United States Patent r 19J
`Birkofer
`
`[75]
`
`[54] MILD THICKENED SHAMPOO
`COMPOSITIONS WITH CONDITIONING
`PROPERTIES
`Inventor: Roger Clarence Birkofer, North
`Bend, Ohio
`[73] Assignee: The Procter & Gamble Company,
`Cincinnati, Ohio
`Apr. 8, 1975
`[22] Filed:
`[21] Appl. No.: 566,154
`
`Related U.S. Application Data
`[ 63] Continuation of Ser. No. 313,907, Dec. II, 1972,
`abandoned.
`
`[52] U.S. Cl ................................................... 424/70
`Int. CJ.2 ............................................ A61K 7/06
`[51]
`[58] Field of Search ....................................... 424/70
`
`[II]
`
`[45]
`
`3,962,418
`June 8, 1976
`
`[56]
`
`3,496,110
`3,590,122
`
`References Cited
`UNITED STATES PATENTS
`2/1970
`Shumway et al... ................... 424/70
`6/1971 Roberts eta!. ....................... 424/70
`
`Primary Examiner-Sam Rosen
`Attorney, Agent, or Firm-Robert B. Aylor; Ronald L.
`Hemingway; George W. Allen
`
`ABSTRACT
`[57]
`Mild thickened liquid shampoo compositions with
`conditioning properties comprise anionic surfactants,
`specific zwitterionic and amphoteric surfactants,
`polyethoxylated nonionic surfactants and a cationic
`cellulose ether thickening and conditioning agent.
`18 Claims, No Drawings
`
`1
`
`

`

`1
`
`3,962,418
`
`2
`alcohol sulfosuccinate monoester wherein said fatty
`alcohol contains from about 8 to about 16 carbon
`atoms, preferably from about 10 to about 14 carbon
`atoms, and said polyethoxylated fatty alcohol contains
`5 from about 1 to about 10 (preferably 1 to 5) ethoxy
`moieties per molecule, (3) a water-soluble (e.g., so(cid:173)
`dium, potassium, ammonium, triethanolammonium,
`etc.) N-fatty acyl sarcosinate containing a fatty acyl
`group containing from about 8 to about 16 carbon
`I 0 atoms, ( 4) a water-soluble alkyl sulfate containing from
`about 8 to about 16 carbon atoms, and (5) a water-sol(cid:173)
`uble N-fatty acyl-N-methyl taurine containing a fatty
`acyl group containing from about 8 to about 16 carbon
`atoms;
`B. a surfactant selected from the group consisting of
`( 1) a zwitterionic surfactant having the formula
`
`MILD THICKENED SHAMPOO COMPOSITIONS
`WITH CONDITIONING PROPERTIES
`
`CROSS-REFERENCE TO RELATED
`APPLICATIONS
`This application is a continuation of Application Ser.
`No. 313,907, filed Dec. 11, 1972, now abandoned.
`
`15
`
`BACKGROUND OF THE INVENTION
`1. Field of the Invention
`This invention relates to thickened liquid shampoo
`compositions with conditioning properties, particularly
`those which are very mild.
`2. Prior Art
`Compositions containing the reaction products of
`ethoxylated anionic surfactants and certain specific
`amphoteric surfactants and polyethoxylated nonionic
`surfactants have been disclosed in U.S. Pat. Nos.
`2,999,069 and 3,055,836, Masci and Poirier. Similar 20 wherein A, B, and Care each selected from the group
`consisting of 0 and 1, wherein A is 0 when B is 1 and A
`disclosures are contained in the corresponding foreign
`is 1 when B is 0, wherein C can only be 1 when Y is a
`patent applications such as British Pat. Nos. 850,514,
`sulfonate group, wherein each R2 is selected from the
`850,515, and 921, 122; and Canadian Pat. No. 595,532.
`In each of these patents, the disclosure is of a reaction
`group consisting of alkyl groups containing from about
`product formed between the anionic surfactant and the 25 8 to about 16 carbon atoms and a moiety having the
`- C(O)NH- R6
`- wherein R5 is an alkyl
`formula R 5
`amphoteric surfactant which contains ternary nitrogen
`groups, and there is no disclosure of thickeners.
`group containing from about 8 to about 16 carbon
`atoms and R6 is an alkylene group containing from 1 to
`Similarly, U.S. Pat. No. 3,580,853, Parran, discloses
`the cationic cellulose ether thickening and condition-
`about 5 carbon atoms (preferably 2-4 carbon atoms
`ing agents ofthis invention in shampoos to improve the 30 and most preferably 3 carbon atoms), wherein each R3
`deposition of particulate materials, but without.a spe-
`is selected from the group consisting of alkyl, hydroxy-
`cific disclosure of the surfactant systems disclosed
`alkyl and alkoxyalkyl groups which can be connected
`herein. The cationic cellulose ethers of this invention
`to form a ring and each of which contains from 1 to
`are known, having been generically disclosed in U.S.
`about 3 carbon atoms, wherein Y is selected from the
`Pat. No. 3,472,840, Fred W. Stone and John M. Ruth- 35 group consisting of sulfonate and carboxylate groups,
`and wherein R4 is an alkylene group containing from 1
`erford, Jr.
`The compositions of this invention are all mild. This
`to about 5 carbon atoms when Y is a carboxylate group
`is a very desirable characteristic. The mildness appar-
`and is selected from the group consisting of alkylene
`ently results from having a combination of anionic and
`and hydroxyalkylene groups containing from about 2 to
`cationic species present. However, as a result, many 40 about 5 carbon atoms when Y is a sulfonate group and
`anionic, cationic, and nonionic polymers are incompat-
`wherein the hydroxy group is on a secondary carbon
`ible with such formulas. It is extremely difficult to
`atom,
`,B-aminopropionate
`2. a water-soluble N-alkyl
`thicken such formulas and keep a single-phase clear
`composition. It is even more difficult to prepare a thick
`wherein the alkyl group contains from about 8 to about
`clear shampoo composition comprising anionic, zwit- 45 16 carbon atoms, and (3) a water-soluble N-alky1 {3-
`terionic or amphoteric, and nonionic surfactants which
`iminodipropionate wherein the alkyl group contains
`has good conditioning properties.
`from about 8 to about 16 carbon atoms;
`C. a polyethoxylated nonionic surfactant selected
`THE INVENTION
`from the group consisting of: ( 1 ) polyethoxylated alco(cid:173)
`This invention relates to the discovery of a thickened 50 hols, said alcohols containing an alkyl group either
`mild liquid shampoo composition having conditioning
`primary or secondary and either straight or branched
`properties comprising:
`chain, containing from about 8 to about 16 carbon
`A. from about 4% to about 8% of an anionic surfac-
`atoms and said polyethoxylated alcohols containing
`tant selected from the group consisting of
`from about 10 to about 45 ethoxy moieties per mole-
`1. a surfactant of the formula R(OC 2H4)n0S03M, 55 cule, (2) polyethoxylated a1kylpheno1s wherein the
`wherein R is a hydrophobic group selected from the
`alkyl group contains from about 6 to about 15 carbon
`group consisting of alkyl groups containing from about
`atoms and wherein the polyethoxylated alkyl phenol
`8 to about 16 carbon atoms, alkyl phenyl groups
`contains from about 10 to about 45 ethoxy moieties per
`wherein the alkyl group contains from about 6 to about
`molecule, (3) polyethoxylated mono fatty acid esters of
`15 carbon atoms, and fatty acid amido groups wherein 60 sorbitol wherein said fatty acids contain from about 8
`the fatty acid contains from about 8 to about 16 carbon
`to about 18 carbon atoms and said polyethoxylated
`atoms, wherein n is a number from about 1 to about 10
`mono fatty acid ester of sorbitol contains from about
`(preferably 1 to 5) and M is a non-toxic cation which
`10 to about 45 ethoxy moieties per molecule, ( 4)
`makes the surfactant water-soluble, preferably a cation
`polyethoxylated polypropylene glycol having a molecu-
`selected from the group consisting of sodium, potas- 65 lar weight of from about 2,000 to about 6,000 and
`sium, ammonium and triethanolammonium cations,
`containing from about 40% to about 60% by weight of
`(2) a water-soluble (e.g., sodium, potassium, ammo-
`polyethoxy groups, and (5) polyethoxylated fatty acids
`nium or triethanolammonium) polyethoxylated fatty
`wherein said fatty acid contains from about 8 to about
`
`2
`
`

`

`3,962,418
`
`3
`16 carbon atoms and said polyethoxylated fatty acid
`contains from about 10 to about 45 ethoxy moieties per
`molecule;
`D. from about 50% to about 85% water; and
`E. as a thickener and hair conditioning agent, from 5
`about 0.2% to about 4% (preferably from about 0.4%
`to about 2%) of a quaternary nitrogen-containing cellu(cid:173)
`lose ether having substituent groups of the formula
`
`4
`y( 3) ether sulfate, the sodium salt of polyethox(cid:173)
`ylated(3) C10-C14 mono fatty alcohol 'sulfosuccinate,
`the sodium salt ofC10-C 14 fatty acyl amido polyethox-
`y( 4) ether sulfate. Other suitable polyethoxylated an(cid:173)
`ionic surfactants are disclosed hereinafter in the exam(cid:173)
`ples.
`3. The zwitterionic surfactants. The zwitterionic sur(cid:173)
`factant provides major lather benefits while modifying
`the nature of the composition so that it i~ less ,strongly
`10 anionic. The molecular ratio of the anionic to zwitter(cid:173)
`ionic surfactant is from about 1:1 to about 4:1, prefer(cid:173)
`ably from about 1: 1 to about 3:1, most preferably from
`about 1:1.to about 2:1.
`Preferred zwitterionic surfactants are propylamido
`15 betaines derived from C 10-C 16 fatty acids, and the cor(cid:173)
`responding propylamido sultaines, and C 10-C16 alkyl
`sultaines wherein the cationic and sulfonate anionic
`groups are separated by a propylene group and the
`remaining groups are methyl groups. Specifically, pre-
`20 ferred zwitterionic surfactants are (a) those having the
`formula
`
`R6CO-NH- C3H 6 - N'+'(R7 ), - R8 -
`
`y<->
`
`(C,H,O- lmi-CH,CHO(CH,N'+'(R7 ),CI1- '
`)-].(C,H,O- ).H
`
`wherein each R7 is selected from the group consisting
`of methyl and ethyl groups, m + p ranges from about I
`to about 10 (preferably from about 1 to about 4, most
`preferably from about I to about 2), n is from about 0.1
`to about 0.5, the degree of substitution of the cationic
`group on the cellulose is from about 0.1 to about 0.5,
`and the viscosity of a I% solution of the cellulose ether
`at 25°C. ranges from about 100 to about 2000 centi(cid:173)
`poises, the molecular ratio of (A} to (B) being from
`about I: I to about 4: I; the weight ratio of (A)+ (B) to
`(C) being from about 2: I to about I :2; and the pH of
`the composition being from about 6.0 to about 8.0.
`
`25 wherein R 6 is an alkyl group containing from about 9 to
`about 15 carbon atoms, wherein each R 7 is selected
`from the group consisting of methyl, ethyl, and 2-
`hydroxyethyl groups, wherein Y is selected from the
`group consisting of sulfonate and carboxylate groups,
`30 and wherein R8 is a methylene group when Y is a car(cid:173)
`boxylate group and is selected from the group consist(cid:173)
`ing of propylene and 2-hydroxypropylene groups when
`Y is a sulfonate group; and (b) those having the for(cid:173)
`mula
`
`DESCRIPTION OF THE INVENTION
`I. The Thickener. The products of this invention are,
`in part, described in the co pending application of Ray(cid:173)
`mond Edward Bolich, Jr. and Robert Benson Aylor
`entitled "MILD SHAMPOO COMPOSITIONS," Ser.
`No. 313,908, filed Dec. 11, 1972. These compositions,
`and other compositions disclosed herein are very mild.
`However, it is very difficult to thicken such composi(cid:173)
`tions while maintaining the composition in a clear,
`liquid single-phase form. Most anionic, cationic and 35
`nonionic polymers are incompatible with such formu(cid:173)
`las. It was discovered, however, that the quaternary
`wherein R9 contains from about 10 to about 16 carbon
`nitrogen-containing cellulose ether described hereinbe-
`atoms~ wherein each R 10 is selected from the group
`fore is unique in its ability to thicken the compositions
`of this invention while maintaining the clarity of these 40 consisting of methyl, ethyl, and 2-hydroxyethyl groups,
`compositions. In addition, it has been discovered that a
`and wherein X is selected from the group consisting of
`surprising result is obtained upon dilution of the com-
`hydrogen and hydroxyl groups. Examples of other zwit-
`positions of this invention with water, as occurs during
`terionic surfactants are given in the examples hereinaf-
`use of the shampoos. Upon dilution, an effective hair
`ter.
`conditioning precipitate is obtained which conditions 45
`4. The polyethoxylated nonionic surfactant. The
`the hair to provide, e.g., superior wet-combing proper-
`polyethoxylated nonionic surfactant provides a mild-
`ties. Thus, the thickener is also a hair conditioner.
`ness benefit. It also contributes to the character of the
`Specific thickeners are described hereinafter. Those
`lather, although in general, the nonionic surfactant
`thickeners with lower degrees of substitution of the
`tends to control and diminish the amount of the lather.
`cationic group, e.g., from about 0.15 to about 0.25, are 50 The ratio of the polyethoxylated nonionic surfactant
`and zwitterionic surfactant to the polyethoxylated non-
`preferred. Also preferred are those thickeners having a
`value of m + p of about 1.5 and those thickeners whose
`ionic surfactant is from about 2: 1 to about 1:2, prefer-
`1% solutions have a viscosity of 125-1000 centipoises
`ably from about 1: 1 to about 1:2, and most preferably
`at 25°C.
`from about 1: 1 to about 1: 1.2.
`2. The anionic .surfactant. The polyethoxylated an- 55
`Preferred nbnionic surfactants include polyethox-
`ionic surfactants of this invention are very mild. It is
`ylated (15-40) sorbitan monoacylate (Cur~16; prefer-
`essential that the anionic surfactant be mild since it is
`ably monolaurate), polyethoxylated
`(40-80% by
`used in a molar excess over the amount of zwitterionic
`weight of the molecule) polypropylene glycol (M.W.
`surfactant present so as to minimize the amount of
`about 3-5,000), and polyethoxylated ( 15-40) fatty
`cationic species present. The anionic surfactant pro- 60 alcohols ( Cio-C14 ). Other examples of nonionic surfac-
`vides good lather properties. Typically, the composi-
`tants are disclosed hereinafter in the examples.
`tion will contain from about 4% to about 8% of the
`5. Water. 'Water is used to make up the shampoo
`anionic surfactant. The sodium salts of the polyethox-
`compositions to the desired physical form. For liquid
`ylated anionic surfactants are preferred, but any non-
`shampoos, there will normally be from about 50% to
`toxic, water-soluble salt can be used, including potas- 65 about 85% of water presen~, preferably from about
`sium, triethanolammonium, and ammonium salts.
`65% to about 80%.
`The preferred polyethoxylated anionic surfactants
`6. Other ingredients. In addition to the ingredients
`are the sodium salt of C 10-C 14 fatty alcohol polyethox-
`described hereinbefore, the shampoo compositions of
`
`3
`
`

`

`3,962,418
`
`5
`this invention can also contain other conventional
`shampoo components, including dyes, preservatives
`such as ethanol, perfumes, opacifiers, antibacterial
`agents, antidandruff agents, buffering agents, condi(cid:173)
`tioning agents, etc. Desirably, only ingredients which
`are not irritating to the eye are added.
`It is especially desirable and preferred to have buffer(cid:173)
`ing agents present to maintain the pH of the composi(cid:173)
`tion within the range from about 6.0 to about 8.0, pref(cid:173)
`erably from about 6.5 to about 7.5. Such buffering
`agents include NaOH, HCl, NaHP04, boric acid, etc. It
`is also very desirable to include antidandruff agents
`such as zinc pyridinethiol N-oxide.
`
`5
`
`6
`The choice of a proper thickener is complicated by
`the fact that the ingredients react with many anionic
`to
`thickeners and many nonionic
`thickeners fail
`thicken the compositions. The compositions of this
`invention can also contain another nonionic thickener,
`e.g., a hydroxyethyl cellulose (e.g., one with a D.S. of
`about 2.5 whose 1% solution has a viscosity of 3-4,000
`centipoises at 25°C.). This auxilary thickener is desir(cid:173)
`able in that it also tends to provide clear, single-phase
`I 0 compositions.
`All patents and applications referred to herein are
`specifically incorporated by reference.
`All percentages, ratios, and parts herein are by
`weight unless otherwise specified.
`
`EXAMPLE I
`
`Ingredient
`3-( N,N-dimethyi-N-Iaurylamino) propane-
`1-sulfonate (sultaine)
`Sodium salt of sulfated polyethoxylated
`coconut fatty alcohol (AE3S)
`Polyethoxylated( 20)tridecyl alcohol
`(f:l-methyl dodecanol) (PTA)
`Ethanol
`Cationic thickener ·2 (cationic cellulose
`ether of Claim 7 of U.S. Pat. No. 3,472,840,
`wherein a is 2, b is 2, q is 0, m + p
`is about 1.5, n and the degree of substi(cid:173)
`tution (D.S.) of the cationic group are
`about 0.2, and the viscosity of a I% solu(cid:173)
`tion is 125-1000 centipoises at 25°C.)
`Water
`
`pH adjusted to 7.0 with HCI
`EXAMPLE II
`
`Ingredient
`N-( 3-coconutacylamidopropyl)-N,N-
`d i( 2-hydroxyethyl)-3 -am inopropane(cid:173)
`sulfonate
`Sodium salt of sulfated polyethoxylated( 4)
`lauroylamide (ethoxylated amido sulfate)
`Tween 20
`Natrosol 250 HH [A hydroxyethyl cellulose
`(D.P.- 2.5) having a viscosity at 1%
`in water at 25°C of 3-4,000 centipoises]
`Cationic thickener -2
`Ethanol
`Water
`
`Ingredient
`Sultaine
`AE3S
`Polyethoxylated(50% )polypropyleneglycol.
`(molecular weight 3,000) (PPG)
`Cationic thickener -2
`Ethanol
`Perfume
`Distilled water
`
`Adjusted pH to 7 .0 with HCI.
`EXAMPLE IV
`
`Ingredient
`N-( 3-coconutacylamidopropyi)-N,N(cid:173)
`dimethyl-2-aminoacetate
`( Amido betaine)
`Sodium polyethoxylated(3 )Iaury! sulfo(cid:173)
`succinate (Ethoxylated sulfosuccinate)
`Polyethoxylated(20)sorbitol monolaurate
`(Tween 20)
`Cationic thickener -2
`Ethanol
`Distilled water
`
`Adjusted to pH of 7.0 with NaH 2P03
`EXAMPI_E Ill
`
`Adjusted pH to 7.0 with NaOH.
`EXAMPLE V
`
`Ingredient
`3-[ N-undecyl-N-ethyi-N-(2-hydroxyethyl)
`ammonio ]-butyrate
`Potassium polyethoxy lated( 3)
`tridecanolether sulfate
`Pol yethoxylated( 30 )sorbitol
`monococonutacylate
`Ethanol
`Cationic thickener -I (same as thickener
`of Example I except having a D.S. of
`the cationic group of 0.4 and a
`viscosity at 25"C. with a I% solution
`of about 1,500-3,000)
`Water
`
`Adjusted pH to 7.0 with HCI.
`
`Percent by Weight
`4.5
`
`7.0
`
`14.0
`
`7.0
`1.25
`
`balance
`
`Percent by Weight
`5.0
`
`8.0
`
`13.0
`0.5
`
`0.5
`7.0
`balance
`
`Percent by Weight
`4.00
`5.50
`14.00
`
`.60
`7.00
`0.25
`balance
`
`Percent by weight
`3.00
`
`7.00
`
`15.00
`
`0.50
`7.00
`balance
`
`Percent by Weight
`4.5
`
`6.6
`
`17.0
`
`6.0
`1.0
`
`balance
`
`4
`
`

`

`Ingredient
`AE3S
`Tween 20
`Amido betaine
`Cationic thickener -I
`Water
`
`Ingredient
`Sultaine
`AE3S
`Tween 20
`Cationic thickener -2
`Ethanol
`Water
`
`Ingredient
`Amido betaine
`Ethoxylated sulfosuccinate
`PTA
`Ethanol
`Cationic thickener -2
`Na3HP0,.12H 20
`NaH2PO,.H20
`Water
`
`Ingredient
`Amido betaine
`AE3S
`PTA
`Cationic thickener -I
`Water
`
`Ingredient
`Sultaine
`AEaS
`PTA
`Ethanol
`Cationic thickener -I
`Water
`
`Ingredient
`Amido betaine
`Ethoxylated sulfosuccinate
`PTA
`Ethanol
`Cationic thickener -I
`Water
`
`Ingredient
`Sultaine
`AE3S
`PTA
`Ethanol
`Cationic thickener -2
`Water
`
`Ingredient
`Amido betaine
`Ethoxylated sulfosuccinate
`Tween 20
`Ethanol
`Cationic thickener -2
`Water
`
`7
`
`EXAMPLE VI
`
`EXAMPLE VII
`
`EXAMPLE Vlll
`
`EXAMPLE IX
`
`EXAMPLE X
`
`EXAMPLE XI
`
`EXAMPLE XII
`
`EXAMPLE XIII
`
`EXAMPLE XIV
`
`EXAMPLE XV
`
`Ingredient
`Sodium N-alkyi(C 12;C,.) ,8-aminopropionate
`AE3S
`Tween 20
`Ethanol
`Cationic thickener -2
`Water
`
`Ingredient
`Sultaine
`AE3S
`Tween 20
`Ethanol
`Natrosol 250 HH
`Cationic thicke ncr -2
`Water
`
`EXAMPLE XVI
`
`Ingredient
`Sultaine
`Sodium N-coconut acyi-N-methyl tau rate
`PTA
`Cationic thickener -2
`Distilled water
`
`EXAMPLE XVII
`
`Ingredient
`
`3,962,418
`
`-continued
`
`8
`
`Percent by Weight
`6.50
`14.0
`5.00
`1.00
`balance
`
`Percent by Weight
`4.90
`6.60
`14.0
`0.50
`7.00
`balance
`
`Percent by Weight
`4.00
`8.15
`14.00
`7.00
`0.48
`0.65
`0.35
`balance
`
`Percent by Weight
`5.00
`7.15
`14.00
`0.50
`balance
`
`Percent by Weight
`4.90
`6.60
`14.00
`7.00
`0.50
`balance
`
`Percent by Weight
`4.00
`8.15
`14.00
`7.00
`0.50
`balance
`
`Percent by Weight
`4.50
`7.00
`14.00
`7.00
`0.46
`balance
`
`Percent by Weight
`4.00
`8.15
`14.00
`7.00
`0.46
`balance
`
`Percent by Weight
`4.00
`6.70
`14.00
`7.00
`0.50
`balance
`
`Percent by Weight
`4.50
`7.00
`14.00
`7.00
`0.30
`0.30
`balance
`
`Percent by Weight
`5.00
`5.50
`14.00
`0.50
`balance
`
`Percent by Weight
`
`5
`
`

`

`10
`
`9
`
`EXAMPLE XVIIJ
`
`EXAMPLE XIX
`
`C-cetyl betaine
`AE3S
`Tween 20
`Cationic thickener -2
`Water
`
`Ingredient
`Amido betaine
`Na N-lauroyl sarcosinate
`PTA
`Cationic thickener -2
`Distilled water
`
`Ingredient
`Amido betaine
`Sodium coconut ·alkyl sulfate
`Tween 20
`Cationic thickener -2
`Distilled water
`
`3,962,418
`
`-continued
`4.00
`7.50
`14.00
`0.50
`balance
`
`Percent by Weight
`5.40
`5.20
`14.00
`0.50
`balance
`
`Percent by Weight
`5.00
`6.00
`14.00
`0.50
`balance
`
`polyethoxylated( 6 )pentadecylphenol
`
`30
`
`When in the above Examples I-XIX the following
`zwitterionic surfactants are substituted for the specifi(cid:173)
`cally named zwitterionic surfactants, substantially 20
`equivalent results are obtained in that the shampoos
`are exceptionally mild to the eyes.
`1.
`4-[N-coconutacylamidopropylene-N,N-di(2-
`hydroxypropyl)-ammonio] butane-1-sulfonate;
`2.
`2LN-pentadecylamidopropylene-N-(3-hydroxy- 25
`propyl )-N-propylammonio ]ethane-1-sulfonate;
`3. 4(N-Iaurylmorpholino )2-hydroxybutanoate;
`4. 3-(N-Iaurylmorpholino )propane-1-sulfonate;
`5. 3-(N-tridecyi-N-methyl-N-propyl)-aminopropano(cid:173)
`ate;
`6. 4-( N ,N ,N-trimethylammonio )stearate;
`7.3-[N-methyi-N-(2-hydroxyethyi)-N-propylam(cid:173)
`monio ]eicosane-1-sulfonate;
`8. 5-[N,N-(3-hydroxypropyl)-N-methylammonio ]-3-
`hydroxydocosane-1-carboxylate;
`9. N-coconutalkyl betaine;
`10. C-cetyl betaine;
`11. C-hexadecyl betaine;
`12.
`3-(N ,N-dimethyl-N-coconutalkylammonio )-2-
`hydroxypropane-1-sulfonate;
`13.
`6-coconutacylamido-3-trimethylammoniohex-
`anoate;
`14. 7 -coconutacylamido-4-tri( 2-hydroxyethyl )-hep(cid:173)
`tane-1-sulfonate;
`15.
`3-[ N -( 3-coconutacylamidopropyl )-N ,N-dime-
`thylammonio ]-propane-1-sulfonate;
`16.
`3-[ N-( 3-coconutacylamidopropyi)-N,N-di( 2-
`hydroxyethyl )ammonia ]-2-hydroxypropane-1-sulfon(cid:173)
`ate;
`17. 6-(N-coconutalkyl-N ,N-dimethyl)hexanoate;
`18. 5-(N,N-dipropyi-N-dodecylammonio )pentane-1-
`sulfonate;
`19. 3-( N-methylmorpholino )stearate;
`20. Potassium N-coconutalkyl ~aminopropionate;
`21. Ammonium N-coconutalkyl ~iminodipropion­
`ate.
`When in the above Examples I-XIX, the following
`ethoxylated anionic surfactants are substituted for the
`specifically named ethoxylated anionic surfactants,
`either totally or in part (e.g., a 1:1 ratio), substantially 60
`equivalent results are obtained in that the shampoos
`are exceptionally mild to the eyes:
`I. Ammonium polyethoxylated( 10 )octanol ether
`sulfate;
`2. Triethanolammonium polyethoxylated(2)2-ethyl- 65
`tetradecanol sulfate;
`3. Potassium polyethoxylated(4) octylphenol ether
`sulfate;
`
`45
`
`50
`
`Sodium
`4.
`ether sulfate;
`5. Diethanolammonium polyethoxylated( 4 )dodec(cid:173)
`ane-2-ol ether sulfate;
`6. Monoethanolammonium polyethoxylated( 5 )tetra(cid:173)
`propylene phenol ether sulfate;
`7. Sodium polyethoxylated(8)3-nonylphenol ether
`sulfate;
`8. Potassium polyethoxylated( 4 )octoylamide ether
`sulfate;
`9. Triethanolammonium polyethoxylated( 5 )hex(cid:173)
`adecoylamide ether sulfate;
`10. Potassium polyethoxylated(2)octanol sulfosuc-
`cinate monoester;
`11. Triethanolammonium polyethoxylated( I 0 )hex(cid:173)
`adecanol sulfosuccinate monoester;
`12. Potassium N-coconutacyl sarcosinate.
`35 When in the above Examples I-XIX, the following
`ethoxylated nonionic surfactants are substituted for the
`specifically named ethoxylated nonionic surfactants,
`either totally or in part (e.g., a 1:1 ratio), substantially
`equivalent results are obtained in that the shampoos
`40 are exceptionally mild to the eyes:
`1. Polyethoxylated( 40 )octanol;
`2. Polyethoxylated( 10 )hexadecanol;
`3. Polyethoxylated( 25 )2-ethylnonanol;
`4. Polyethoxylated( 18 )dodecane-2-ol;
`5. Polyethoxylated(35)hexylphenol;
`6. Polyethoxylated( 30 )pentadecylphenol;
`7. Polyethoxylated( 40)tetrapropylenephenol;
`8. Polyethoxylated( 25 )3-nonylphenol;
`9. Polyethoxylated(35)sorbitan monostearate;
`10. Polyethoxylated( 25 )sorbitan monooctanoate;
`11. Polyethoxylated(25)polypropylene glycol (M.W.
`1QOO);
`12. Polyethoxylated( 25 )octanoate;
`13. Polyethoxylated( 30)hexadecanoate.
`55 What is claimed is:
`1. A thickened mild liquid shampoo composition
`having conditioning properties comprising:
`A. from about 4% to about 8% of an anionic surfac(cid:173)
`tant selected from the group consisting of ( 1 ) a
`surfactant of the formula R(OC2H4)n0S03M,
`. wherein R is a hydrophobic group selected from
`the group consisting of alkyl groups containing
`from about 8 to about 16 carbon atoms, alkyl(cid:173)
`phenyl groups wherein the alkyl group contains
`from about 6 to about 15 carbon atoms, and fatty
`acid amido groups wherein the fatty acid contains
`from about 8 to about 16 carbon atoms, wherein n
`is a number from about 1 to about 10, and M is a
`
`6
`
`

`

`3,962,418
`
`12
`· containing cellulose ether having substituent
`groups of the formula
`
`wherein each R7 is selected from the group consisting
`of methyl and ethyl groups, m + p ranges from about 1
`to about 10, n is from about 0.1 to about 0.5, the de(cid:173)
`gree of substitution ofthe cationic group on the cellu(cid:173)
`lose is from about 0.1 to about 0.5, and the viscosity of
`a 1% sol uti on of the cellulose ether at 25°C. ranges
`from about 100 to about 2,000 centipoises, the molecu(cid:173)
`lar ratio of (A) to (B) being from about 1:1 to about
`4:1; the weight ratio of (A)+ (B) to (C) being from
`about 2: 1 to about 1 :2; and the pH of the composition
`being from about 6.0 to about 8.0.
`2. The composition of claim 1 wherein the quater(cid:173)
`nary nitrogen containing cellulose ether has a degree of
`substitution of the cationic group of from about 0.15 to
`about 0.25.
`.
`3. The composition of claim 1 wherein m + p has a
`value of about 1.5.
`4. The composition of claim .1 wherein the viscosity
`of a 1% solution of component Eat 25°C. is from about
`125-1000 centipoises.
`·
`5. The composition of claim 1 wherein the molecular
`ratio of the anionic surfactant to the zwitterionic sur(cid:173)
`factant is from about 1:1 to about 3: 1.
`6. The composition of claim 5 wherein the molecular
`ratio of the anionic surfactant to the zwitterionic sur(cid:173)
`factant is from about 1 : 1 to about 2: 1.
`7. The composition of claim 1 having a pH of about
`7.0.
`8. The composition of claim 1 wherein the zwitter(cid:173)
`ionic surfactant has the formula
`
`11
`non-toxic cation which makes the surfactant water(cid:173)
`soluble, (2) a water-soluble polyethoxylated fatty
`alcohol sulfosuccinate monoester, ( 3) a water-sol(cid:173)
`uble N-fatty acyl sarcosinate containing a fatty acyl
`group containing from about 8 to about 16 carbon 5
`atoms, ( 4) a water-soluble alkyl sulfate containing
`from about 8 to about 16 carbon atoms, and (5) a
`water-soluble N-fatty acyl-N-methyl taurine con(cid:173)
`taining a fatty acyl group containing from about 8
`to about 16 carbon atoms;
`B. a surfactant selected from the group consisting of
`(I) a quaternary ammonium zwitterionic surfac(cid:173)
`tant having
`the formula
`(R2)AN<+l(R3 h-ACH-
`2-B(R2)B(R4)cYH
`wherein A, B, and C are each selected from the group 15
`consisting of 0 and I, wherein A is 0 when B is 1 and
`A is 1 when B is 0, wherein C can only be 1 when Y is
`a sulfonate group, wherein each R2 is selected from the
`group consisting of alkyl groups containing from about
`8 to about 16 carbon atoms and a moiety having the
`formula R5 - C(O)NH- R6 - wherein R5 is an alkyl
`group containing from about 8 to about 16 carbon
`atoms and R 6 is an alkylene group containing from I to
`about 5 carbon atoms, wherein each R3 is selected from 25
`the group consisting of alkyl, hydroxyalkyl and alkoxy(cid:173)
`alkyl groups whieh can be connected to form a ring and
`each of which contains from I to about 3 carbon atoms,
`wherein Y is selected from the group consisting of
`sulfonate and carboxylate groups, and wherein R4 is an 30
`alkylene group containing from I to about 5 carbon
`atoms when Y is a carboxylate group and is selected
`from the group consisting of alkylene and hydroxyalky(cid:173)
`lene groups containing from about 2 to about 5 carbon
`atoms when Y is a sulfonate group and wherein the
`hydroxy group is on a secondary carbon atom, and (2)
`a water-soluble N-alkyl ,8-aminopropionate wherein
`the alkyl group contains from about 8 to about 16
`carbon atoms, and ( 3) a water-soluble N-alkyl .B-
`iminodipropionate wherein the alkyl group contains 40 wherein R 6 is an alkyl group containing from about 9 to
`about 15 carbon atoms, wherein each R7 is selected
`from about 8 to about 16 carbon atoms;
`C. a polyethoxylated nonionic surfactant selected
`from the group consisting of methyl, ethyl, and 2-
`from the group consisting of: ( 1) polyethoxylated
`hydroxyethyl groups, wherein Y is selected from the
`alkyl alcohols, said alcohols containing an alkyl
`group consisting of sulfonate and carboxylate groups,
`and wherein R8 is a methylene group when Y is a car(cid:173)
`group containing from about 8 to about 16 carbon 45
`boxylate group and is selected from the group consist-
`atoms and said polyethoxylated alcohols contain-
`ing of propylene and 2-hydroxypropylene groups when
`ing from about 10 to about 45 ethoxy moieties per
`Y is a·sulfonate group.
`9. The composition of claim 6 wherein Y is a carbo~-
`(2)
`polyethoxylated
`alkylphenols
`molecule,
`wherein the alkyl group contains from about 6 to
`.ylate :group.
`.
`10. The composition'of claim 6 wherein y is a sulfo-
`about 15 carbon atoms and wherein the polyethox- 50
`ylated alkylphenol contains from about 10 to about
`nate group.
`u. The composition of claim 1 wherein the zwitter-
`45 ethoxy moieties per molecule, ( 3) · polyethox-
`ylated mono fatty acid esters of sorbitol wherein
`ionic surfactant has the formula
`said fatty acids contain from about 8 to about 18
`carbon atoms and said polyethoxylated mono fatty 55
`acid ester of sorbitol contains from about 10 to
`about 45 ethoxy moieties per molecule, ( 4) polye(cid:173)
`thoxylated polypropylene glycol having a molecu-
`lar weight of from about 2,000 to about 6,000 and
`containing from about 40% to about 60% by weight 60
`of polyethoxy groups, and (5) polyethoxylated
`fatty acids wherein said fatty acid contains from
`about 8 to about 16 carbon atoms and said polye(cid:173)
`thoxylated fatty acid contains from about 10 to
`about 45 ethoxy moieties per molecule;
`D. from about 50% to about 85% water; and
`E. as a thickener and hair conditioning agent, from
`about 0.2% to about 4% of a quaternary nitrogen-
`
`(C,H,O- lml -CH,CHO(CH,N'+'(R 7)aCI'_,_
`)-].( C2H40- ),H
`
`10
`
`20
`
`35
`
`R9 N'+' (R 10 ), CH,CHX CH,SOa<->
`
`wherein R 9 contains from about 10 to about 16 carbon
`atoms, wherein each R 10 is selected from the group
`consisting of methyl, ethyl, and 2-hydroxyethyl groups,
`and wherein X is selected from the group consisting of
`hydrogen and hydroxyl groups.
`·
`12. The composition of claim 1 wherein the anionic
`surfactant is a sodium salt of a fatty alcohol polyethoxy
`ether sulfate 'containing a fatty alkyl group containing
`65 from about 10 to about 14 carbon atoms and about 3
`ethoxy moieties per molecule.
`13. The composition of claim 1 wherein the anionic
`surfactant is a sodium salt of a polyethoxylated fatty
`
`7
`
`

`

`3,962,418
`
`13
`alcohol sulfosuccinate monoester wherein the polye(cid:173)
`thoxylated fatty alcohol contains about 3 ethoxy moi(cid:173)
`eties per molecule and a fatty alcohol moiety contain(cid:173)
`ing from about 10 to about 14 carbon atoms.
`14. The composition of claim 1 wherein R is a fatty 5
`acid amido group containing from about 10 to about 14
`carbon atoms and n is about 3.
`15. The composition of claim 1 wherein the nonionic
`surfactant is a polyethoxylated mono fatty acid ester of
`sorbitol wherein the fatty acid contains from about 10
`to about 16 carbon atoms and wherein there are from
`about 15 to about 40 ethoxy moieties per molecule.
`16. The composition of claim 1 wherein the nonionic
`surfactant is a polyethoxylated fatty alcohol wherein 15
`
`14
`said fatty alcohol contains from about 10 to about 14
`carbon atoms and wherein there are from about 15 to
`about 40 ethoxy moieties per molecule.
`17. The composition of claim 1 wherein the nonionic
`surfactant is a polyethoxylated polypropylene glycol
`wherein said polypropylene glycol has a molecular
`weight of from about 2000 to about 6000 and contains
`from about 40% to about 60% by weight of polyethoxy
`10 groups.
`18. The composition of claim 1 wherein the anionic
`surfactant contains a cation selected from the group
`consisting of sodium, potassium, ammonium, and trie(cid:173)
`thanolammonium cations.
`* * *