~erably at least twice b. Thi8 latter condition on the ~tructure o~ use~ul block copolymer~
is designed to include only those wh~ch are suf~iciently hydrophilic to give adequate ~table ~oam. The u~eful block copolymers should also have a molecular weight ~r~m about 1,000 to about 20,000.

.
me preferred type of nonionic sur~actant is a member aelected from class "a", above, more preferably .~ polyoxyethylene ~orbitan monolaurate havlng about 44 ;-i polyoxyethylene moietie~, called polyoxyethylene (44) ~orbitan monolaurate. ThlB pre~erred nonlonic sur~ac-tant is a c~mplex mixture, the hydrophobe o~ which i~
derived from aingle dl~tilled stripped coconut oil.

-~ The detergent composition of the in~entlon comprises a ~urfactant betaine, an anionic ~urfactant, .`;20 and a nonionic 6urfactant in a certain relationship to be deflned below. Applicant~ belleve, without intending to be bound thereby, that the amphoterlc ~ur~actant betaine and the anionlc sur~actant form a 1:1 complex ln the detergent compo ition o~ the invention. It is there~ore preferred that the molar ratio o~ ~ur~actant '' ~77~

`~ betalne to anionic surfactant fall between about 0.9 and about 1.1. A slight molar excess o~ betaine iB more ` pre~erred. I~ the betaine and the anionic sur~actant ~re selected to have similar molecular weights then formulation of the detergent composition in terms of equal weights, thereo~ i~ valid. Should there be a signific~nt di~p~rity between their molecular weights~
however, an equlmolar ~ormulation must be used. While a mo~ar r~tio between the above values i8 preferred, one could devlate there~rom at the cost o~ a slight increa~e in ocular irritation.

; Considered in terms o~ thls complex or comblna-tion o~ surfactant betalne and anionic sur*actant, the nonionic urfactant comprises ~rom about 0.5 to about 2.5 `;15 times th2 combined welght of said surfactant betaine and said anionic surfactant, preferably from about one to about two times~ and most pre~erably about 1.5 tlmes. If the æur~actant betaine and the anionic surfactant are selected - to have sub~tantially ~imilar molecular weightsg as the pre~erred surfactant betaines and anionic surfactants do, than the ratio of surf~ctant betaine to anionic surfactant to nonionic sur~actant should be from about 1:1:1 to 1;1:5, preferably from about 1:1:2 to ~ 4, and more pre~erably about 1:1:3.

~5 The detergent compo~itions of the invention are prepared by first mixing the surfactant betaine and the anionic surfactant at ambient temperature until a homogeneous mlxture i~ formed, and then addlng the nonionic surfactant and mixing the whole at elevaked tem-:'' _g_ ~0 7~
peratures (about 50C) ~or about ten minute~ untll a homogeneou~ mixture is ~ormed. The pH i~ then ad~u~ed to 7.2 + 0.3 by addltlon of a strong acid (e.g~ hydro-chloric acid) or a strong base (e.g. aqueous sodium hydroxide solutlon) as needed.

It i~ of course contemplated, and considered to be a part o~ the pre~ent invention, that one could u~e more than one of the sur~actant betaines, or more than one of the anionic surfactants, or more than one of the nonionic sur~actants in the detergent composition o~ the invention 80 long as the ~bove teaching about ; relative amounts o~ each type o~ sur~aetant 1~ fol~owed~ -The detergent compoaitions o~ the invention may be u~ed to cle~n hair and produce high ~oan volume and good ~oam ~tability whlle al~o having low ocular irrltation. The detergent compositions of the invention may al~o be u~ed as liquid soaps or clean~ers for cleaning other parts o~ the human body, animals, inanimate ob~ect~
and the like.

The detergent compositions o~ the invention may be combined with water or other suitable solvents to yield the hlgh lathering ~hampoos of the invention, which have good foam ~tability and low ocular irritation.

The shampoo of the invention comprises ~rom about 2~ to about 15% by weight of surfactant betaine, from about 2~ to about 15% by weight of anionic ~ur~ac-tant, and from about 5~ to about 30~ hy welght o~
nonionic sur~ctant baaed upon the weight o~ the entire composition. The remainder of the shampoo la es~entially water~ but the ~hampoo may al~o contain :

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thickeners, dyes, per~umes, preservatlves, pH ad~u~ter~, and the like, as desired. The pre~erred composition ~or the shampoo of the invention 1~ ~rom about 2% to abou~ 8% by weight o~ sur~actant betaine, ~rom about 2% to about 8% by weight of anionic surfactant and from about 10~ to about 20% by weight of nonionlc sur~actant based on the weight of the compo6ition. The most preferred shampoo comprlses about 5% by weight o~ surfactant betalne, about 5% by weight o~
~ anionic surfactant ~ , and about 15% by weight o~
nonionic surf~ctant based on the weight of the composition.

The shampoo o~ the invention is prepared by mix-ing the surfactant betaine and the anionic surfacta~t to-gether wlth a small amount of deionized water, preferably at ambient temperature, to form the above-mentioned complex.
Then the nonionic surfactant and a thiskener ~if de~ired) CJ~o/oy e~
are mixed ln. Elevated temperatures may be ~q~ ff}} at this ~tageto promote easier mixing of the ~ngredients, Then more delonized water i~ mixed in to bring the weight ~-~ of the compo6ition to about three-quarters of it8 ~inal we~ght, and the pH is ad~usted to 7.2io.3 by addition of a mineral acid (e.g., hydrochloric acld) or a solution of a Rtrong base ~e.g., sodium hydroxide). Finally, the remalnder o~ the deioniæed water ls added and the pH is again ad~u~ted. Other ingredients, such as pre~ervatives, dyes, perfumes, and the like may be added in any o~ the ^~ last three ~teps.

The shampoos o~ the invention po~ess low ocular irritation as shown by the ~ollowing modl~ied Draize test (See J.H. Draize, et al., Toilet Good~ A~sociations ~17, May, 1952, #1 Proc. Sci, Sect,):

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778~i9 .:

A 0~1 ml~ 6ample~ o~ the ncutral compoa~tion under test is dropped into one eye o~ ea~h of slx rabbits.
D~ily administration o~ the same quantity o~ each of the sample8 i6 continued for 3 con~ecutive days. Observations are recorded after one hour, one day, two days, three days, ~our days and seven days after sample6 are dropped into the eyes. The extremes o~ the re~ults either show sub-st~ntially no chan~e ~r æhow only a slight irritation (forelgn body effect) in the appearance o~ the rabbits' eye~ a~ter ~even d~ys, or se~ere irrit~tion or complete corneal opacity, as the case may be.

` The ~h~mpoo8 prepared in ~xamples I through XII
were tested by this procedure and were ~ound to be only sllght ~rritant~, even though they each contain about 25% by weight of surfactants and would therefore be expected to be severe irritants.

The shampoo of the invention moreover posse~ses both a high foam volume and foam stability as mea6ured by the following modification of the well-known Ros~-Miles foam test ["Oil and Soap", lô, g9-lo2 (1941)]:

(1) Lanolin, anhydrous, cosmetic grade is mixed with dioxane (technical grade) in the proportion o~ 2 5 gr~mR lanolin and 100 grams o~ dioxane. The lanolin iB ~ir~t mixed wlth 25 cc. of dioxane. ThiB
` 25 mixture is heated o~er a ~team bath to 45 C in order to dissolve the lanolln in khe dloxane. The rema~nder ~`"

, ". , ~7~

o~ the dloxane is then added and mix~d. This lano-lin~loxQne solutlon, which ls ~tored in an amber bottle, should be prepared fresh on the day that the tests are - run.

(2) The shampoo to be te~ted is diluted by addlng 376 cc. o~ distilled water to 4 gram~ of the ~hampoo, and then adding 20 cc. o~ the lanolin-dioxane .. solution de~crlbed in (1) above while mixing. Heat is produced ~hen the lanolin-dioxane solution is added to 10 the solution o~ the ~h~mpoo in water and care must be taken in ad~usting the termperature of thls solution to 24~25C. Both o~ the~e intermediate ~olutions should therefore be ~d~u~ted to 23C, be~ore mixlng. The cool-: lng o~ the lanolin-dioxane solution ~hould be gradual ln order to ~void preclpitation of the lanolin. Thlæ
will produce ~ ~inal solution with a temperature of 24_25~, (3~ m e ~inal solution of shampoo, water, dioxan~ and lanolin de~cribed in (2~ 1~ then run in 20 the Ro~s~Miles ~oam column in the u6ual way. All te~ts are conducted in duplicate, and the average of the two results i~ taken.

(4) Fo~m ~tabllity iB determined by measur-ing the decay in fo~m height after ~ive minutes, ~5 - expres~ed a~ a percentage o:~ the orlgln~l height, :~ The ~hampoo o~ the invention i~ a ~uperlor : high-lathering ~hampoo by thi~ te~t when compared to, ~or example, the prlor art shampoo ~ Ma~ci, et al : -13 -- i ' because lt exh~bits a much smaller percent~ge decay then the prior art shampoo.

`; The shampoo of the lnvention is further descriked and illustrated in the following examples, wh~ch are set forth by way o~ lllustration only and not to limit the scope o~ the present lnvention. The betaines in the ~ollowing exampleæ are 30-32% active aqueous solutions, All parts are by weight unless otherwise indicated. --~ , .

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~L~7784~
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EXAMPLE I
.. .
In~edient~ ~ _ :j:
~ Tegobetaine C~ r~J~ ) 17.1 : , Tridecylalcohol ether sulfate2) (A) (65% active aqueous solution) 8.3 .~ Deionized water 5.0 (B) ¦ Polyoxyeth~lene (44) 60rbitan monolaurate 15.0 Deionized water 300 (C) Dye 0.002 (D) Deionized water, preservation, ~10 perfume, and thickener . ~ .
: 1) Formula:
1l IH3 stripped coco - C-NH-(~H2)3+ N - ~H C00~
;: CH3 2) Formula:

- R-~CH2CH 0~ _soV _ Wherein R is a branched 2 4.4 3 chain aliphatic hydro-carbon having 13 carbon `. atom~

: .
` ' . ~ . .

~(~77~

.... .

The ~irst three ingredients (Group A) are homogeneously mixed at ambient temperatureS after which the next ingr~di~t (Group B) is added, and the ; whole is mixed with heatlng ~t 50C ~or about 10 minute~
untll homogeneouæ. Then the nexk two ingredients .~ ~
(Group C) are added, the whole is mixed at ambient temperature, and the pH iB ad~usted to 7. 2 + 0.3 by addition o~ h~drochlorlc acid. Finally, the remaining ingredients (Group D) are added and the pH i8 again lQ ad~usted to 7.2 + 0,3 if necessary, yielding a high lathering ~h~mpoo with excellent foam ~tability and low ... ; ocuIar irritation.

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EXAMPLE II

a~ %

Lonzaine CSl) ~'tfqd~nar~) 19.0 c (~) Tridecylalcohol ether sulfate (as in Example I) 9.2 Delonized water 5.1 (B) ¦ Polyoxyethylene (40) ~orbitan monolaurate 12.6 (C) ¦ Deionlzed water 30.0 .. (D) ¦ Dye, per~um~, deionized water, preservatlves, and thickener q. 9 1) Formula:
ll IH3 stripped coco - C~ (CH2~3-~ CH2 T 2 3 . .
The ingredients are combined as in Example I
1~ to yi~id a hlgh-lathering shampoo with very good ~oam stab~llty and low ocular irritatlon, ' .

. -17-. .

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1077B~
' EXAMPLE III

~: %
.
~ Lonzaine CS (as in Example II) 17.0 (A) Tridecyl~lcohol ether sulfate . (as in Example I) 8.2 Deionized water ~B) ~ Polyoxyethylene (20) sorbitan 12.6 monolaurate Deionized water 30 . O
(C) Dye ' 5 (~) Deionized water, perfume, .:~ pre~ervatives, a~ thickener qcs.
~ 1005~

.... . .
The ingredient~ are comblned a6 in Example I
to yield a high-lathering shampoo with acceptable ~oam stability and low ocular irritation.
~; .

, .
`, ,:

.~ -18-.

.
:`

-' ~-~ 7 7 ~ ~

; EXAMPLE IV

Ex~mple III i~ repeated substituting trl-decyl alcohol ether sulfate o~ ~ormula R-O[CH CH20]3S03 for that used ~herein~ wherein ~ is as defined in Example I, The resulting shampoo is high-lathering and has acceptable ~oam stability and low ocular irritation.
.

EXAMPLE V

Following the procedure of Example III, but substituting Lonzaine C
O CH

(~ormula: stripped coco - C-NX-(CH2)3-7 -COO~) ~``~ for the Lonzalne CS~ u~ed therein, a high-lathering sh~mpoo ls produced which has very go~ ~oam stability and low ocular irritation.

EXAMPLE VI

Following the procedure of Example V, but sub-~tltuting the tr~decylalcohol ether sulfate o~ Example IV
~or that used therein, ~ h~gh-l~theri~g ~hampoo i~ pro-duced which has very good ~oam stability and low ocular irritation.

.. ~ .

~778~5~
EXAMPLE VII

. ~: %
.
5 VariOn CADG~ roJe~A~I~) 17.2 (A) ¦ Tridecylalcohol ether sulfate (As in Example I) 15~7 Deionized water 4.5 ;
(B) Polyoxyethylene (83) sorbitan .. monolaurate 15.0 Deionized water 30 0 ~C) Dye 5 (D) ~ Delonized water, per~ume, t preservatives, and thickenersq.sO_ ~ .
' 1007~
';
. ~ .
. 1) Formula:
-. ~ CIH3 whole coco C-NH-(CH2)3i7_ CH2C0 3 ~ CH3 ;. - Ashland Chemical Company ., :
- The ingredients are combined as in Example I~
.-15 but uaing sodium hydroxlde solution to ad~ust the pHg to yield a high~lathering shampoo with excellent foam stabillty and low ocular irritation.

. . .

;,,`
~ ~20_ ':

-7~

EXAMPLE VIII

- The procedure of Example VII is repeated twice, except that the ~irst time only 12.0~ polyoxy-: ethylene (44) sorbit~n monolaurate is used instead o~
15.0% and the second time 12.0% o~ a propylene oxide-ethylene oxide block copolymer sold by Wyandotte Co.
1Lra c/e)nA r K
~ under the ~ Pluronic F-68 1B sub~tituted for the - 15.06~ polyoxyethylene (44) sorbit~n monolaurate used therein. In both repetltion~, high-l~thering shampoo~
having excel~en~ ~oam stability and low ocular irritation are produced.

EXAMPLE IX

In~redient~:
. ..
Tegobetaine C ~r6~e~Ar~ ) 17.0 (A) Tridecylalcohol ether ~ul~ate (as in Example I) 8.3 Deionized water 5.0 (B) ¦ Polyoxyethylene (44) sorbitan I monolaurate 15.0 ¦ Delonized water 30.0 Dye 5 (D) ¦ Deionized water, perfume, ~0 preservatives, and thickeners _~ s.
1006j~
:
_21-.
. . ' .

~77~
` , , . .
~' The lngredients ~re comblned as in Fxample I~
except that ~odium hydroxide solution i~ ueed lnetead of hydrochloric acid to correct pH3 to yield a high lather-lng 8h~mp~0 with very good ~oam ~tabillty and low o~ular irritation.

, ,;. EXAMPLE X
'`" ' .
The procedure of Example IX iB repeated, except . , i .
that ~egobetaine L ~-tr~e~rlc) (Formul~ laurlc - C-NH~ 2)3~1 -CE2COO ) H

i~ substituted ~or the Tegobeta~ne C used therein3 to yield a high-lathering shampoo with excellent ~o~m 3tabillty und low ocular irritation.

~22-:

..

77B4~
EXAMPLE XI

Ingredlent~: %
-;~ Lonzaine 12CS~ r~le~ 17.1 i.i,~., (A) Trldecylalcohol ether sul~ate . (A~ in Example I) 8.3 Deionlzed water 5.0 (Bj ¦ Polyoxyethylene (20) sorbitan monolaurate . 12~7 Deionized water 30.0 (~) ~ye 0.5 (D) ¦ Deionized water~ p~rfume, ~ pre~ervatives9 and thickeners q~
100%

1) Formula: fH3 ,. atripped coco I - CH2- CH - CH2S03, . CH3 OH

The ingredients are combined a~ in Examine I~
except that ~od~um hydroxide ~olution i~ used instead o~ hydrochloric acid to correct pH~ yielding a high lathering ~hampoo with excellent ~oam stabillty and low ocular irrltation.

" -23-;
- EXAMPLE XII

In~redients:
.': .
Carboxybetaine 15 . O
(A) Tridecylalcohol ether ~ulfate ; (as in Example I) 15.0 ,. Deioniz0d water 5.0 ~., 5(B) ¦ Polyoxyethylene (20) sorbitan monolaurate 12.6 ¦ Delonized w~ter 30.0 . ~ (C) Dye O.5 (D) 3 Deionized water~ pre6er~atlve~
10~ perfumes, and thickener~ ______9 ~ ___ ` 100%
!~, : 1) Formula: CH3 stripped coco I - CH2- COG-CH
: 3 . The ingredient~ are combined a~ in Example I
to yield ~ hlgh lathering shampoo with good foam stabl~lty 15and low ocular irritation.
.
. .

-24_ ..
.,'.
,:

.

~' ~ 7 7 8 ~
:`

~XAMPIE XIII

The shampoo~ prepared in Examples I-XII are all tested ~or foam volume and foam stabillty by the Ross-Mile6 ~oam te~t described above. me resultB are tabulated below, EXAMPLE

III 85 41~
IV 91 40%
V 90 15%
~10 VI 88 14~
111 11%
VIIIA g2 7%
VIIIB 113 5~ ~ :
IX 99 19%
X 111.5 7.5%
XI 95 15%

For comparlson, the prlor art no~-irr~tating ~hampoo~
i o~ the Mascl, et al., p~tent exhibit about 50% decay in ~oam height after 5 minutes.

.: EXAMPL~ XIV

ExQmple I i~ repeated, but u~ing 25.0 parts of polyoxyeth~lene (44) aorbi~n monolaurate in place of the 15.0 parts used therein. The resulting high , .

1 ~7B91~
.

lathering ~h~mpoo has low ocular irritation and good foam stability.
''`

, EXAMPLE XV
;''' __ . ~. %
. ~
.
,~3 Lo~ ne CS~ r~le~Ar~) : Tridecylalcohol ether sul~ate . (as in Example I) 21.0 Polyoxyethylene (40) sorbltan ,~ monolaurate 2800 : Dye~ per~ume, preservative~, and thickeners ~ ~_ 100%
,.. .

1 ) Formula:

~trlpped coco ~ (CH2)3~ CH2-CH-CH2-S03 CH3 O~I

The ~ir t two ingredients ~re combined together and mixed~ after which the re~t are added and the whole "` i8 mixed with heatlng at 50 C ~or about ten minutes until homogeneous. The pH is ad~usted to 7,~ i 0.3, yielding a high latherlng dekergent compo~itlon wlth good foam stability and low ocular irritation.
` ' , ~ 7~89~9 EXAMP~E XVI

~: %
~`~rade~
~ ~ Tegobetalne J~(as ih ~xample I) 40.0 ,~ Trldecylalcohol ether sul*ate (a8 in Example I) 18.5 ~B) 1 Polyoxyethylene (44) Borbitan I monolaur~t0 30,0 (C) ¦ Dye 0.002 (D) Deionlzed water, preserv~ti~es, . perfume and thickeners ____g ~
100%

~ The ~ngredient~ are combined ~ in Example I ~. :
`10 to yleld a high latherine BhampOO wlth good ~o~ st~blllty ~nd low ocul~r irritation.
.~

EXAMPLE XVII

The procedure of Example I is repeated 3 but sub~tituting ~n equal weight o~ polyoxyethylene (80) sorbitan monolaurate ~or the polyoxyethylene (44) sorbitan monolaurate used therein, The resulting high lathering ~hampoo ha~ low ocular irritation and excellent foam ~' ' stability.
,'..................................................................... :

; .

.~

7~8~
' EXAMPLE XVIII

%
, .
.~ Tegobetaine C ~ro.de~ ) 17,O
~: (A) Tridecylalcohol (4.4) ether sulfate 8.3 Deion~zed water 5.0 .; Polyoxyethylene (100) sorbltan . 5 monol~ur~te 7 . 5 (B) ~
~: . Polyoxyethylene (80) ~30rbltan . monolaurate 7 . 5 ~, . Delonized water 30.0 ;' tC~
. : Dye 0.002 ` 10 (D) ~ Deionized water, preserVati~e8 ~ ~
and per~ume ___g ~ ___ ' 100%

The ingredients are combined a~ in Example I
to yield a h~gh latherlng shampoo with exçellent foam atabllity and low ocular irrltation.

.'` ~ / ~
Tegobetalne C ( ~ ~e~ 17.1 (A) ~ridecylalcohol (4.4) ether ~ul~ate 8.3 . Deioni~ed water 5 .0 ~:: Polyoxyethylene ~44) sorbltan m4nolaurate 9.0 (B) Polyoxyethylene (80) ~orbitan monopalmitate 6.o . ~ Deionized water 30.0 :.~. (C) Dye 0.002 . (D) ~ Deion~zed water, preservative~, 1 8,nd per~u~ne q. B .

.. _28-~771 3~

The ingredients ~re combined as in Example I to `; yield a high lathering ~hampoo with excellent foam skabillty ; and low ocular irritation.
' While the above examples have been given for lllustrative pUrpo~e~ one skilled ln the ~rt could make many modificati~n~ and deviations therefrom within the BCope of the pre~ent invention, which scope i6 de~ined only ln the appended claims.
'`.

.'' .
'` ~

, _~9_ ~`

Claims (12)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1) A detergent composition having good foam stability and low ocular irritation consisting essen-tially of:

a) a surfactant betaine having the formula:

wherein R1 is a member selected from the group consisting of COO? and , R2 is loweralkyl, R3 is loweralkyl, R4 is a member selected from the group consisting of hydrogen and loweralkyl, R5 is higher alkyl, Y is loweralkyl, m is an integer from 2 to 7, and n is the integer 1 or 0;
b) an anionic surfactant; and c) a water soluble polyoxyethylene derivative of a hydrophobic base as nonionic surfactant, the molar ratio of said surfactant betaine to said anionic surfactant being from about 0.9:1 to about 1.1:1 and the weight of said nonionic surfactant being from about 0.5 to about 2.5 times the combined weight of said surfactant betaine and said anionic surfactant.

2) A detergent composition as in claim 1 wherein the anionic surfactant is an alkyl ether sulfate of formula R(OCH2CH2)pOSO3X

wherein R is higher alkyl; p is an integer from about 2 to about 6; and X is a member selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, and ammonium ions substituted with from one to three loweralkyls.

3) A detergent composition as in claim 1 wherein the nonionic surfactant is a member selected from the group consisting of the reaction products of 9-20 carbon atom fatty acid monoesters of aliphatic polyhydric alcohols, which polyhydric alcohols contain at least three hydroxyls, with at least ten moles of ethylene oxide.

4) A detergent composition as in claim 1 wherein the surfactant betaine has the formula:

5) A detergent composition having good foam stability and low ocular irritation which consists essentially of:

a) a surfactant betaine having the formula:

wherein: R1 is a member selected from the group con-sisting of COO? and , and R5 is higher alkyl;
b) an alkyl ether sulfate of formula:
R(OCH2CH2)pOSO3X

wherein: R is higher alkyl;
p is an integer from about 2 to about 6; and X is a member selected from the group consist-ing of alkali metal ions, alkaline earth metal ions, ammonium ions, and ammonium ions substituted with from one to three loweralkyls.
as anionic surfactant; and c) a water soluble polyoxyethylene derivative of a hydrophobic base as nonionic surfactant, the molar ratio of said surfactant betaine to said anionic surfactant being from about 0.9:1 to about 1.1:1 and the weight of said nonionic surfactant being from about one to about two times the combined weight of said surfactant betaine and said anionic surfactant.

6) A detergent composition as in claim 5 wherein said surfactant betaine has the formula:

wherein R? is derived from single-distilled stripped coconut oil.

7) A high-lathering shampoo having good foam stability and low ocular irritation which comprises:

a) a surfactant betaine having the formula:

wherein R1 is a member selected from the group con-sisting of COO ? and , R2 is loweralkyl, R3 is loweralkyl, R4 is a member selected from the group con-sisting of hydrogen and loweralkyl, R5 is higher alkyl, Y is loweralkyl, m is an integer from 2 to 7, and n is the integer 1 or 0;

b) an anionic surfactant; and c) a water soluble polyoxyethylene derivative of a hydrophobic base as nonionic sur-factant, the molar ratio of said surfactant betaine to said anionic surfactant being from about 0.9:1 to about 1.1:1, and the weight of said nonionic surfactant being from about 0.5 to about 2.5 times the combined weight of said surfactant betaine and said anionic surfactant, said surfactant betaine comprising from about 2% to about 15% by weight of the weight of the shampoo, said anionic surfactant comprising from about 2% to about 15% by weight of the weight of the shampoo, and said nonionic surfactant com-prising from about 5% to about 30% by weight of the weight of the shampoo.

8) A shampoo as in claim 7 wherein the anionic surfactant is an alkyl ether sulfate of formula R(OCH2CH2)pOSO3X

wherein R is higher alkyl; p is an integer from about 2 to about 6; and X is a member selected from the group consisting of alkali metal ions, alkaline earth metal ions, ammonium ions, and ammonium ions sub-stituted with from one to three loweralkyls.

9) A shampoo as in claim 7 wherein the nonionic surfactant is a member selected from the group consisting of the reaction products of 9-20 carbon atom fatty acid monoesters of aliphatic polyhydric alcohols, which polyhydric alcohols contain at least three hydroxyls, with at least ten moles of ethylene oxide.

10) A shampoo as in claim 7 wherein the sur-factant betaine has the formula:

11) A shampoo having good foam stability and low ocular irritation which consist essentially of:

a) a surfactant betaine having the formula:

wherein: R1 is a member selected from the group con-sisting of COO ? and , and R5 is higher alkyl;

b) an alkyl ether sulfate of formula:

R(OCH2CH2)pOSO3X

wherein: R is higher alkyl;
p is an integer from about 2 to about 6; and X is a member selected from the group con-sisting of alkali metal ions, alkaline earth metal ions, ammonium ions, and ammonium ions substituted with from one to three loweralkyls.
as anionic surfactant, and c) a water soluble polyoxyethylene derivative of a hydrophobic base as nonionic surfactant, the molar ratio of said surfactant betaine to said anionic surfactant being from about 0.9:1 to about 1.1:1 and the weight of said nonionic surfactant being from about one to about two times the combined weight of said surfactant betaine and said anionic surfactant, said surfactant betaine comprising from about 2% to about 8% by weight of the weight of the shampoo, said anionic surfactant comprising from about 2% to about 8%
by weightof the weight of the shampoo, and said nonionic surfactant comprising from about 10% to about 20% by weight of the weight of the shampoo.

12) A shampoo as in claim 11 wherein said surfactant betaine has the formula:

wherein R5 is derived from single distilled stripped coconut oil.