J. Soc.

CosmeticChemists, 17, 157-169 (1966)

of Surface ModifyingEffects
Lanolin Derivatives
LESTER I. CONRAD, B.S., HENRY F. MASO, B.S. and SHIRLEY A. DERAGON, B.S.* Presented March 1O, 1965, A ustralian Societyof Cosmetic Chemists, Sydney

Synopsis--The influence of lanolin derivatives on the physical aspects of dispersionsis discussed. Particular reference is made to pigment wetting, rheological patterns in emulsion

systems,solubilization, emulsificationand spreadingcoefficients. Practical applications of

these phenomena are illustrated by typical cosmetic formulations.

INTRODUCTION

This presentation is concernedprimarily with the influence of lanolin derivatives on the physical aspectsof dispersions. Lanolin is known to contain many chemicalgroupsand configurations which are potentially surface-active. However, due to the manner in which these groupsare chemically bound, they cannot achieve that potential. As a result, lanolin itself is relatively poor when consideredfrom the viewpoint of surfaceactivity. Fortunately, by meansof chemicaland physical procedures lanolin can be convertedinto very usefulfunctionalderivatives of predictable surface activity. Whereas formerly lanolin was employed mostly for the marketing advantages of having "Contains Lanolin" on the label, derivatives of lanolin are now widely usedfor their ability to modify the surfaces of dispersed systemsaswell asfor emollient
effects on the skin.

* American CholesterolProducts, Inc., Edison, N. J.

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CHEMISTRY

OF LANOLIN

For a clear understanding of the subject it is necessaryto review briefly the chemistry of lanolin and its derivatives. Unfortunately, the composition of lanolin fluctuateswidely, both qualitatively and quantitatively, from lot to lot. Variables such as heredity, environment, and food supply affect the complexchemistry of this natural secretionof the sheep's sebaceous glands. Additional variations are introduced by aging, wool storageconditions,and scouringmethods.
Esters

Lanolin consists of approximately95% esters,4% free alcohols, and free fatty acids and hydrocarbons. The ability of lanolin to form W/O emulsionsis due to the small free alcohol and fatty acid content.

Figure 1.

Composition of lanolin
esters

The ester fraction contributes very little to surface activity but is important as a chemicalintermediate and raw material of unique composition for the synthesisof derivatives. The nature of the estersis presentedgraphicallyin Figure 1, which showsa 50/50 divisionof the alcohols and acidswhich compose the esters. There are presentboth monoand dihydric alcoholsas well as normal, branched, and hydroxy acids. This assortmentof reactive groupsin compounds having a wide rangeof molecularweights (Co to C3,) resultsin an extremely large variety of
esters.

Alcohols

The composition of lanolin alcohols is detailedin Table I. Cholesterol, of course,is the best known of these, but there are many other useful alcohols present. It is interestingthat squalene, the highly unsaturated hydrocarboncharacteristic of human sebum,is not found in the unsaponifiable fraction of lanolin. Glycerolis alsocompletelyabsent.

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Table

Composition of Lanolin Alcohols

A liphatic AIcohols Normal (Cs to C.,) Branched chain (C17 to C.,) Diols (C1 to C.,4)five members isolated in 1951
Sterols

18%
4-5%
25% 5%
snall amount

Cholesterol

C.,7H460

Dihydrocholesterol (cholestanol) Cerebrosterol

C.,,H4sO C27H4702
C.0H500

Triterpene Alcohols
Lanosterol

Dihydrolanosterol Agnosterol Dihydroagnosterol

Hydrocarbons

Ca0H520 C30H4sO Ca0H00

o% lo% 1% 4%
<% 20%

-Unclassified--at present

Table

II

Composition of Lanolin Fatty Acids (from Weitkamp)

Number

of Acids
9

Series
Normal

Structural Formula

Hydroxy

CH--(CH,,),n--COOH (n -- 4 to 12 incl.) CH--(CH2)n---CH--COOH (n = 6, 7)

OH

9.5 4.2

10

Iso

CH--CH--(CH,),,COOH

(n = 3 to 11 incl.)

29.3

I
CH3
11 Anteiso

CHa--CH2--CH--(CH,,)2n--COOH

(n = 2 to 13 incl.)

37.3

I
CH3
Distillation Loss 6.0

Residue

13.0
99.3

Acids

Table II presentsdata on the compositionof the lanolin acidsas obtained by Weitkamp (1). Sincehis publicationmany additional acids have been identified. This laboratory found that hydroxy acids can compriseas much as 40% of the total lanolin acids (2). These fatty acids offer interesting opportunities for the synthesisof functionally
active preparations for use on skin and hair.

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Flow Diagram

The Lanolin Derivatives Flow Diagram (Fig. 2) graphicallyportrays

the chemical andprocessing relationships between the various derivaacylation (acetic)

LANOLIN

Acetylated fanolin Ethoxylated lanolin

Lanolin oil

ethoxylation(75 molesEO)
solvent fractionation

saponilfication
ACIDS IALCOHOSl TOAL IIIFA}T
--further

esterification (isopropanol)

Isopropyl lanolate

Liquid multi-sterol extract L blending

fractionation -

Solid multi-sterol extract

Absorption base

fraetionation

--crystallization
SURFACE

Cholesterol USP

ethoxylation (24 moles EO)Ethoxylated cholesterol

-- ethoxylation 1
I-(25

adsorption

(16 moles EO)

moles EO)--

--

Ethoxylated lanolin alcohols Ethoxylated lanolin alcohols

extraction

ACTIVE

--esterification
ALCOHOL

(acetie)--fractionation--Aeetylated lanolin alcohols

Lanolinalcohols ricinoleate

I-(ricinoleic)

r- acetylation
thoxylation-]
I_ acetylation

Partially acetylated ethoxylated ester

Completely aeetylated ethoxylated ester

Figure 2. Flowdiagram showing theusual processes employed for themanufacture of different lanolin derivatives

tives. It will be notedthat there are four general processes applicable

tolanolin directly. These areacylation, ethoxylation, solvent fractionation,andsaponification. An additional process, rearrangement, is also being used toproduce new products bytheacidolysis oflanolin (3). The lanolin fatty acids lendthemselves to esterification, neutralizationtoform soaps, and ethoxylation. Thelanolin alcohols aresubjected to manyprocesses including fractionation, adsorption, and extraction

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DERIVATIVES

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to obtain the surface-activefraction, which can then be processed further to form multi-sterol extracts and absorptionbases. Cholesterolis producedfrom this fraction by crystallization. By ethoxylating cholesterol, a derivative with hydro-alcoholic solubility properties is obtained. Other lanolin alcoholproductsare prepared directly from the surfaceactive alcohol fraction by ethoxylation. Another processemployed is esterification. Stepssuchas ethoxylation and acetylation are then carried out on esterified lanolin alcohols. g2uaternizationhas resulted in

interestingexperimentalproductswith unusualsubstantivitywhen applied to skin and hair.

KSULTS AND DISCUSSION

Pigment Wetting The effect of lanolin derivatives on the wetting and dispersingof finely ground solidsin variousliquid vehicleshas been exploredextensively. Lanolin products differ considerably in their pigment wetting action, a number of them being outstandingin this regard. It was assumedthat wetting and dispersing implied deflocculation or reductionof

agglomerated particlesto the primary particlestate. Consideration was givento the role of the derivativein termsof its orientationto and adsorptionon the particle surface. The hydrophilic-lipophilic contrast
within the moleculeand association tendenciesof portions of the derivative molecule were all regarded as important factors contributing to

compatibilitybetweenthe particle surface,the lanolin derivative, and the vehicle. Lanolin products probably also function by lubricating the particle surfaceand by displacing therefrommaterialswhich might interfere with their adsorptiononto the surface. Wetting is regardedas a significantinterfacial phenomenon involved in dispersing solids. After preliminarystudies,a simpletechnique was selected to evaluate the comparative wetting performance of lanolin derivatives. The method employedwas adapted from the paint industry whereit hasbeenused extensively (4). Recentstudies havealsoap-

pliedthismethod to materials of interest in cosmetics (5).

The test consistsof adding increments of vehicle from a burette to

powders containing lanolinderivatives as additives. The incorporation of eachincrementis accomplished manually, and the mixture is worked
to a uniform consistency. When a cohesivemass is formed, an end

point is read, referredto asthe "Wet Point." Further vehicleadditions softenthe mixture until a point is reachedat which it flows; this volume
is called the "Flow Point."

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The Wet Point and the Flow Point are indicative of the wetting ability of a particular additive for a specificsystem. Since the wetting activity is inversely proportional to the volume of liquid vehicle added, a lower value signifiesgreater activity. The ratios of derivatives to powders employed were in practical ranges for eventual use in finished formulations. The Wet and Flow Points were found to be reproducibleand demonstrateda quantitative relationship in each specificsystem. Table III showsthe comparative efficiency of three lanolin derivatives in the wetting of several powdersin mineral oil (70 Saybolt).
Table III

Wet and Flow Points in Mineral Oil (70 Saybolt)

TiO2
Wet Flow Wet

Tale
Flow

Oxy Red
Wet Flow

D&C Red #9
Wet Flow

Deriv./powder ratio
Amerchol L-101

Pt.

Pt.

Pt.

Pt.

Pt.

Pt.

Pt.

Pt.

10% of powder 20% of powder

A cetulan

30 12 34 14

238 47 242 34

31 18 28 15

174 165 198 184

30 7 30 7.5

113 58 129 109

28 16 32 18

105 83 98 86

lO% of powder 20% of powder

A merlate P

10% of powder 20% of powder Control(Min. Oil) 10% of powder 20% of powder

23 16
44 36

61 51
258 249

27 18
33 23

127 106
259 247

11 3
38 26

43 35
124 112

3,5 20
33 23

93 81
108 96

The results are given in terms of cc. of mineral oil per 100 g. of powder. Controlsat 10 and 20% showthe effect of usingmineral oil insteadof the derivative in the powdermixture. The data in Table III represent only

onephaseof the work on pigmentwetting and are includedhereto show the value of the test method as a screeningtechnique. Differencesin wetting performance are shown. Theseare validatedby actualexperience with finished formulations employing the above materials. Microscopicexaminationwas also employedand found to be very usefulfor supplementing Wet and Flow Point data. Systemsexamined microscopically at the Flow Point exhibitedcompletedeflocculation and good dispersion when the Flow Point was low. At high Flow Points

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incompletedefiocculation and poor dispersion were apparent under fairly low magnification (100X). Sedimentation studies were utilized for estimating the influence of lanolin derivatives on the deflocculationof agitated liquid dispersions. It is apparent at this stageof the investigation that Amerlate P is an outstanding dispersingagent for pigments in both emulsified and anhydrous systems. This may be attributed to its chemicalcomposition, consisting of the isopropylestersof branchedand hydroxy lanolin fatty acids in a broad range of carbon lengths. The unique lubricity resulting from this compositionmay play a significant role in the dispersingactivity of the product. These factors alsocontribute to a reduction of shear requirements in formulations containing Amerlate P. The data in Table III confirm empirical findings which had led to the extensiveuse of this material in pigmented products. The following formulas (a and b) illustrate the practical application of these principles in makeup items:
(a) Anhydrous Makeup
Acetulan
Amcrlate P

(b) Liquid CrearnMakeup (Highly Pigmented)

6%
3 Amerchol L-101 4.0

Amerlate

3.0

Mineral oil (70 Saybolt) Microwax, m.p. 170 F Talc, TiO2, Pigments
Perfume

36 15 40
q.s.

Stearic acid, XXX Glyceryl monostearate Mineral oil (70 Saybolt)

Triethanolamine

2.0 1.0 15.0

0.8

Propylenc glycol
Water

5.0
69.2

Perfume

q.s.
100.0 Parts

Pigments

15-25 Parts

These are elegant emollient preparations with good application propertieson skin. They spreadwell with matte coverageand without streaking or leathering. Acetulan in the anhydrousmakeup acts as a degreasingagent for the waxy vehicle. The lubricant properties of Amerlate P help to overcome the frictional drag of the high pigment
levels of these two formulations.
RHEOLOGICAL ACTIVITY

Lanolin derivatives influencethe rheologicalpattern of emulsionsystems in a profound manner. They participate as emulsifiersin the formation and stabilization of an emulsionand can also affect development of its ultimate viscosity. Such viscosity trends are often thought of only in terms of the external phase. Elementary emulsion considerations point to crowding of the external phase by the volume of the dis-

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persedphaseand the useof external hydrocolloids as the prime sources of viscosity control. These studiesshow that the incorporation of lanolin derivatives in the interfacial film is an effective way to modify viscosity behavior and simultaneouslyadd emollient properties. The formulations shown in Table IV utilize Solulan C-24, an O/W emulsifier,together with cholesterol,a W/O emulsifier,in various ratios which determine the viscosity pattern of a cosmetically elegant O/W lotion. Brookfieldreadingsshow the dramatic influence of slight adTable IV

Viscosity Changes in O/W Lotion

Cholesterol USP ...

0.5%
.. 3.0 3.0 25.0

0.5%
0.15 3.0 3.0 25.0

0.5-
0.3 3.0 3.0 25.0

0.5%
0.75 3.0 3.0 25.0

Solulan

C-24

...

Stearic Acid XXX Glyceryl monostearate (pure) Mineral oil (70 Saybolt)
Triethanolmnine

3.0%
3.0 25.5
1.0

1.0 4.0

1.0 4.0

1.0 4.0

1.0 4.0

Propylene glycol
Water

4.0
63.5

63.5

63.35

63.2

62.75

Observations after one

month:

Appearance at room
temp.

medium heavy
flow

no flow

heavy flow medium heavy

flow

medium
flow

Viscosity readings Brookfield--cps. #3 spindle 3 rpm Room temp. stability Incubator stability (42C)

23,000

off-scale 39,000 (solid)

good good good fair

26,000

9,400

good good

good good

good fair

justments in concentrationof Solulan C-24 [ethoxylated (24 moles) cholesterol]on the reduction of the viscosity of the system. Extended time studiesof this formula showthat an optimum concentrationof 0.3% Solulan C-24 prevents the undesirablethickening of this formula while maintaining its stability. This antigellingeffect is a very usefulproperty whichmay be appliedto many lotionsystems.
SOLUBILIZATION

Transparent gels involve the use of microemulsions in modern cosmetic technology. Lanolin derivatives are essential componentsin many of these interesting systemsin which the dispersedphase is invisible to transmittedlight (theoretically a particle sizeof lessthan one-

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fourth of the wavelength of light). Extensive studies of this type of solubilizationhave been reported previously (6). The followingformulas (c and d) illustrate someof the transparent gels; in these cases,the lanolin derivative promotes stability in the presenceof a large amount of both oil and water phasesat a relatively low surfaetant to oil ratio, important from irritation considerations.
Ernollient Clear Gels (c and d)

Solulan C-24 Isopropyl myristate Oleyl alcohol Atlas G-1292 Propylene glycol Water

15% 25 5 15 5 35

Solulan 16 Atlas G-1292 Mineral oil (70 vis.) Oleyl alcohol Propylene glycol Hostaphat KL340
Water

10% 10 20 4 5 4
47

Experiencewith transparent colloidal dispersions indicates that, although they are generally consideredto be thermodynamically stable, they must be formulated very carefully if they are to survive the temperature extremesto which commercialproducts are normally exposed. Aging tests with microemulsions shouldtake this into consideration,and the formulator should examine his experimentsclosely for changesin their physicalstateindicatedby gradualopacification, lossof consistency, and a lossof their resonantor vibrating character. The latter often appearsfirst and may precedeother adversechanges.
EMULSIFYING EFFECTS

The performance of lanolin derivatives as emulsifiers has been re-

ported previouslyin somedetail (7). More recently theselaboratories have been concerned with the participation of lanolin derivatives in associationphenomenarelated to the construction of emulsion interfaces. Much of this work has been of an empirical nature, and many formulas have been developedin which so-calledtheoretically balanced systems (e.g., HLB) utilizing conventionally paired O/W and W/O emulsifiers have been supplemented by the addition of lanolin derivatives. For

example,use of one of the Amerchols(W/O) together with a Solulan (O/W) will add stability by associatingat the interface with the other hydrophilic and lipophilic emulsifiers. This can be demonstrated in
both nonionic and ionic systems and, in addition, leads to added bene-

fits in terms of improvedfeel and texture. This work is actually an outgrowth of the classicalexperiments demonstrating the interfacial coupling of cholesterolwith anionic emulsifiersof the sodium alkyl sulfate type (8). Examplesof emulsionformulas (e, f, and f) having well as-

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sociated interfaces, with lanolin derivativesas the key auxiliary emulsitiers, are given below:
(e) Anionic Lotion O/W Hair Dressing Waxolan 5.0%
Amerchol L-101 4.0

(f) CationicLotion O/W Amerchol L-101 5.0%

Solulan 98 2.0

(g) NonionicLotion O/W Roll-On Antiperspirant Amerlate P 1. $%

Amerehol L-101 3.5

Amerlate P 3.0 Stearic acid 2.0 Mineral oil (70 10.0 Saybolt) Glyceryl monostearate 1.0 Ucon 50 HB 660 5.0 Water 68.86 Carbopol 941 0.15

Cetyl alcohol Arlacel 165 Emcol E-607S Glycerol Water Perfume

1.0 4.0 0.1 2.0 85.9 q.s.

Solulan 98 Cetyl alcohol Glycerol Polyoxyl 40 stearate Veegum HV Water Chlorhydrol, 50% Alcohol

2.0 2.0 2.0 4.0 1.0 38.0 36.0 10.0

Triethanolamine
Perfume

1.0
q.s.

Perfume

q.s

Formula e is a heavy bodied lotion with goodgroomingqualities for hair. It behaves like a cream-oil type but is washable and non-oily. The cationiclotionf may be usedfor generalhand and body applications or for removing static from hair for good manageability. The roll-on g is a relatively non-tacky system which resists crystallization on the ball applicator and depositsa flexible antiperspirant film on skin.
SPREADING PROPERTIES

Surface activity can be expressed in terms of spreadingcoefficient (S) calculated from the following equation:
S = ?B3A3'A

where B is the surface tension of water; A surface tension of the oil;

and % is the interfacial tensionbetweenoil and water. The following Table V presents surfaceand interfacial tension data determined on mineral oil solutions of severalproducts; thesedata are comparedwith the calculated spreading coefficients. The higher the value of S, the greater the tendency for the oil to spreadover the water surface. It is interestingto note here that several lanolin derivatives,which do not fit the classical descriptionof emulsifiers becausetheir molecular configurations show no hydrophilic-lipophilic contrast,nevertheless reduceinterfacial tensionconsiderably and show correspondingly high spreadingcoefficients. This indicates that there are other factorswhich may determinethe interfacial activity of lanolin derivatives. An example of this is a comparisonof the value of Acetulan with that of isopropyl myristate: Acetulan demonstrates a

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Table

Spreading Coefficients (S)

7A(oil)
5% Solutions in mineral oil (70 Saybolt)
Acetulan Amerchol L-101 32.0 32.8

-AB(oil/water)

S(calculated for 7B = 72.3 for water)

21.2 7.6

19.1 31.9

Modulan

32.5

15.0

24.8

Polylan
Ricilan B

31.7
32.6

16.8
19.1

23.8
20.6

Ricilan C Viscolan

32.4 31.8

21.7 5.7

18.2
34.8

Isopropyl myristate
PEG 400 dilaurate

31.7
32.7

32.9
0.4

7.7
39.2

100% Materials
Acetulan 32.9 17.2 22.2

Isopropyl myristate Mineral oil (70 Saybolt)

30.9 32.4

16.7 45.3

24.7 -- 5.6

depressant effect on interfacial tensioneven after dilution to 5% in

mineral oil; isopropyl myristate does not show this effect.

[[ Thefollowing formulas (h,i and 1') forbathoils utilize these principles

to promote their spreadingcharacteristics on water. This action of the lanolin derivatives can be fortified, if desired, by the addition of an oil soluble surfactant which will, in turn, promote emulsification of bath oil throughout the bath water. The above formulas are surface orienting. Reducing the surfactant, in this case polyethylene glycol 400 dilaurate, favors migration of the dispersedoil droplets to the surface of the water.
Emoilient Bath Oils

Acetulan
Modulan

h 5%
5

i ......
......

Viscolan Polylan
PEG 400 dilaurate

... ......
5

10%
5

... 3.5%
4.5

Isopropyl myristate Mineral oil (70 Saybolt)

25 60

25 60

37.5 54.5

SUMMARY

Various aspectsof studiesconcernedwith the participation of lanolin derivatives in surfacephenomenawere presented. These surfaceactive effectsare valuable supplementalpropertiesto the establishedemollient
character of these derivatives.

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Data on pigment wetting performance were presented utilizing a simple technique which permits the comparative evaluation of lanolin derivatives in a quantitative manner. The influenceof lanolin derivativeson the rheological pattern of emulsion systemswas illustrated by the viscosity and stability behavior of these systems. Solubilizing and emulsifying effects of lanolin derivatives were discussed, and formulas were presented illustrative of the principles involved.

Finally, data on the spreading propertiesof severallanolin derivatives along with their practical applications were presented.

(Received April 21, 1965)

REFERENCES
(1) (2) (3) (4) Weitkamp, A. W., J. Am. Chem. Sac., 67,447 (1945). Conrad, L. I., Am. Perfumer, 64, 177 (Sept. 1954). British Patent//965,849; U.S. and other foreign patents pending. Daniel, F. K., Qc. Dig. FederationPaint Varnish Production Clubs, 344, 635 (Sept. 1953). Bews, I. C., and Fisk, N. R., Am. Perfumer Cosmetics, 79, 89 (Oct. 1964). Conrad, L. I., Motiuk, K. and Maso, H. F., roc. Sci. Sect. Toilet GoodsAssoc.,29, 14 (1958). Conrad, L. I., Am. Perf. 71, 70 (June 1958). Schulman, J. H., and Cockbain, E.G., Trans. Faraday Sac., 36,651 (1940). APPENDIX

(5) (6)
(7) (8)

Raw

Materials

Used

(A) Lanolin Derivatives*

Acetulane Amerchol L-101

Amerlate
Modulan

Acetylated lanolin alcohols Liquid multi-sterol extract lsopropyl lanolate Acetylated lanolin
Lanolin alcohols linoleate

Polylan
Ricilan B

Lanolin

alcohols

ricinoleate

Ricilan Solulan

C 97

Soluln 16
Solulan 98 Solulan C-24
Viscolan Waxolan

Acetylated lanolin alcohols ricinoleate Ethoxylated lanolin alcohols

Completely acetylated, ethoxylated lanolin alcohol-esters Partially acetylated, ethoxylated lanolin alcohol-esters Ethoxylated cholesterol
Lanolin oil

Lanolin

wax

* The above products are manufactured and the Trade Marks are owned by American Cholesterol Products, Inc., Edison, N. J.

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(B) Miscellaneous ingredients

Arlacel 165

Glyceryl monostearate, acid type, self emulsifying, Atlas

Chemical Industries.

Carbopol 941 Chlorhydrol 50%

Emcol Atlas E-607-S G-1292

Carboxy vinyl polymer, B. F. Goodrich Chemical Co. Aluminum chlorhydroxide complex, Reheis Co., Inc. N-(Stearoyl colamino formyl methyl) pyridinium chloride, Emulsol Division, Witco Chemical Co. Ethoxylated hydrogenated castor oil, Atlas Chemical
Industries.

Hostaphat KL340

Microwax (m.p. 170F)

Ucon 50 HB 0

Tertiary ester from o-phosphoricacid and lauryl tetraglycol ether, Hostachem Corporation. Microcrystalline hydrocarbonwax, white, 170F m.p.,
Bareco Wax Co.

Polyalkylene glycol, Union Carbide ChemicalsConpany.

Magnesium aluninum silicate, R. T. Vanderbilt Co. Purified grade of ferric oxide, Whittaker, Clark and
Daniels.

Veegum HV Oxy Red