ELSEVIER

Chemistry of Soaps and Detergents:

Various Types of Commercial
Products and Their Ingredients
MARCEL
FRIEDMAN,
RONNI
WOLF, MD

PhD

Soapmaking from the Romans to the

20th Century
Soap is probably the oldest skin cleanser. For thousands
of years, this product has been obtained from the saponification of oils and fats by alkali.
As is true for most human discoveries, the first
chemical saponification was found by chance. According to a Roman legend, soap was discovered accidentally near Mount Sapo, an ancient location for animal
sacrifices not far from Rome. The animal fat, mixed
with wood ashes (the ancient source of alkali) and rainwater, created an extraordinary soap mixture. Roman
housewives noticed that the strange yellow mixture of
the Tibers waters made their clothes cleaner and
brighter than ordinary water.
Soapmaking became an art in the time of the Phoenicians and saw significant advancement in the Mediterranean countries, where olive oil of a local origin was
boiled with the alkali ashes. The famous Marseilles soap
probably had its roots 1000 years ago in local soapmaking facilities.
The real breakthrough in industrial soap production
was made by a French chemist and doctor, Nicolas Leblanc, who invented the process of obtaining soda from
common salt (L.eblanc process, 1780):
2NaCl+ H,SO, + Na,SO, + 2HCl
Na,SO, + 2C --f Na,S + 2C0,
Na,S + CaCO, + Na,CO, + CaS

facture. Soap, which had been a luxury item affordable

only to royalty and the rich, became the main product
for everyday personal hygiene.
Nowadays,
soap remains the essential base for
cleansing solid bars. Even during the tough economic
times of the 199Os, annual bar soap sales in the United
States amounted to $1.5 billion. The total annual toilet
soap market in Western Europe is more than 340,000
tons, giving an average of 0.82-kg consumption per person per year.

The Chemistry of Natural Soaps

It is surprising that in spite of technical achievements
and scientific developments,
classic soap is still based
on the same chemistry as that of ancient soaps.
Soap is chemically defined as the alkali salt of fatty
acids. In general parlance, the term soap has taken on
a more functional definition, by which any cleansing
agent, regardless of its chemistry, is considered a soap.
This sometimes misleading
definition will be further
considered as we deal with the chemistry of the synthetic detergents and the soapless soap revolution.
Soap is manufactured by the saponification process,
by which triglycerides (fats and oils) or fatty acids are
transformed into the corresponding alkali salt mixtures
of fatty acids. Today we can differentiate among three
methods.
1. Direct neutral fut saponification, in which oils and fats

(sometimes after purification

with various agents,
such as active earth) are directly~saponified
with alkali in a boiled or semiboiled kettle process.

In this process, table salt was mixed with sulfuric acid,

producing sodium sulfate, which was further heated at
about 950C with coal and limestone to get a mixture
from which the carbonate was extracted with water.
Leblancs process increased the availability
of alkali
at reasonable cost, transforming
soapmaking
from a
cottage industry into a commercial industrial manu-

CH,OOCR
CHOOCR
CH,OOCR
Triglyceride

2. Fatty acid suponificution, in which the fatty acid distillates (obtained from triglycerides by hydrolytic splitting) are neutralized.

From Neca Chemicals, Ltd., Petach Tikva, Israel, and the Sacklzr Faculty
of Medicine,
Tel Aviv University,
Tel Aviv, Israel.
Address correspondence
to Dr. Marcel Friedman,
Neca Chemicals, Ltd.,
P.O. Box 333, Petach Tikva, Israel.

0 1996 by Elsevier Science Inc.

655 Avenue of the Americas, New

York, NY 10010

+ 3NaOH

3RCOONa
Soap

CH,OH
CHOH
CH,OH
Glycerol

The resulting mixture of soap and glycerin is treated

with salt to precipitate the soap, which is then separated
from the glycerin solution, washed, and dried.

RCOOH

+ NaOH

-+ RCOONa

+ H,O
0738-081X/96/$32.00
SSDI 0738-081X~95JOO102-6

The soap bases obtained by the above two processes

have a fatty acid content of 63 to 75%. They are then
continuously
dried to a final mass of 78 to 80% fatty
acid content. These processes account for more than
95% of world soap production.
In Japan, however,
a
third manufacturing
process is used:
3. Fatty acid methy ester saponificatiorl.
RCOOCH3
methyl ester

+ NaOH

-+

3RCOONa
soap

CH30H
methanol

The methyl esters are obtained by catalytic transesterification of triglycerides

with methanol or direct catalytic esterification of fatty acids with methanol. The end
product of this process has a higher fatty acid content,
at the expense of a more costly process. For economic as
well as for toxicologic and ecologic reasons, the process
must be carried out in sealed equipment with recycling
of methanol.

Formulation

of Natural

Soaps

The formulation
of soap bars involves a skillful combination of scientific thought and artistic creativity in the
selection of appropriate ingredients of the formula. The
typical components of a soap bar needed to achieve the
expected performance
are shown in Table 1.
The challenge to a soap formuIator
goes far beyond
the production of an effective cleansing agent. To fulfill
consumers
expectations
and needs, a broad range of
qualities are demanded of a soap.
In addition to cleansing properties, color, and odor,
which are always thought of as the main attributes of
soap, other qualities have to be taken into consideration:
1. Lathering
(foam performance&--amount,
quality,
density, and stability.
2. Skin compatibility.
3. Soap bar texture.
4. Soap bar mushing (to overcome the tendency of the
soap to form a gelatinous material on its surfacesoap mush, in contact with water).
r
Soap bar erosion rate (bar wear rate).
6: Chemical stability (odor, color, rancidity, and effluorescence) .
7. Physical stability (cracking).
8. Rinsability (from skin and bathtub).
The desired benefits of the finished soap product are
governed by a professional selection of appropriate surfactant cleansing raw materials (in this case soap) and
of manufacturing
process and by the marriage between
the two.
The type of the alkali used determines the hardness
and solubility of the finished product. Sodium soaps are
known as hard, being the workhorses
of normal bars,
cakes, and powders.
Potassium soaps have a greater

Tddc 1. Toilet Soup lngredierits

Ingredients
Cleansing

surfactants

Moisturizers
Superfattening
agent
Bar-hardening
agent
Fillers
Antioxidnnts
(preservatives)
Chelating
agents
Whitening
agents
Deodorants
Fragrance
Dyes and pigments
Water
~
_-.- --._-----___

Soap

Synthetic
detergent
Glycerin,
lanolin
Fatty acid
Salt

PJaCl)

Starch
BHT (butyiated
hydroxytoluene)
EDTA
Titanium
dioxide
(TiO,)
Triclosan,
trichlorocarban

solubility in water and are used in liquid and soft soaps.

Triethanolamine
soaps are known for their lower pM
(because of the less alkaline nature of the cation), which
allows the formulation
of a milder transparent
soap
with a lower pH.
The nature of triglycerides
and fatty acids plays A
key role not only in the performance
and features of the
end product but also in its cost. The commercial triglycerides used for soap manufacture
are of animal origin
(fats of tallow, lard, etc) and of plant or vegetable sourcle
(oils of coconut, palm kernel, olive, etc). Most toilet
soap bars are made of a mixture of feedstocks derived~
from tallow fat (75 to 85%) and coconut oil (15 to 25%?.
The modern back to nature consumer trend created rt
demand for vegetable soaps, mostly based on mixtures
of palm oil (75 to 85%) and coconut oil (35 to 25%:), The
toilet soaps contain about 80% of that mixture and
about 12 to 14% water. For geographic considerations,
local feedstocks,
mostly vegetable-such
as olive oil,
rice bran oil, and sunflower
seed oil-are
successfullv
used.
The final performance is determined by length ot the
hydrophobic
fatty chain moiety, saturation extent of the
fatty acid chain (number of double bonds), and fatty
acid distribution
and composition
of the triglycerides.
The most commonly
used tallow fat is predominantly composed of 40 to 50% Cl8 fatty acids and 25 to
30% Cl6 fatty acids, about 5% of which are unsaturated.
In many countries, soaps in solid form are strictly
defined according to their purpose, toilet and laundry
bars being the majority. Toilet soaps contain more than
80% fatty acids and about 12 to 14% water.
Clearly, the formulation
of soap is still a challenge.
Todays formulators
are still waiting for some exciting
development to happen, even by chance, as in the wellknown story of Ivory soap. In 1878, after four years ct
development,
the Gamble brothers finalized the formula for a white soap. During the mixing of a large
batch of this soap, the soapmaker went to lunch, leaving
the mixer running. When he returned, he noticed that

Clinics in Dermatology

1996;14:7-13

CHEMISTRY

air had been incorporated into the mass of the molten

soap. As he thought that his error would not be noticed,
he did not discard the batch but proceeded to mold, cut,
package, and ship the soap. A few weeks later, letters
from pleased customers began to arrive at Procter &
Gamble, asking for more of the soap that floated on
water.

Cleansing Soapless Bars-A

Breakthrough

The alkali pH of natural soap is produced by the hydrolysis of soap in aqueous solution, by which a quantity of alkali is released, raising the pH of the water to
about 10 or 11. The pH is further increased by residual
amounts of alkali retained in the soap during manufacture. The high pH of natural soap is probably the main
cause of the well-known negative soap effect.
Another major disadvantage of natural soap is its
behavior in hard water or saltwater. Historically,
this
was the major reason for the first replacement of alkali
soap by the new generation of alkali-free neutral soapless soaps.
During the Second World War, sailors who spent
months at sea under severe freshwater restrictions had
to use seawater for washing. Under these conditions,
they realized, normal soap did not foam. This was actually the main motivating factor in the search for a new
type of foaming cleansing agent.
The answer was provided by the synthetic detergents (syndets) that became commercially
available in
the late 1940s and early 1950s.
The difference in the behavior of the syndets in hard
water or saltwater is correlated to the solubility of the
soap. Natural soap forms insoluble and inactive salts in
the presence of magnesium and calcium, contained in
hard water:
2 RCOONa + Mg + (RCOO),Mg + 2Na
2 RCOONa + Ca++ -+ (RCOO),Ca + 2Na
When water is very hard or contains a high level of
electrolytes (as in seawater), the foaming performance
of soap is seriously inhibited, if not eliminated. In addition, the insoluble salts precipitate on the surfaces of
sinks and bathtubs as a gray fatty mass, unsightly and
difficult to remove. Unfortunately,
the same happens in
the cleansing of the skin, on which calcium and magnesium salts precipitate. The dermatologic drawback of
this is obvious.
The synthetic surface-active agents (surfactants) do
not have these important disadvantages, and it is for
this essential reason that they have been used in the
manufacture of dermatologically
recommended
syndet
bars.

Chemistry of Synthetic Surfactants

A surface-active agent is defined as a chemical substance that, even at low concentration, absorbs at the
surface, reducing the free surface energy at the interface

OF SOAPS

AND

DETERGENTS

of any two-phase system, such as gas-liquid, liquidliquid, or liquid-solid.

To achieve this, the surfactants must dissolve in each
of the two phases. This is accomplished by the presence
of two distinct groups in their molecular structure. In a
water-oil system, one group will be easily soluble in
water (hydrophilic); the other will be insoluble in water
(hydrophobic) but soluble in oil (lipophilic)
(Fig. 1).
The balance between hydrophobic
and hydrophilic
features governs the application of the surfactant as a
detergent, wetter, or emulsifier.
A known scale, characterizing the surfactant according to its hydrophilic-lipophilic
balance (HLB), was presented by Griffin. According to this system, highly hydrophobic surfactants have low HLB values, starting at
1, whereas highly hydrophilic molecules are given high
HLB values, up to 40. Detergents, for instance, have
values in the range of 13 to 15, compared to only 4 to 6
for water in oil emulsifiers.
There are four main types of surfactants, classified by
the nature of their hydrophilic
head: anionic, cationic,
amphoteric, and nonionic. The first three are charged
molecules.
Anionic surfactants possess a negative
charge that has to be neutralized with an alkaline or
basic material before the full detergency is developed.
Cationic surfactants are positively charged and therefore have to be neutralized by a strong acid before they
can develop surface properties. Amphoterics
include
both acidic (negative) and basic (positive) groups in
their molecules
and are positively
or negatively
charged, according to the pH of the solution. The nonionic surfactants contain no ionic constituents, having
no electric charge (Fig. 1).
Soap is the simplest anionic surfactant. Since the saponification reaction is a simple hydrolysis of natural
materials, soap is often considered a natural surfacFigure 2.
Lipophilic

My

Hydrophilic

chain

end

/-----\/m-l//-\.

-.

Anionic surfactant

mu

\-e-v.>

-
Cationic surfactant

-z;

:/^---(I
3Amphoteric sutfactant

10

FRIEDMAN

AND

ihics

WOLF

tant. All other surfactants, obtained by many simple or

highly sophisticated
reactions, are considered synthetic
surfactants.
Like soap, most surfactants
used in personal cleansing bars are anionic. A list of the anionic surfactants
(including soap) that are used as active ingredients
in
cleansing bars is given in Table 2.
Examples of some other surfactants used in personal
cleansers,
for different
synergistic
roles other than
cleansing (such as plasticizing,
moisturizing,
binding,
and filling) and for improving
the overall performance
of the finished bar, are presented in Table 3.
The cationic surfactants
have only minor use in personal cleansers, primarily because of their incompatibility with anionic surfactants,
as the anion and cation
precipitate each other.

Mass-Market

Syndets of Combars

Soapless cleansing bars have come a long way since

they were first developed more than 40 years ago. It
was then that a West German doctor formulated a mild
cleansing bar for his patients who, because of sensitive
skin, were unable to use ordinary, natural soap. The bar
of those times, however,
was made from surfactants
similar to those popular and still widely used in shampoos. In fact, some soapless soap manufacturers
defined their bars as solid shampoo,
promoting a successful marketing
approach. A similar approach was
adopted by the Israeli market, the only one in which the
syndet cleansing bar covers more than 50% of the total
soap bar market. This market share is greater than in
any other market, although the European and American markets of syndet bars have been growing
immensely during the past three years. According to 1991
Table 2. Aniorlic
Cleansina Bars

Surfactads

Used 61s Actioe Ingredients

SurfacfantName
Sodium carboxylate
(soap)
Sodium alkyl sulfate
Disodium
alkyl
sulfosuccinate
Disodium
amido
sulfosuccinate
Sodium
acyl taurate
Sodium
acyl isethionate
Sodium
alkyl sulfoacetate
Sodium alkyl sarcosinate
Disodium
acyl glutamate
Sodium monoglyceride
sulfate
n-Sulfo fatty acid esters
Sodium dodecyl
benzene
sulfonate
Sodium alkyl ether sulfate
ol-Olefin
sulfonate

ChemicalFormula
RCOONa
ROSO,Na
ROCOCH6O,NaKH,COONa
RNHCOCHKXI,NaKH,COONa
RCON(CH,)CH,CH,SO,Na
RCOOCH,CH,SO,Na
ROCOCH,SO,Na
RCON(CH,)CH2COONa
RCONHCH(COONa)CH,CH,COONa
RCOOCH,CHOHCH,OSO,Na
RCHfSO,NaKOOCH.,
RC,HsSO,Na
ROfCH,CH,O),SO,Na
RCHRCH-CHCHCH,SO&a

~1

Table 3. hurediewts

ill Uermatology

0 1996;74:;--

1.3

of Soav

lngredienf7

---

Surfactants
Plasticizer
and binders
Lather enhancers
Fillers and binders
Water
Fragranct
Opacifying
agents

reports, Germany appeared to be the major European

soaplesscleansing bar manufacturer, with consumption
of about 30 million bars per year. Although this accounts for only 5 to 6% of the total volume of the German soap market, it may account for up to 20% of the
total value market, since syndet bars are substantially
higher priced.
The high price of the syndet bars is due not only to
the more expensive formulation than that of the natural
soaps but also to the marketing positioning and strategy. Most of the successful brand names in Germany
are positioned on a dermatologic platform as premiumpriced, upscale products, focusing on their benefits to
the skin.
These premium-priced products are sold primarily
through pharmacies and drugstores, whose high margins results in a final consumer price of $2 to $3.0~per
100-gm bar. In France, where the soapless soaps are
categorized as pair1 dermatologique, leading brands account for about 2% of the total soap market and are
priced similarly to their German counterparts.
Thirty years ago, Neca, an Israeli manufacturer, took
an entirely different approach. Neca was the first to
recognize the mass-market potential of a bar with the
benefits of a synthetic soap but sold at a popular price.
In 1964 the company introduced Neca 7, a soapless
cleansing bar with a dermatologic value similar to the
European synthetics but priced at 50 to 70 cents per
100-gm bar and marketed as an all-purpose cleansing
bar through all distribution channels. Neca 7 quickly
became the leading brand in Israel and now commands
35% of the total soap market, with consumption of 2
million bars per month by a population of 5 million.
Neca 7 can probably be considered the worlds bestselling soap per capita.
The same marketing approach has been successfully
applied in the United States by Lever Brothers, which
followed the same strategy of mass-market distribution,
pricing, and promotion for its soaplessand combination
cleansing bars, especially Dove and, more recently, I,+
ver 2000. In 1955, Dove was introduced as different
from other toilet bars because it looks like a soap, it3
used like a soap, but it is not a soap. Later, Lever began
emphasizing that Dove contains one quarter moisturizing cream and wont dry your skin like soap,

Clinics in Dermatology

1996;14:7-13

which remain the slogans of the present advertising

campaign.
In 1993, Dove was the best seller, accounting for
16.4% of the U.S. bar soap market. The success of soapless and combo bars in United States was so dramatic
and sustained that in 1991 Lever Brothers was able to
oust Procter & Gamble from the leadership position in
the toilet soap market.
A comparison between the two giants shows a market share increase from 24.1% in 1983 to 31.5% in 1991
for Lever Brothers (based on dollar volume), as compared to a decrease from 37.1% to 30.5% at the same
time for Procter & Gamble. The Wall Street Journal dramatically reported buoyant sales of Lever 2000 soap
bring sinking sensation to Procter & Gamble. Two
years later, in 1993, Procter and Gamble gave a prompt
answer in this soap war, regaining the leadership
with the success of its Whitewater Zest and, especially,
Oil of Olay cleansing bath bars. The marketing strategy
of the Oil of Olay bar-a beauty bar at a competitive
price-helped
Procter and Gamble to take over the top
position by May 1993 with a 32.5% share, compared to
31.5% for Lever Brother. The key to Procter and Gamble
success was mostly due to over 10 years of research and
development,
which enabled the creation of a unique
formula, which contains a specially engineered synthetic cleansing system.
This emphasizes again the importance of a properly
chosen formulation
for a targeted cost-effective product.

Formulation

of Soapless Cleansing Bars

The list of surfactants presented in Table 2 gives only a

few of the thousands of synthetic detergents and innumerable plasticizers, binders, moisturizers,
and fillers
available for formulating
syndets. It follows, therefore,
that todays formulators are limited only by their own
degree of imagination
and chemical skills.
Constructing the formula of a syndet or combination
bar is a complex challenge, as the final qualities and
requirements are numerous and sometimes contradictory. The properties required from the finished bar have
been already mentioned here and will be further exposed in the following chapters of this issue.
A major requirement for the formulation
of syndets
is workability
(processibility). This is the ability of the
base to be converted into bars by the use of the appropriate soap equipment. The formula ingredients should
provide sufficient plasticity necessary for extrusion
(plodding) and stamping of the bar.
To achieve all these requirements and properties, a
good syndet bar is essentially composed of a blend that
includes the ingredients listed in Table 3.

CHEMISTRY OF SOAPS AND DETERGENTS

11

Surfactan ts
The choice of surfactants and their proportions not only
determines the cleaning and lathering characteristics
but also influences mushing, plasticity, and, of course,
skin compatibility.
European and Israeli formulations are based mostly
on a blend of alkyl sulfates and alkyl sulfosuccinates,
reaching about 40 to 50% surfactant content. The pH of
the bar is normally adjusted between 5.5 and 7.0. It has
been found that the potassium salts give much better
mushing and plasticity properties than the sodium
salts, and there is an optimum K:Na ratio for minimum
mushing.
The U.S. mass-marketed brands are based on other
surfactants. The leader, Dove, is based on fatty acid
isethionates, specifically sodium cocoyl isethionate. As
this is an expensive ingredient,
the formulation
includes about 30% of fatty acid (specifically stearic acid
and a minor proportion of coconut acid) and fatty acid
soap, mostly neutralized to a final pH of 7 to 7.5. The
product contains some dodecyl benzene sulfonate (1 to
2%) as a lather enhancer. This overall surfactant blend
reduces the final cost of the formulation but, because of
the price of cocoyl isethionate, still keeps it expensive.
Compared to European bars, Dove has a rather soft and
dull appearance and might seem somewhat slimy to the
European consumer. Oil of Olay is also cocoyl isethionate based, but in a more sophisticated,
well-performing formulation.
Since the mildness concept has been strongly advertised by Lever Brothers as an intrinsic property of isethionate bars, a serious change has taken place in the
formulation
of bars in Western Europe in the past few
years. Products have been reformulated, and more expensive isethionate bars, claiming even milder properties, have been introduced.
The drawback of the cocoyl isethionate bar, easily
consumer perceived, lies in its strong, characteristic
odor. This odor, recalling the coconut source of the fatty
acid, needs a higher dosage of fragrance to be covered,
which creates a problem in the fragrance-free hypoallergenic formulations.
The other major surfactants used in U.S. formulations are sodium cocomonoglyceride
sulfate (in Colgates Vel) and sodium cocoglyceryl ether sulfonate (in
Procter & Gambles Zest combo bar).
In Japan, acyl glutamate, made by Ajinomoto, is the
basic surfactant of Minon, a very expensive soapless
cleansing bar, sold at about $6 per 75 gm.
An interesting evaluation of the cleansing effect of
various bars indicates that alkyl sulfate and sulfosuccinate blends have the highest cleansing power, followed by acyl glutamate and triethanolamine
soaps.

Natural sodium soaps were ranked last in this evaluation.

Most of the surfactants used, as well as plasticizers or
binders, are of vegetable origin, which is a valuable
marketing
advantage, offering Kosher and natural formulations (Tables 2 and 4).

Lather Enhancers
The foaming properties of different surfactants and finished syndet formulations
can be checked by several
methods whose description is beyond the scope of this
article. The most common and reliable of these is the
mechanical inversion test. By this test a higher foam
performance
was found for alkyl sulfates and sulfosuccinates than for isethionate and natural soap.
To enhance the lather performance
of the primary
surfactant in lather formation speed, lather stability, or
cold water performance,
some foam enhancers can be
used. Dodecyl benzene sulfonate, sodium lauryl sulfate,
alkanolamides,
and even fatty acids perform this function well.

Plasticizers

and Binders

To obtain good processibility

and usage properties, the
formulation
is stabilized with plasticizers
and binders.
Plasticizers
are included to facilitate better extrusion
and stamping of the syndet bar. The plasticizers act by
lowering
the viscosity of the material at the manufacturing temperature,
providing flow under pressure.
Binders prevent separation
of macroscopic
aggregates, caused by local stress, providing
cohesion and
anticracking
behavior of the solid product.
Natural
soap does not have plasticity problems, as the soap itself is a classic plasticizer, beyond its cleansing surfactant role. Plasticizers
and binders strongly
influence
lathering, mushing, and wear characteristics.
Generally,
the plasticizers and binders are used together and one
material can perform at least two roles. They are capable of absorbing some, or all, of the free water of the
syndet, binding the various ingredients
together, plasticizing the mass, and acting as emollient, all at the
same time. The plasticizers
most commonly
used are
long-chain fatty alcohols (higher than C16), polyol esters (glycerol monostearate,
sorbitan stearate, and giycerol mono- and distearate), polyethylene glycol, sodium
Table 4. Surfactants Used for lmaruuementof SoaaPerforuzance
Surfactant Name
Fatty acid alkanol amide
Fatty acid ethoxylate
Fatty alcohol
Polyethylene
glycol
Fatty alcohol ethoxylate
Glycerol
monostearate
Alkyl amido propyl
betaine

ChemicalFormula
RCONH,
RCOO(CH,CH,O),,CH,CH~OH
ROH
HO(CH,CH,O),H
RO(CH,CH,O),H
RCOOCH2CHOHCH,0H
RCONHCH2CH,Nf(CH&IHzCOOH

stearate, stearic acid, fatty acid ethoxylate, hydrogenated castor oil, paraffin wax, fatty alkyl ketones, and a
combination of hydrogenated triglycerides with fat!v
alcohols or acids.
The plasticizers and binders have high melting
points and high molecular weights. It seems that their
binding activity is obtained when the melting point of
the massis simply raised. Ingredients such as gums and
gum resins provide additional cohesion by acting a>
binders.

Fillers
The so-called fillers are, by definition, cheaper ingredients, used to reduce the bar cost. In the case of syndets,
the fillers are not inert ingredients but participate in
improving the internal structure and hardness of the
finished product. The fillers can therefore be called additional binders. The best-known fillers are dextrin,
starch, and modified starch (degraded, ethoxylatedb.
Talcum powder has also been used as a filIer against
mushing, while buffered borax is added to reduce specific gravity and lower wear.
The drawbacks of the fillers are a rough surface trx
ture, loss of slip, and loss of attractive overall appearance. For this reason, one should not exceed an optimal
concentration of these substances.

Performance-

and Appearance-lmprooing

Additives

One perceptible drawback of the syndets is their solubility and mushing in water, due to the high solubility
of the surfactants. A syndet bar behaves much like
paste, not like structured gel. Under certain formulations, this pastelike mush is unable to return to a solid
state by losing water from the mush layer. One major
solution used for alkyl sulfate syndets is to use their
potassium salts, which give a low mush and an economical base.
Other low-solubility improvers are inorganic salts,
such as sodium sulfate and sodium chloride, together
with dimmer linoleic acid. Aluminum triformate is also
effective in sulfosuccinate formulations.
A desirable property like slipping has been obtained
by the addition of zinc stearate and ethoxylated sorbitan ester.
Sodium isethionate is added in an acyl isethionate
formulation to reduce the wear rate.
Antibacterial additives, such as trichlorocarbanilide
and triclosan, are further examples of successful additives for deodorant bars.
The humectants and moisturizers are very important
for skin afterfeel and for dermatologic marketing
claims. A variety of such additives have been researched, including glycerin, methyl glucose ethers,
lanolin derivatives, mineral oil, isopropylmyristate,
glutamates, and lactates.

Clinics in Dermatology

1996;14:7-13

Conclusions
The soap industry is an ancient one whose origins go
back to the days of the Phoenicians. At the end of the
1940s and beginning of the 195Os,the industry took a
giant step forward when it introduced the soapless
soaps, and since then it continues to advance and to
improve.
The demands made on a good soap are many and
varied and sometimes even contradictory. Preparation
of soap formulas is extremely complicated and requires,
together with knowledge of chemistry and engineering,
both imagination and inspiration. In the limited amount
of space available to us, we have tried to give the reader
an idea of the different ingredients of soaps, their functions, and their effects. The formulation of soaps today
is the result of research and development, as well as
trial and error, done over many years by large research
teams. It is not surprising, therefore, that in a review of
the present kind it should be possible to reveal only a
small fraction of the secrets of this huge industry-all
the more so, since the article is intended for physicians
who are not familiar with the sophisticated chemistry
and equipment used in this industry.
The formulation of a soap is as closely related to its
marketing strategy (the consumer needs, the targeted
consumer segment, the purposes for which it is intended, and the chosen distribution) as it is to the production process chosen and its intended technical characteristics. Indeed, a soaps marketing strategy and

CHEMISTRY

OF SOAPS

AND

DETERGENTS

13

technical requirements are closely linked, influencing

each other in a circular fashion. Thus, while the marketing strategy will dictate a soaps target, price, and
characteristics, these must be executed by way of a formulation that in turn affects the final products actual
price and characteristics. There is thus a close and reciprocal relationship between formulation and manufacturing, on the one hand, and marketing and the commercial aspect, on the other.
Soap formulation and production are totally commercial, not theoretical processes, forming the backbone of a worldwide, multibillion-dollar industry. We
thus considered it necessary to deal with this aspect as
well, without which no discussion of the subject could
be satisfactory or thorough.

General References
1. Spitz L. Soap technology for the 1990s.Champaign, IL:
American Oil ChemistsSociety, 1990.
2. Osteroth D. Production of toilet soap. Darmstadt: GIT
Verlag, 1986.
3. Davidsohn AS, Milwidsky B. Synthetic detergents.7th Ed.
Essex,England: Longman Scientific & Technical, 1987.
4. Hollstein M, Spitz L. Manufacture and properties of synthetic toilet soap.7 Am Oil Chem Sot 1982;59:442-8.
5. Milwidsky B. Syndet bars. HAPPI 1985;22:58-70.
6. Colwell SM. Soap wars. SoapsCosmeticsChemical Specialties 1993;69:22-8.
7. SchoenbergT. Formulating of mild skin cleansers.Soaps
CosmeticsChemical Specialties1983;59:33-38.