CLASSIFICATION OF SURFACE-ACTIVE AGENTS

BY "HLB"t

By Wx•,•,x• C. G•,•FFx•r
,/it/asPowderCompany,//Filmington,
Del.

SINCE rH•. •NXUODtrCX•ON of A completesystem for selecting

the "HLB" system of classifying an emulsifierwould providethe best
and selectingemulsifiers(6) numer- emulsifierto give the desiredform of
ous requests have been received product for the desired raw ma-
concerning its derivation. The terials. Thus, knowing the materi-
term "HLB" comes from the words als to be emulsified,the most ef-
hydrophile-lipophile balance.Emul- ficient emulsifiercould be chosenfor
sifiers consist of a molecule that the desiredtype of emulsion.
combinesboth hydrophilicand li-
pophilic groups(or polar and non- AcTioN ov EMtrzsiviZl•S
polar groups)and it is the balance
An emulsifier has two actions
of the size and strength of these
two opposinggroups that we call that are distinctly different. The
HLB. acceptedactionis that of promoting
Surface-activeagents have been the formationof an emulsion; mak-
classifiedin many ways: including ing the emulsioneasierto.prepare;
chemical types and accordingto producinga finer particle size; and
ionization. Classificationby HLB aiding the stability of the emulsion.
permitssomepredictionof behavior The second action, which occurs
and reduces the amount of work in- along with the preparation of the
volved in the selection of an emulsi- emulsion, consists in controlling
fier, wetting agent,or other type of the type of emulsionthat is to be
agent.
formed, O/W or W/O. This second
Emulsifiers constitute one of the action appears to be a function of
HLB.
widest used subdivisions of surface-
active agentsand we will use this In evolvinga systemfor the selec-
groupasan illustrationof themanip- tion of emulsifiers,we will first con-
ulation of the HLB system, with sider brieflythe theoryof emu}sifica-
referenceto other applications
later. tion. For practical purposes,an
emulsion consists of two immiscible

)Presented at theOctober i'1, 1949,liquids, one being dispersedas a

Meeting,ChicagoChapter,Chicago,I11. multitude of small particlesin the
311
312 JOURNAL
OFTHE SOCIETYOF COSMETIC'CHEMISTS

other. The former is called the dis- emulsionformed. In our study and
persedphaseand'thelatter is called use of emulsifiers,it appearsthat
the continuous phase. Industry the action of emulsifiersmay be
demands further that an emulsion relatedto their structureroughlyas
must exhibit a certain stability follows:
under a variety of conditions. First, "what the emulsifieror sur-
Emulsifiers and stabilizers are face-activeagentswill do," that is,
addedto attain the desiredstability. make an O/W or W/O emulsion,
Between the two phasesof an act as a detergent,or solubilizean
emulsion, a large area or interface oil, or have someother action, seems
exists which surroundseach parti- to dependon what we call the HLB
cle. The adsorptionof emulsifiers of the emulsifier. This value is an
at the emulsion interface has been expression
of the relativesimultane-
established. The nature of this ous attraction of an emulsifier for
interface, whether mono- or multi- water and for oil (or for the two
molecular in thickness,is still in phasesof a systemto be emulsified).
questionaspointedout by Schwartz Emulsifiers consist of a molecule
and Perry (5) in their new book. that combines
both hydrophilicand
Sincethe particlesof an emulsion lipophilic groups and it is the bal-
are considerablylarger than molecu- anceof the sizeand strengthof these
lar in size, we may considerthe in- two opposinggroups that we call
terfacethat surroundseachparticle HLB. For purposes of convenience,
as being similar to the interface the effectivebalanceof thesegroups
which separatesthe phaseswhen is assigneda numericalvalue.
present in bulk. If we were to Second,howefficientlythe emulsi-
shake mineral oil with water we ob- fier will work s•ems to be related to
tain an emulsion that will break over-all chemical structure, that is,
quickly into its two phases. Ex- whether the emulsifieris a soap, a
amination of the interface would re-
partial ester, a complete ester,
veal that the interfacial tension is
whetherthe lipophilicgroupis satu-
high, approximately45 dynes/cm. rated, and so forth. This latter ac-
With the addition of an emulsifier of tion appears to be quite specific
suitable type this would drop to al- and no "rules" have been estab-
most zero. This reduction in inter- lished.
facial tension primarily assistsin
forming the emulsionthoughit also DEVELOPMENT OF HLB SYSTEM
promotesstability.
As mentioned above, the assist- In our presentsystem,an emulsi-
ance in emulsion formation and
fier that is lipophilicin characteris
subsequentstabilization appearsto assigneda low HLB numberand an
be only part of the action of an emulsifier that is hydrophilic in
emulsifier. In addition, the emulsi- characteris assigned a high number.
fier usually establishesthe type of The midpoint is approximatelyten
 CLASSIFICATION OF SURFACE-ACTIVE AGENTS 313

and the assignedvalueshave ranged one direction than the other. This
from one to forty. When two or would seem to decide the type of
more emulsifiers are combined or emulsion that is formed--whether
blended,the HLB values are addi- O/W or W/O. Presumably,the be-
tive in behavior. Thus, if we blend havior of an emulsion could be ex-
threepartsof emulsifier"A" having pressed by observing the proper
an HLB of 8 and one part of an characteristics of this interface.
emulsifier"B" having an HLB of It occurred to us that the "bend-
16, the resultingHLB of the blend ing" tendencyof the interfacemight
willbethesumof three-quarters of be observedby determining the in-
8 andone-quarterof 16, i.e. (6 4- 4) terfacial tension in different direc-
or 10. tions (i.e., up and down), from one
We should note that chemical phase to the other and vice versa.
hydro- A literature search revealed that
typealonedoesnot establish
balance.Thus,soaps Roberts (4) had already made a
phile-lipophile
may.range fromstronglyhydrophilic brief study of this effect in relation
for sodiumlaurate to strongly lipo- to natural petroleumemulsions. In
philic for aluminumoleate; esters, his work, differencesin interfacial
ether-esters,and ethers may range tension were observed whether the
from low to high HLB's, sulfates duNouy ring was pulled up or
and sulfonates may range from pusheddown throughthe interface.
mediumto high. However, the existenceof a differ-
HLB is not the sameassolubility, ence in interfacial tensionis ques-
thoughthereis an over-allrelation- tioned since interfacial tension is in
ship. Thus, materialshaving low itselfthe differencein free energiesof
values tend to be oil soluble and the two phases. It is possiblethat
materials having high values tend the observed differences are due to
to be.water soluble. However, two the introduction of a third phase,
emulsifiers may have the sameHLB the platinum ring. Whether or not
andexhibitdifferentsolubilitychar- this is true, with efficientemulsifier
acteristics. systems,observationsare most dif-
In the preparation of an emul- ficult because,by their very nature,
sion, the reduction of interfacial these systems have an interfacial
tensionmakes it easier to disperse tensionof almost zero (sincethey
oneof the phasesin the other. The form emulsionsspontaneously)and
nature of the interface established thereforethe precisionof measure-
by the adsorptionof the emulsifier ment is low. Hence, this phaseof
at the interface in some •manner the study was not considered
influencesthe two immiscibleliquids further.
to such an extent that one breaks Other experimentalmeansof esti-
up into dropletswhile the otherre- mating HLB have been considered.
tains its continuity. The interface Lambert and Busse (2) recently
apparently"bends"moreeasilyin publisheda rapid methodof deter-
314 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

mining the "dye solubilization"ef-
ficiencyof surface-activeagentsas
previouslydescribedby McBain (3).
A comparisonof our estimatedHLB
values and some of the data pub-
lishedby Lambert and Busseis most
interesting. In their derivation of
an equation for a solubilizingiso-
therm, n and K are constantswhich
tiers most often used as O/W emul-
sifiers had assigned HLB values
within the range of about nine to
twelve. The values of our surface-
active agents used for other pur-
poses were then correlated, with
the results shown in Table 2. After
TABLE 2

are characteristicfor eachagent. In HLB

Range Use
Table 1 wecompare
HLB valuesand
4-6 W/O emulsifiefs
7-9 Wetting agents
TABLE I 8-I 8 O/W emulsifiers
t3-• 5 Detergents
Esti- 5-• 8 Solubilizing
log K mated
Agent n (2) (2) HLB
Igepal CA 0.80 o.•9 •2.8 we had conceived the idea of HLB
EmulphorELA 0.83 o.3 t t3.3 as applied to our own materials
Emulphor ON o. 9•; o. • • • 5.4
Sodium Oleate • .06 0.24 18 and had assigned
valuesto many of
them we beganinvestigatingexpan-
sion of the idea's usefulness.
their data for n and K for several The Atlas Span and Tween emul-
agents. While there is no apparent sifiers had found their way into
relationshipbetween HLB and K, industry as detergents, wetting
there is remarkable agreementbe- agents, etc., by every conceivable
tween HLB and n. This is being method and there were a multitude
studied further in an effort to es- in the developmentstage aimed at
tablish the existenceof the agree- these various uses. When our lab-
ment. However, until this or some oratory began correlating HLB of
other system of estimation is de- industrially used compoundsand
vised,estimationby crossreference developmentstage materials versus
of a large number of emulsification their use, there occurred a self-
testswith establishedmaterials ap- alignment that was remarkable to
pears to be the most satisfactory, see.

thoughlaborious,method. One could appreciatethe poten-

Our originalestimationof empiri- tial advantages of any method
cal HLB valuesfor many Atlas sur- whereby we could connect HLB
face-active
agents
wasbased
•n re- data on our own materials to HLB
suitsobservedin a large numberof data for all surface-activeagents.
emulsification studies conducted Widely applied,this couldsimplify
over several years. These studies immenselythe choiceof emulsifiers
were predominatelyof O/W emul- for a given industrial task.
sions. We found that the emulsi- Considerationof thesepossibili-
 CLASSIFICATION OF SURFACE-ACTIVE AGENTS 315

ties led to the realization that here optimum•

we may have a commondenomina- /42'•tHLB•t+/4•BHLB• \ ratio !
tor that would enable us to relate
/4/•t+/.•B = HLBoil
and pin togetherall surface-active wherein:
agentsregardlessof type which /'•l = the amount (weight) of the first
emulsifier(At) used,and
heretofore at best were considered /4• = the amount(weight)of the second
by groups. emulsifier(B) used at the "op-
timum ratio," giving the best
emulsion
ESXlMATION OF HLB V^LUES HLB•t, HLB• = the assigned
HLB values
EMULSIFIERS AND OILS for emulsifiers At and /•
HLB oil = the "requiredHLB" of the oil
In our proposedsystem, HLB for the type of emulsionbeing
studied
values for new emulsifiers are esti-
mated from a series of tests in which Since good emulsificationmay
actual emulsification behavior is occurover a wide rangeof emulsifier
compared. Comparison,by means ratios, or since emulsificationin the
of blendsor mixtures, is made with entire seriesmay be only mediocre,
agentsof known HLB values, such the optimumratio may be obscured.
as the series of Atlas emulsifiers. By averaging results with several
Emulsifiers,
asusedin industry,are emulsifiers and several oils the esti-
almostalwaysblends. The blend is mation is made more precise. In
usually most efficientif it combines conductinga number of these tests
lipophilicand hydrophilicemulsi- it will be apparent that the infor-
fiers. We usuallyrecommendthat mation will have relationship to
Span* and Tween* emulsifiers be many factors.
used blended. Glyceryl mono- To establishthe necessarycross
stearate,self-emulsifying
grade, is relationships, series of emulsions
a blend. Even the monovalent were prepared over a standard for-
soaps, generally used for O/W mula. The emulsion in these tests
emulsification, are blendsof soap were prepared in a uniform manner
and hydrolyzedfatty acid. in so far as possible. Ten gramsof
Variation of the proportionsof emulsifier, or the appropriate
the blended emulsifiers has been amountof fatty acidfor a soap,was
taught as preferredpracticeto ob- weighed into an 8-oz., tall form,
tain best results. When two emulsi- wide-mouthedjar. Ninety-five
fiersof knownHLB are thusblended grams of oil, or molten wax, was
for usewith a givenoil thereis an added and the jar and contents
optimum ratio that gives best agitated until the ingredientswere
emulsification and the HLB at this well mixed. Ninety-five cubic cen-
ratiois saidto be the requiredHLB timeters of water was then added
for the oil (to give that type'of at one time (coldor hot depending
emulsion,
whetherO/W, W/O solu- uponthe meltingpoint of the oil or
bilization,etc.) This is expressedwax) and thejar cappedandshaken.
by theequation: If required,alkali or amineis added
316 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

TAsLe 3
Material Trade Mark Manufacturer or Distributor

Beeswax Beehive Brand Will and BaumerCandleCo., Inc.

Cetyl Alcohol .......... E. I. du Pont de Nemours& Co., Inc.
Cottonseed Oil Wesson Oil Wesson Oil and Snowdrift Sales Co.
Lanolin, anhyd., U.S. P........... Botany Mills, Inc.
Mineral Oil, heavy Nujol StancoDistributors,Inc.
Mineral Oil, light Marcol GX StancoDistributors, Inc.
Paraffin Paraseal Socony-Vacuum Oil Co., Inc.
Petrolatum,white White Perrecta L. SonnebornSons,Inc.
StearicAcid, D.P. Emersol•so Emery Industries,Inc.

with the water. After a few minutes hours due to the poor quality of
the emulsion was reshaken and then of emulsions in an entire series.
storedovernight. Storagewas again Sincethe data are comparativethis
either at room temperaturefor oils is consideredpermissible when an
or at 60-70øC. for waxes. Observa- entire series is handled as a unit.
tions (and pictures) were usually O/W or W/O emulsionsmay result
taken after twenty-four hours. and this behavior must be checked.
Further storage appeared to affect Usually the differenceis readilyap-
results little. In a few cases the ob- parent,in fact is expecteddepending
servations were taken before 24 upon the HLB of the emulsifiers.

Figure l.--Effect of ratio of low and high HLB emulsifierson emulsi-

fication (the sameweight per cent of emulsifieris not best)
 CLASSIFICATION OF SURFACE-ACTIVE AGENTS 317

The amountof emulsifierused in products required are not similar

thesetests,10 gm. for 95 gin.of oil, for best emulsification and that the
is much more than is usually re-
quiredto obtainemulsification.
Usuallyin a givensystem,the de-
gree
ofemulsification
increases
with
increasing
amountsof emulsifier
to a
point.Beyond
thispoint,thead- ß
__
25'1,'•.

dition of emulsifierdoes not im-

proveor harmtheemulsion.The
highproportion
of emulsifier
was
selectedas providing maxim ex-
pectedemulsification from the
agentsundertestsothatthosehay-.
inga poorover-allefficiency
would
indicatetrends. The oilsand waxes
usuallyincludedin an evaluation
seriesare listed in Table 3.
These values may be utilized
more completelythan for a gross
estimate of the behavior of the
emulsifier. In Fig. 1, we show sev-
eralseriesof samplesin whichheavy
mineral oil is emulsifiedwith several
combinationsor blends of emulsi-
fiers. In eachseries,the only differ-
enceis the types of emulsifiersem-
ployed. Two emulsifiers
are used
in each row, one having a low and
onea highHLB. The sampleson
the extreme left are emulsifiedwith
100% of low HLB agents; the
samples
on .the extremeright are
emulsifiedwith 100% of high HLB
agents.Blendingpermitscoverage
of the completerangeof valuesbe-
tween the two emulsifiers. From
top to bottom,the emulsifiers
are :'%'; .. • •; ..
blendsof laurate, palmirate, stea- , .

rate, and oleate ether-esters

(the
latter in addition being tri esters).
You will note that the weight per- oneFigure 2.--Behavior of various oils with
pair of emulsifiers(different ratios best
centages
of the low and highHLB for different oils)
318 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

grossefficiencyof the systemsare The optimum requiredHLB val-

not identical. The important fact ues indicated in Fig. 2 were for
to us is that in each instance, the O/W emulsions. It will be noted
best emulsion is obtained at about that at tintes a W/O emulsion is
an HLB of 10. This is one of the formed. This usually appearsat
major pointson which this system the extreme left-hand side of the
is based. A given oil has an opti- figure. When this occurs,the oil
mum HLB for a given type of emul- is suitable for use in W/O formula-
sification. tions in major amounts. Often
Different oils require different goodemulsionsare obtainedof both
valuesas ,nay be seenin Fig. 2. In typesand the-oil can have an opti-
mumHLB foreithertype
of emulsion. When we
speakof a requiredHLB,
referenceis usuallymade
to the O/W type.
,,o0 Fortunately, the range
covered by the inverse
• . orW/O typeappears
to
..• be quite narrow and in
-'.,• the low HLB's so that
•o,.o the differenceis readily
apparent.
•."-'- Required HLB values
:T;• for blendsof oils•nay be
calculated in a manner
similar to that tbr blends
of entulsifiersso long as
the requirementsfor the
Figure 3.--Effect of blendingoils and waxes components are known.
Basis for this is illustrated
this figure, one of the pairs of non- in Fig. 3 in which all mineraloil is
ionic emulsifiers used in Fig. 1, emulsifiedin the top row, 50/50
Span40-Tween40, is picturedwith mineral oil-stearic acid in the middle
eight different oils or waxes; cot- row, and all stearicacid in the bot-
tonseed oil, lanolin, petrolatum, tont row. The optimum emulsifier
mineral oil, paraffin, cetyl alcohol, blendprogresses
front about10 for
.beeswax,and stearic acid. It will 100% mineral oil to about 16 for
be apparentthat to choosean emul- 100% stearicacid.
sifter for a formula we need to know A natural questionis the adher-
the requiredHLB for the oil blend, enceof the HLB systemto ionic or
aswell as that of the proposedemul- soapemulsions.Monovalentsoaps,
sifiers. generallyusedfor emulsification,
ex-
 CLASSIFICATION OF SURFACE-ACTIVE AGENTS 319

. .

Figure 4.--Behavior of soaps--varyingratios of oleic acid and NaOH

hibit high HLB's, higher than re- total amountof fatty acid and a re-
quired for optimum emulsification. ductionof the amount of soap.
However, soap alone is seldom, if Goodey (1) has studied the be-
ever, the sole emulsifier in a for- havior of emulsifiers and has ex-
mula. Weknowthatsoaps hydrolyze, plained,in part, their actionby de-
and the true emulsifieris a mixture, fining a part of the emulsifieras a
or blend,of soapand freefatty acid. coupler. This is not couplingaction
This is illustrated in Fig. 4: where as the word is generally used (the
the sampleswith the arrowsare the addition of an agent to promote
theoreticallyneutralizedsoaps,but clarity of solutionof a concentrate
in eachinstance,the samplesto the or emulsion). He suggests that
left in which there is excessfatty there are four constituents of an
'acid are the better emulsions. O/W emulsion: oil, water, emulsi-
The emulsifier,so-called,in these fier, and coupler. In his explana-
series ranges from all fatty acid tion, the emulsifieris alwaysa highly
at the left to all base at the right. hydrophilic substance and the
This might be consideredas repre- coupler is always oil-soluble. The
senting increasingHLB from left couplingaction of which he speaks
to right, thoughit is only true to a is promotion of solubility of the
point slightly to the right of the emulsifierin the oil phaseto further
theoreticalsoap. At this point suf- the reduction of interfacial tension
ficient base has been added to mini- and improve emulsification. We
mize hydrolysisof the soap. Any prefer to considerall of this action
higher ratio of base to fatty acid under the term emulsification and
merely resultsin a reductionof the to call both components emulsifiers.
320 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

Goodey'sdata and oursagreethat

the agentsinvolvedmust have the
properhydrophile-lipophilebalance.
lie suggestsfurther that a proper
ß
ß

hydrophile-lipophile balance for

both the coupler and emulsifieris
neededand that a given concentra-
tion of coupleris neededin the oil
phaseto "attract" the hydrophilic
emulsifier to the interface. There-
fore, a 20% oil emulsionwould con-
tain twiceasmuchcoupleras a 10%
oil emulsion.
The emulsionsin Fig. 5 indicate
that this is not true. Rather, for a
givenoil and water thereis oneHLB
for the total emulsifier that is best
without regard to the concentra-
tions of ingredientsin the usual
ranges. By way of illustration, the
two pah'sof seriesof samplescon-
Figure 5.--Comparisonof fixed "coupler" tain various amounts of oil and
content us. fixed HLB at different emulsion
concentrations water, the amount of oil decreasing
TABLE4•PERCENTAGECOMPOSITION
OFEMULSION
IN FIG. 5

SampleNo. I • 3 4 5
Row 1

Oil 60 50 40 25 10
Water 34.3 45.0 55.8 71.9 88.05
Span20 HLB 8.6 4.5 3.8 3.0 1.9 0.75
Tween 20 HLB 16.7 1.2 1.2 1.2 1.2 1.2

Row 2

Oil 60 50 40 25 10
Water 34.0 45.0 56.0 72.5 89.00
Span20 HLB 8.6 4.5 3.8 3.0 1.9 0.75
Tween 20 HLB 16.7 1.5 1.2 1.0 0.6 0.25

Row 3
Oil 60 50 40 25 10
Water 34.5 45.0 55.5 71.2 87.0
Span40 HLB 6.7 3.0 2.5 2.0 1.3 0.5
Tween 40 HLB 15.6 2.5 2.5 2.5 2.5 2.5

Row 4
Oil 60 50 40 25 10
Water 34.0 45.0 56.0 72.4 89.0
Span40 HLB 6.7 3.0 2.5 2.0 1.3 0.5
Tween 40 HLB 15.6 3.0 2.5 2.0 1.3 0.5
 CLASSIFICATION OF SURFACE-ACTIVE AGENTS 321

fromleft to right. The samplesin a blend of non-ionic and ionic emul-

the first and third rows were pre- sifters. These blends are satisfac-
paredwithafixedpercentage of low tory whenno electrolytes antagonis-
HLB emulsifierin the oil phase to tic to the ionicportionof the blend
conform with Goodey's require- are to be employed. In suchcases
mentsfor a "coupler." In the sec- a totally non-ionicemulsifiershould
ond and fourth rows, all of the be used.
sampleshad the sameratio of low TABLE
andhighHLB emulsifiers.The per- Esti-
centages
are shownin Table 4. It mated
is seen that a constant HLB for the Emulsifier HLB

total emulsifierprovidesa moreuni-. Anionic

form emulsification. T. E. A. Oleate xz
In Table 5 we have listed several Lecomene
O •z.7*
Sodium Oleate •8
estimated HLB values for emulsi- Potassium Oleate 20
fiers. These were determined and Cationic
correlatedby preparing vast series Atlas G-zs• z5-35
of emulsifier-blend tests as in the Non-Ionic

illus.trations.Groupingin thistable OleicAcid App. I

Span 85 t .8
is accordingto compositionas well ArlacelC 3- 7
as HLB since both are influential Span 8o 4.3
Span60' 4,7
in choosingan emulsifier.We hope Span 2o 8,6
Tween 8• •o.o
to extendthis list, and expectto do Tween 6o i4. 9
so. The magnitudeof this type of Tween8o •5.o
study is understoodwhen you real- Tween•o • 6.7
ize that each of these values was Othervalueslistedin booklet,"Surface
Active Agents," published by Atlas
derived from approximately 75 Powder Co.
emulsions. A more extensive tab- * Tentative value.
ulation of estimated HLB values
for Atlas productsis availablein The various types of emulsifiers
the Atlas SurfaceActive Agents representedin Table 5 may be
Booklet (6). We have found the blended,observingthe usual pre-
chart,Fig.8, mosthelpfulforrapid cautionsof incompatibility. In ad-
calculation of HLB values of blends dition, there are indications that
ofemulsifiers.
Thelocation
ofglyc- someemulsifiers
arenot compatible,
eryl monostearatein Table 5 is of or perhaps co-operativeis a better
interest. This reference is to the word, in a surface-activesense. This
pure form and not to the self-emul- action is probablyrelated to over-
siftable varieties. The available all efB_ciency of the emulsifier and
self-emulsifiabletypesare not non- is therefore not conclusivelyindi-
ionic,sir•ceionicemulsifiers
(soap, cated.
etc.) are added to render them self- Chemical reactivity of an emui-
emulsifiable.This is an exampleof siftercan modify the behaviorof an
322 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

PERCENTAGE OF "•B"
0 S I0 15 20 25 30 35 40 45 50 55 60 65 70 75 •0 85 90 95 I00

27
ATLAS HLB COMPUTOGRAPH 27
FOR COMBINATIONS OF SURFACE ACTIVE AGENTS
26 26

25 -- 25

24 24

2• 2•

22 • 22.•
2l 21"

2O 20 0

19 19 ../

<{lB 18
O 16 -- 16
• ,40
...I 15 15-TW[EN•0
14 14

13 -TWœEN
21
12 12

II I-TWEEN •5
65

9
SPAN 20 --
10 -
-- J. IO-'TWEEN
,
BI
7 •-- 7
SPAN '-- -
6
SPAN 62 -- -

5 5
SPAN, -- -
SPAN 4 4

SPAN 65-
_-2: - z
SPAN
I

0 0
0 .5 I0 15 20 25 30 35 40 45 50 55 60 65 70 75 8,0 65 90 95 100
PERCENTAGE OF "B"

SPAN• TWF...œN:
RE.•. U.S. PAT. OFF,

emulsifierimmensely. In the case of acidic constituents lowered the

of soaps,tracesof multivalent ions HLB of the emulsifiermarkedly.
completelychangethe HLB. An- Likewise, in Table 6 we have
other instance that we have ob- listed the estimatedrequiredHLB
served was with an amine-neutral- values for several of the more com-
izedaryl sulfate,wherethe presence monly used oils and waxes. These
 CLASSIFICATION OF SURFACE-ACTIVE AGENTS 323

T. BL• 6

RequiredHLB for
o/w w/o
Oil or Wax Emulsion Emulsion

Cottonseed Oil
Carbontetrachloride
ParafFin(household) . 9
Microcrystallinewax (MicropacQ, S-V) 9.5*
MineralOil, White, light (MarcolGX) io
MineralOil, White, heavy(Nujol) Io.5
Mineral Seal Oil Io.5'
Petrolatum,white (White Perrecta) xo.5
SiliconeOil (G. E.) Io.5'
Kerosene
Naphtha I3'
ßCetyl Alcohol I3
Orthodichlorobenzene
•' i3'
Beeswax,white io-i6
Carnauba Wax I4.5'
Candelilla Wax i4.5'
Lanolin,U.S. P., anhyd. I5
Dimethyl Phthalate i5'
Orthophenylphenol
Stearic Acid 17

* Tentative.
•' Plussmallamounts(3-5%) of pineoil andisopropylalcohol.

values are reported only in half- If the properties,particularlythe

unit incrementsdue to lack of pre- requiredHLB, of the oil phaseare
cision in measurement. However, unknownas in the first condition,a
the values are amply accuratefor preliminary exploratorytest is set
use with the HLB values for the up. This is usually done with a
enmlsifiers in a selection of an non-ionic emulsifier combination,
emulsifier combination. The oils suchas Span 60 and Tween 60, of
and waxes are tabulated in ascend- known HLB values.
ing order of requiredHEWs. As The first series of determinations
would be expected similar values are prepared with various ratios of
are noted for like chemicaltypes. theseemulsifiersusing a maximum
amount of total emulsifier. Usu-
METHOD OF USE OF HLB VALu•.s
ally a series,resemblingthose in
We have developed a "refined the top row of Fig. 6, is obtained. It
trial-and-error system" based on appearsthat the optimumHLB for
HLB values. In any emulsification this systemis betweensamples3
problem one of two conditions can and 4. A more accurate determina-
exist: (1) the problem can be to tion of the required HLB is next
emulsifyan oil phaseof unknown obtained by the preparationof a
composition,or (2) the approximate secondseries,usingsmallincrements
desiredformula may be known in- of this same pair of emulsifiersas
cluding the compositionof the oil shown in the second row of tests.
phase. After determinationof the opti-
324 JOURNAL
OFT•IE SOCIETY
OFCOSMETIC
CHEMISTS

the chosen chemical type at the

most favorable HLB and at the
minimum required total concen-
tration. This last seriesof samples
is usually put throughmore exten-
sive and more stringent stability
tests.

If the required HLB of the oil

phaseis known approximately,the
first series of tests may be elimi-
nated. If it is knownwith greater
.., '•-•
accuracy,both the first and second
ß

'seriesof testsmay be omitted.

For an example, an All-Purpose
Cream has beenchosenwith a pro-
ß H H ]man . • • • JlaL •,) q, II ,+
posedformula of:
Beeswax ...................... 5
Mineral Oil .................... 26
Hydrogenareal
VegetableOil ..... 18
Polyol ........................ 4
--

Emulsifier ..................... 5-10

Water,q. s. to make............ 100
The oil phase,then consistsof the
followingapproximatepercentages.
Esti-
mated
Re-
Figure &--Example HLB use emulsions, quired % X
alLpurpose cream Oil or Wax % HLB HLB
(Top Row) Preliminarydetermination of Beeswax 10 15 1.5
requiredHLB of oil phase. (Middle Row) Mineral Oil 53 10 5.3
Final estimationof requiredHLB, value10.4. Hydrogenareal vege-
(BottomRow)Comparison of variouschemical table oil 37 9 3.3
types,all at sameHLB
Figure 7.--Effect of polyol on all-purpose Average estimated
cream
requiredHLB 10.1
(Top Row.)Various amountsof Arlex.
(BottomRozo)Variouspolyols. Calculation of an estimated re-
quiredHLB givesa value slightly
mum point, the chemicalclassifica- over 10. Therefore, the initial
tion for the emulsifieris studied by
serieswith thisoil phasecanbe pre-
preparinga third test series,as in paredcombining Span60 andTween
the third row, in which emulsifiers 60 to giveHLB valuescloseto 10, as
of selected differentchemicaltypes in the secondrow, Fig. 6.
are tried, all of which have been
Span60-Tween
60 Calculated
HLB
previously
blendedto the required 50-50 9.8
HLB. After choosing the chemical 45-55 10.3
40-60 10.8
type, a final seriesusuallysuffices 35;--65 11.3
to providea blendof emulsifiers
of 25-75 12.4
 CLASSIFICATION OF SURFACE-ACTIVE AGENTS 325

The best ratio in this seriesis 45% fected by the type and amount of
Span60 and 55% Tween60 at a polyol.
calculated HLB of 10.3. The dividing line between in-
The evaluation of different chemi- gredients and emulsifie•:sis often
cal typesof emulsifiersis then con- not clear. Stearic acid, lanolin,
sidered as previously mentioned. cholesterol,and beeswax are just
For thisexample,the stearateblend a few examplesof materials that
is the best chemicaltype. Usually may servea dual role. An example
it will be desirable to cover a much of this is in soap-emulsified-facial-
wider range of alternate chemical creams in which the stearic acid is
typesthan the spacelimitationper- partially neutralized. In this, the
mitted us in the third row of Fig. 6. stearic acid forms a bulk of the oil
It must be remembered that all phase, but portions of the stearic
blends must be at the correct acid are present as emulsifier,both
HLB. neutralizedand as free acid. By
It is interestingto note that the examining a system, it is usually
addition of polyol to the aqueous possibleto evaluateeachingredient
phaseof an emulsionsuch as was in the terms of its uses.
just studieddoesnot appearto alter
APPLICATIONS OTHER THAN EMUL-
the HLB appreciably. The samples
SI FICATION
in the top row of Fig. 7 show the
effectof adding various amountsof (1) Atntifoaming
commercialsorbitolsirup. The per- Antifoaming is quite a specific
centagesare the amount of Adex* action, therefore it is surprising
in the total formula, not the amount when most of the Atlas agentsthat
in the aqueousphase. Therefore, have found success as antifoam
for the fourth samplethe aqueous agentsfall in the rangeof 1.5-3 and
phasecontainsapproximately40% all are less than 8. No complete
polyolwhichis a sizableproportion. studyof thissubject,aswith emulsi-
In the secondrow, three different fiers, has been made or is contem-
polyols are employed. Little dif- plated.
ference is noted in the emulsifica-
tion,regardless of the type of polyol (2) PI"ettingand Spreading
used. This doesnot imply that the Atlas wetting and spreading
three polyolswill producesimilar agentsfall in the rathernarrowHLB
cosmetic effects. These differences rangeof 7 to 9. We havefrequently
are well known and are due to the tried productsoutside this range,
variations in hygroscopicities, co- but with little success,particularly
solubilities,and otherphysicalprop- when the values were greater than
erties of the polyols themselves. 9. Wetting is usually desiredin an
The dataindicatethat at the proper aqueous solution, suspension,or
balanceof emulsifier,the emulsifi- O/W emulsion,and this is probably
cation will not be appreciably the cause of the narrow effective
326 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS

range. No extensiveselectionwork of the emulsifier,doestell "what it

has been done in this field. will do"--that is, wha't kind of an
emulsionor productto expect. By
(3) Detergents so doing,it enablesus to compare
Atlas detergent materials fall variouschemicaltypesof emulsifiers
into the HLB rangeof 13-15. This at their optimum balance. Esti-
mated HLB values for various
range is in accordwith recent the-
oriesof detergencythat solubilizing types of emulsifiersand fats and
of the soil is a part of the action oils were presentedas well as a
method for their determination.
since13-15 is above the usualO/W
Use of the method was illustrated
emulsifier range and is close to
solubilizers. by choosingan emulsifiercombina-
tion for a typical cosmeticcream.
(4) Solubilizers The HLB systemappearsto be suit-
able for all types of problemsem-
Solubilizingrequires the highest ploying surface-activeagents.
HLB (for common uses) at 15-18.
BIBLIOGRAPHY
For this purpose,singlehigh HLB
agentsare frequently used. Early (1) Goodey, J. H., Australian Chem.Inst.
work has indicated that the HLB y. & Proc., 16 47 (1949).
(2) Lambert, J. M., and Busse,W. F., 5e.
can be too high for efficient solu- Am. Oil Chem.Sot., 26 289-296 (1949),
Table 4.
bilizing. The effective range ap- (3) McBain,J. W., et al., Chem.Abst.,31.
pearsto be narrowevenfor different 16777; 36 34139, 5581a; 38 11606; 42.
4022b.
oils. No thoroughstudy of solubil- (4) Roberts,C. H. M., 7. _Phys.
chem.,36
izing rs. HLB has beenundertaken. 3102 (1932).
(5) Schwartz, Anthony M., and Perry,
James W., "Surface Active Agents;
SUMMARY Their Chemistry and Technology," In-
tersciencePublishers,New York, 1949,
We have describeda system for pp. 346-347.
the choice of emulsifiers based on (6) Atlas Powder Company, "Surface Ac-
tive Agents," Wilmington, Del., 1948.
their hydrophile-lipophilebalance/ Table facingpages26 and 27.
The HLB system, though it does * Nots: Span,TweenandArlex are Reg.
not indicate the over-all efficiency Trade Marks, Atlas Powder Company.