Chapter 3

Formulation of Toilet, Combo, and

Synthetic Cleansing Bars
Edmund D. George
Bradford Soap Works Inc., West Warwick, Rhode Island, USA

Introduction
This chapter discusses soap-based compositions, a brief historical perspective on
traditional soap, and any matrix effects that may affect the formulation process.
Traditional soap is the sodium or potassium salt of triglycerides and fatty acids,
notably from beef tallow, coconut oil, and palm kernel oil and to a lesser extent
such oils as grape seed, sweet almond oil, or rice bran oil. Soap varieties include
transparent, opaque, translucent, and specialty bases, such as shavings, nonmarring
opaque soaps, cream/paste, and powdered soaps. Since the production of these
bases is well documented in the literature (115), they will not be discussed.
Synthetic soap bases are basically detergents plasticized with other ingredients
to yield a solid composition that can be formed into a bar (1624). They are often
combined in various ratios with traditional soaps to form combination or combo
soaps that have similar properties of both bases. Synthetic bases in particular can
be made using one of two methods. The cold method involves the addition of
ingredients into a mixer or blender with no heat. Meltable compounds are melted
separately and added to the mixer with other ingredients. After proper mixing, the
materials are released to the production line. The hot method involves blending the
ingredients, in proper sequence in a melt tank at an elevated temperature and mixing until uniform. The batch is then flaked or chill rolled. The resulting flakes or
pellets are then processed as any other soap base. The mode of the manufacturers
logic depends on the formulation and the availability of equipment.
Over the years, soap bar formulation has become more complex with the need
to incorporate more additives into an ever increasing number of soap bases.
Consumers have become accustomed to multifunctional products that are often
found in the cosmetics industry, such as conditioning shampoos, antiperspirants,
sunscreens, lotions, and creams. Traditional soaps were designed to clean skin and
clothes; as time passed, soaps were used as a delivery system for perfumes and
superfatting agents. Today, the cleaning aspect almost seems secondary to the
effects of various types and amounts of additives that are delivered by the soap
system. The 2002 CTFA International Cosmetic Dictionary (25) lists over 12,000
monographs of INCI names as well as 1,600 suppliers and 28,000 trade names
reportedly used in cosmetic applications.

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As with any drug or cosmetic, matrix effects must be considered when developing soap formulas, such as base-additive interactions, pH effects, additive-additive interactions, fragrance effects, and processing effects. Any combination of
these effects may influence the physical and aesthetic characteristics of the final
product. Sometimes it is difficult to predict the consequences of matrix effects, and
only with time and experience can the formulator begin to understand these interactions.

Base-Additive Interactions
The base-additive interactions include addition of acidic compounds that may
interact with the soap base by changing the physical or chemical characteristics of
the base. Alkaline soap bases may break down into fatty acids if enough acidic
material is added; this would basically render the soap ineffective. The reaction
may not be immediately noticeable since the soap base does not have sufficient
water to behave like a solution, but it can occur with time after processing and storage. The opposite may occur with a synthetic base, especially if the base contains
fatty acids (such as stearic acid) that could be neutralized by alkaline additives, and
could affect the processing characteristics of the formula.

pH Effects
Many of the stability problems due to pH seem to lie with traditional soaps, since
the majority of soap additives found in cosmetic and personal care products are
acidic. Certain compounds, such as some quaternary compounds and some fragrance ingredients, are unstable under the pH conditions found in traditional soaps.
Also, some over the counter (OTC) active ingredients, such as salicylic acid and
benzoyl peroxide, have the greatest stability in combo systems, which have neutral
to acid pH.

Additive-Additive
Additive-additive interactions are similar to the interactions discussed with additive-base interactions and should be handled in the same manner (see the section
on base-additive interactions).

Fragrance Effects
Fragrance effects can develop from fragrance compounds, such as aliphatic and
aromatic acids, esters, ketones, and glycols. They can profoundly affect the processing characteristics by increasing the softness and tackiness of the soap, or in
the case of translucent or transparent soap influence the clarity of the system. For
instance, fragrance diluents or solvents (such as certain glycols) appear to soften
and/or cloud transparent soaps, making an already difficult base to run more difficult. Some of these include diethyl phthalate (DEP) and dipropylene glycol (DPG).

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Vanillin is known to cause severe browning of soaps due to chemical reactions in

the alkaline pH range. Some newer ingredients on the market can be added to the
formulation or fragrance to retard this effect. Therefore it is recommended that
formulators work closely with suppliers to optimize fragrance selections prior to
formula finalization. Fragrance suppliers must be briefed on the type of base that
fragrances will be incorporated in to ensure proper delivery and stability of the
fragrance.

Processing Considerations
Processing considerations must be included when formulating a product. Process
parameters, such as temperature, shear, scrap recycle, viscosity, vacuum, die
refrigeration and shape, type of equipment, milling versus refining, and plodder
speed must be monitored or controlled. Although this subject is beyond the scope
of this chapter, its consideration is essential for a successful product.

Properties of Soap Bases

Chemical Properties
Chemical properties are often influenced by variations in starting materials in the
base formulas. For instance, transparent bases can be made from detergents and fats
and oils using combinations of sodium hydroxide, potassium hydroxide, and alkanolamines (such as triethanolamine). Synthetic systems can be plasticized with saturated fatty acids, fatty alcohols, or a combination of the two. The ratio of fats and oils
(i.e., 80% tallow/20% coconut vs. 70% tallow/30% coconut oil) as well as the manufacturing process (full-boiled vs. semi-boiled, etc.) will also influence the chemical
properties. The choice of the preservation system is critical to the long-term chemical
stability of the cleansing system. As can be seen in Table 3.1, virtually all of the
compounds are chelators. It has been found through work at Bradford Soap Works,
West Warwick, RI, that chelators provide better protection than antioxidants in the
preservation of traditional soap systems at a pH around 10. This is due to the extreme
negative effect of pro-oxidant metals, such as iron, copper, and magnesium, on
chemical stability. Pentasodium pentetate and tetrasodium etidronate are particularly
effective preservatives for color and odor stability in these systems, often at levels
under 0.10% each. The formulator must be familiar with these properties when
developing additive packages that are stable and functional.

Physical Characteristics
Physical characteristics will also influence the amount and type of additives that
will be incorporated into the final formula. It must be noted that the following
characteristics should be established with each formulation to generate complete
product profiles. Wear rate, crack resistance and sloughing, wash down, foaming,

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TABLE 3.1
Typical Soap Preservatives
INCI name
Chelators
Diphosphonic acid
Tertasodium etidronate
Etidronic acid
Tetrasodium etidronate

Pentasodium pentetate
Tetrasodium EDTA
Trisodium EDTA

Tetrasodium etidronate
Tetrasodium etidronate
and
Pentasodium pentetate
Tetradibutyl pentaerythrityl
hydroxyhydrocinnamate
Antioxidants
BHT

Abbreviation

Trade name

Supplier

HEDP
Sodium HEDP
(Na4HEDP)
EHDP
Sodium HEDP
(Na4HEDP)
EDTA and salts
DPTA and salts
HEDTA and salts
Na5DPTA (DPTA)
Na4EDTA
Na3EDTA
NaLED3A (surfactantchelator compound)
Sodium HEDP
(Na4HEDP)
Sodium HEDP
(Na4HEDP) and
NA5DPTA (DPTA)

Dequest 2010
Dequest 2016

Solutia
Solutia

Turpinal SL
Briquest ADPA21SW
Dissolvine E series
Dissolvine D series
Dissolvine H series
Versenex 80
Versene 100
Versenol 120
NaLED3A
Mayoquest 1530M

Solutia
Albright and
Wilson
Akzo Nobel
Akzo Nobel
Akzo Nobel
Dow
Dow
Dow
Hampshire
Chemical (Dow)
Vulcan

Mayoquest 1545M

Vulcan

Tinogard TT

Ciba

Tenox BHT

Eastman Chemical

BHT

color, and odor are important physical characteristics that should be noted. Additives
will tend to influence one or all of these particular aspects of the soap bar, and it
must be determined prior to production if it negatively impacts these particular
characteristics.
Wear Rate. Wear rate essentially describes the lasting power of the soap bar
under use conditions. It is influenced by the various solubilities of the bases, which
is determined by the titer of the fat and oils, the type of alkali used, and the amount
of water for traditional soap to the type of plasticizer and solubility of the detergent
in syndet systems. For instance, transparent soaps have relatively high wear rates
due to the use of high level solvents, such as glycols, water, and alcohols, that are
needed to maintain clarity. These soaps may also contain a surfactant system with
a high solubility that aids in maintaining clarity. This combination tends to let the
bar melt away. On the other hand, syndet systems need plasticizers and binders
to hold the bar together. They are typically waxes, starches, fatty acids, and fatty
alcohols that have very limited water solubility, and make the system less sensitive
to wear rate than other soap types.

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Crack Resistance. Crack resistance relates to the tendency of soap bars to crack
and/or disintegrate when subjected to repeated wet-dry cycles. This is achieved in
the laboratory by submersion of one-half of the bar in ambient water from 4 to 24
h, then air drying until completely dry. Cracks will appear if the system is prone to
cracking. Also the amount of sloughing can be determined by a similar method of
submersion and calculating the weight loss after drying.
Industry experience indicates that translucent soaps traditionally have poor
crack resistance. One theory suggests that translucent systems lack the grain or
internal structure that traditional opaque soaps have. This grain or crystallinity,
allows the soap to hydrate and dehydrate uniformly, whereas translucent soap lacks
sufficient structure to stabilize the effect. Additives, such as sucrose, can promote
cracking as well as certain solvents in fragrances. Syndet systems appear to be less
prone to cracking but can produce a high rate of sloughing. This is the tendency to
form a gel-like material (mush) when hydrated; it depends on the formulation and
is a major drawback of syndet-combo systems.
Wash Down. The feel of a bar during use can be determined by a wash down
test. This is usually performed at a lower temperature, 8590F in order to determine if there is any grit, drag, or sandiness present in the bar. Traditionally, synthetic and combo systems are prone to this problem. Some of the causes include
improper processing at the base- and bar-making stage or hard particles in the surfactant system. Formulas containing sodium cocoyl isethionate appear to be prone
to this problem. Concern arises when the bar is cold; before use the grit may feel
unpleasant to the user in spite of the fact that the grit disappears at a normal use
temperature. Sandiness may occur in a traditional opaque soap base by excessively
dry particles formed during the vacuum-drying process. Various soaps with a higher water range of 1214% will typically reduce this problem.
Lathering. While lathering does not necessarily equate to detergency, consumers
perceive quick, copious foam with quality and cleaning. In reality, foam may be a
visual aid to the consumer, allowing the user to see where the product has been
applied. Foaming characteristics can be influenced by many factors, including fat
and oil type and ratio, or in the case of synthetics, the types of surfactants and plasticizers. Many additives that are oily in nature will tend to act as defoamers if
incorporated at high levels, such as in superfatted bars. Traditional soaps will lather poorly in hard water and seawater while synthetics, if properly formulated, will
foam well. Standard foam height tests should be performed as part of the product
profile.
Color. Soap bases tend to yellow so that the color of the final bar formulations
will also change. This, coupled with additive and fragrance instability, can produce
color variations in a short period of time. Accelerated stability testing in oven, sunlight, or fluorescent light can help predict the stability of this system. A reflectance

Copyright 2004 AOCS Press

colorimeter is useful to record the color of a sample in a computer database. This

instrument mathematically calculates the color as the human eye sees it and allows
the computer to recall the color any time in the future as a reference standard. This
method can be used for all soap types, including translucent and transparent soaps
to determine the yellowness of soap bases. It is a particularly reliable tool to characterize color. Other, more sophisticated color-measuring devices can be employed
that not only measure color, but also formulate and correct soap batches allowing
for more precise and efficient color matching.
Odor. Olfactory evaluation of a soap base and finished product is as important as any
other physical characteristic. Consumers tend to view the fragrance perception as
being as important as any other characteristic. Therefore, it is important that the soap
fragrances are formulated to ensure as much stability as possible. Evaluation for chemical stability can be carried out under similar conditions as color stability. Trained technicians and odor evaluation panels usually perform an olfactory evaluation.

Colorants
Colorants can essentially be divided into three categories: certified, those color
additives subject to certification; noncertifiable, those color additives not subject to
certification; and noncertified, those color additives not certified. The use of colorants depends on the type of product that is being produced and the government
regulations that govern the product. In the U.S., the distinction usually lies in the
application of the Federal Food, Drug, and Cosmetic (FD&C) Act (26) and the Fair
Packaging and Labeling (FP&L) Act where the definition and labeling requirements for drugs and cosmetics are made, and soap is exempt. Drugs must use certified colors, while cosmetics can use certified and noncertifiable colors. Any soap
that makes drug and/or cosmetic claims must have its ingredients labeled accordingly, with the appropriate colorants. Soaps however can use any combination of
colors as long as it meets the definition of soap and is claimed as such. Resources,
such as the CTFA dictionary, can be consulted to determine acceptable and
approved colorants in other countries.
Tables 3.2 and 3.3 list some of the more common certified and noncertifiable
colorants. Certified colors are common for drugs and cosmetics, while noncertifiable colors are primarily used in cosmetic type soaps.
Certified Colorants. Certified colorants (Table 3.4) may be water soluble, oil soluble, or oil dispersible. They also include the corresponding metal lakes. The solutions or dispersions are typically made at the 12% level; higher loads of 3050%
may be obtained from vendors that have specialized equipment for grinding and
dispersion. Solubility and dispersion tables should be consulted to determine the
optimum concentrations in dispersing. It is recommended that sufficient concentration strengths be used to maintain relatively low levels of additives and reduce the

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TABLE 3.2
Color Additives Subject to Certification (March 1990)
Color additives

Color index
number

FD&C Blue 1
FD&C Green 3
FD&C Red 4
FD&C Red 40
FD&C Yellow 5
FD&C Yellow 6
D&C Blue 4
D&C Brown 1
D&C Green 5
D&C Green 6
D&C Green 8
D&C Orange 4
D&C Orange 5

42090
42053
14700
16035
19140
15985
42090
20170
61570
61585
59040
15510
45370

D&C Orange 10
D&C Orange 11
D&C Red 6
D&C Red 7
D&C Red 17
D&C Red 21
D&C Red 22
D&C Red 27
D&C Red 28
D&C Red 30
D&C Red 31
D&C Red 33

45425
45425
15850
15850
26100
45380
45380
45410
45410
73360
15800
17200

D&C Red 36

12085

D&C Violet 2
D&C Yellow 7
D&C Yellow 8
D&C Yellow 10
D&C Yellow 11

60725
45350
45350
47005
47000

Use in cosmetics
Except in eye area
Externally except in eye area

Except in eye area

Externally except in eye area
Externally except in eye area
Externally except in eye area
Externally except in eye area (0.01% max.)
Externally except in eye area
Externally except in eye area
Lip products (5% max.), mouthwashes, dentifrices (GMP)
Externally except in eye area
Externally except in eye area
Except in eye area
Except in eye area
Externally except in eye area
Except in eye area
Except in eye area
Except in eye area
Except in eye area
Except in eye area
Externally except in eye area
Externally except in eye area
Lip products (3% max.), mouthwashes, dentifrices (GMP)
Externally except in eye area
Lip products (3% max.)
Externally except in eye area
Externally except in eye area
Except in eye area
Externally except in eye area
Externally except in eye area

amount of dispersant needed for the soap batch. Certified colorants tend to have
the lowest stability of the three categories. Factors include pH, day and fluorescent
light, heat, and additive interactions. For instance FD&C Green 3 renders a green
color below a pH of 7 but a royal blue above pH 7. Stability stations should be utilized to determine overall stability in the surfactant system.
Noncertifiable Colorants. Noncertifiable colorants (Table 3.4) tend to be very
stable compounds and are used extensively in cosmetics, eye shadows, mascaras,

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TABLE 3.3
Color Additives Exempt from Certification (March 1990)
Color additives
Aluminum powder
Annetto
Bismuth citrate
Bismuth oxychloride
Bronze powder
Caramel
Carmine
Carotene, beta
Chromium hydroxide green
Chromium oxide greens
Copper powder
Dihydroxyacetone
Disodium EDTA-copper
Ferric ammonium ferrocyanide
Ferric ferrocyanide
Guanine
Guaiazulene
Henna
Iron oxides

Color index
number

77163

75470
77289
77288

77510

77489
77491
77492
77499

Lead acetate
Manganese violet
Mica
Potassium sodium, copper
chlorophyllin (chlorphyllincopper complex)
Pyrophyllite
Silver
Titanium dioxide
Ultramarines (blue, green, pink, violet)
Zinc oxide

77742
77019

77891
77007
77497

Use in cosmetics
Externally including the eye area
No restrictions
Scalp hair dye only
No restrictions
No restrictions
No restrictions
No restrictions
No restrictions
Externally including the eye area
Externally including the eye area
No restrictions
Externally including the eye area
Cosmetic shampoo only
Externally including the eye area
Externally including the eye area
No restrictions
Externally except in the eye area
Scalp hair dye only
No restrictions

Scalp hair dye only (0.6% Pb w/v

max.)
No restrictions
No restrictions
Cosmetic dentifrices (0.1% max.)

Externally except in the eye area

Nail polish only (1% max.)
No restrictions
Externally except in the eye area
No restrictions

and facial makeup. In some products they can be used as primary and secondary
colorants; they tend to stabilize color drifting due to certified color use. These
compounds should be dispersed or wet-out before use to maximize their color
value. A dispersion aid, such as a 3040% potassium cocoate solution, gives a
good dispersability to these colorants. The formulator can develop a color by
approximating the amount of dry pigment then dispersing the powder in the
cocoate solution. A blooming effect, where large pigment particles cause a slow
migration of color into the soap system, can occur if the colorant is not dispersed

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TABLE 3.4
Common Soap Colorants
Certified

Noncertifiable

FD&C Green 3
FD&C Red 4
FD&C Red 40
FD&C Yellow 5
D&C Green 5
D&C Green 6
D&C Green 8
D&C Orange 4
D&C Red 17
D&C Red 33
D&C Violet 2
D&C Yellow 10

Caramel
Chromium hydroxide green
Chromium oxide greens
Iron oxides
Mica
Titanium dioxide
Ultramarines (blue, green, pink, red, violet)
Zinc oxide

properly or becomes dried-out before use. Unfortunately this can occur within
hours or days of production and causes a blotched color in the finished product.
Newer materials on the market however contain predispersed colorants for ease of
use. Opacifiers, such as titanium dioxide, zinc oxide, and bismuth oxychloride, are
also used to give uniformity to the color system. Without them the soap may
appear to have light- and dark-colored areas caused by various compression areas
from processing and pressing operations. Titanium dioxide is offered in both rutile
and anatase forms with the water-dispersible anatase USP grade being used most
often. Traditionally, rutile types typically do not give the brightness or the hiding
power that anatase types give. However there are newer rutile versions that appear
to be comparable to the anatase type that give equal opacity, better stability, and
somewhat superior brightness.
Noncertified Pigments. In the U.S., noncertified pigments are often used in bar
soaps, as long as the soaps conform to the definition and labeling requirements of
soap. These colors tend to be very stable, less sensitive to pH, and provide a wide
range of brightness and hues. They often are supplied as dispersions with concentrations of 2550%. Also, only small amounts of these pigments are required to
achieve dark colors in most soap bases. Table 3.5 highlights some of the more
common noncertified colorants that are used in soaps.

Fragrances
Virtually any scent can be created to fit a product profile and marketing concept.
All fragrances should be developed to ensure stability and robustness for use in a
particular soap matrix. Use levels will vary depending on the composition, but a
typical low range is 0.250.50% for masking purposes and 34% for prestige fragrance bars. At high usage levels, it is important to use vacuum in the extrusion

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TABLE 3.5
Common Noncertified Colorants in Soap
Pigment name

Pigment type

Pthalo blue RS
Pthalo blue
Pthalo blue GS
Pthalo green
Quinacridone magenta
Napthol red ITR
Carbazole violet
Hancock yellow G

Blue 15
Blue 15:1
Blue 15:3
Green 7
Red 122
Red 5
Violet 23
Yellow 1

Color index number

74160
74250
74160
74260
73915
12490
51319
11680

process to minimize surface bubbling or blistering caused by the fragrance components. A very small amount of fragrance will be lost with a vacuum system, but the
overall effect will be a uniform extrusion. As mentioned previously, fragrances
will affect soap processing to the extent that they will not extrude or press (stamp)
within the desired process rates. This is seen in synthetic and combo systems, but it
is more dramatic in translucent systems where clarity and firmness are critical. As
indicated earlier, two particular fragrance additives used as solvents cause problems in translucent soaps. Dipropylene glycol (DPG) and diethylphthalate (DEP),
tend to make translucent soaps sticky to the point where the soap does not extrude
or press at all. When these solvents are removed from fragrance formulations, a
noticeable increase in productivity can be seen. Certain resinoid compounds used
in fragrances may cloud translucent systems due to solubility and particulate concerns. Other components may produce similar effects and should be investigated
through experimentation.

Additives
Most soap products include the addition of compounds to achieve a desired functional and/or marketing position. This has become the prime focus of soap formulators. The CTFA Cosmetic Handbook (27) and McCutcheons Functional
Materials (28) contain many of these functional materials. Several important categories will be discussed:

Emollients
Humectants/Moisturizers
Occlusive agents
Dermabrasive agents
Drug components
Anti-irritants
Secondary surfactants
Miscellaneous compounds.

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A difficult task for the formulator is the evaluation of additive benefits in soap
bases. Most often expert panels are used to evaluate performance and aesthetic perceptions. More sophisticated and highly technical techniques can be employed,
such as transepidermal water loss or TEWL, skin elasticity, tracer studies for residual ingredients after rinsing, spectroscopic and florescence studies, and human skin
models. Kajs and Garstein (29) review the use of these methods for evaluating
cleansing products.
Emollients. Emollients are compounds that are used to impart and maintain softness and pliability of the skin and generally improve the skins overall appearance.
Fatty esters, alkoxylated ethers, and alkoxylated alcohols comprise the bulk of the
ingredients in this category (Table 3.6). Typical use levels are 13%. These compounds are stable under normal bar-soap conditions, however care should be taken
to review the physical properties of each of these materials to determine the best
way to incorporate the ingredients into the base, as well as any stability considerations, such as pH and temperature.
Humectants/Moisturizers. Humectants and moisturizers (Table 3.7) are skinconditioning agents that increase the moisture in the skin. Their effectiveness
depends on the humidity in the environment they operate in. Typical use levels
vary widely from 0.1 to 10%. Dahlgren et al. (30) describes the results of instrumental methods and perceived skin benefits of glycerine in various surfactant systems. The results indicate that high levels of glycerine provide improved skin feel
and softness. It should be noted that monosaccharides or simple sugars, such as fructose and glucose, darken under alkaline conditions and accelerate by the small
amount of free alkaline present in traditional soap bases. The neutralization of the
free alkali by the addition of a fatty acid, such as coconut or stearic acid, will help
reduce the darkening effect. The discoloration will vary, and depends on the type and
amount of sugar. Disaccharides, such as sucrose, are relatively stable under mild
alkaline conditions. Water-droplet formation or sweating may occur with high levels
(10% or more) of glycols and alcohols, such as glycerine, sorbitol, and propylene
glycol, under humid conditions. This is a persistent problem with transparent soaps
that employ high levels of multiple humectants that also serve as solvents and solubilizers. This hygroscopic effect appears to be less of a problem with other types of
soap systems that employ lower levels (under 5%) of these materials.
Occlusive Agents. Occlusive agents (Table 3.8) include ingredients that are
designed to prevent moisture evaporation from the skin, and thus help maintain
soft and smooth skin. They typically are lipid in nature and are added to achieve a
desired effect in so-called dry-skin products. Use levels are in the 110% range.
The higher levels may cause extrusion and pressing problems by making the soap
excessively soft and sticky, but this may be reduced by incorporating the ingredients in the base-making stage or pre-milling/refining stage prior to extrusion.

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TABLE 3.6
General Emollient Groupings and Common Ingredients
Esters

Ethers

Alcohols

Oils and oil type

Glycols

Lanolin derivatives

Silicone derivatives

Butyl myristate

Methyl gluceth-1

Cetearyl alcohol

Castor oil

Glycerine

Acetylated lanolin

Dimethicone copolyol

Cetyl palmitate

Methyl gluceth-20

Cetyl alcohol

Jojoba oil

Propylene glycol

Lanolin

Glycerol stearate

PPG-10 methyl
glucose ether

Stearyl alcohol

Mineral oil

Diglycerine

Lanolin esters

Isopropyl myristate

PPG-20 cetyl ether

Mink oil

Lanolin alcohols

Isopropyl palmitate

PPG-20 lanolin
alcohol ether

PEG-glycerides

Lanolin fatty alcohol

Octyl palmitate

PPG-20 methyl
glucose ether

Petrolatum

PEG-lanolin

Tridecyl neopentanoate

PPG-20 oleyl ether

PPG-20 myristyl
ether

Shea butter
Cocoa butter
Sweet almond oil,
wheat germ oil,
olive oil,
grapeseed oil

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slicone fluids

TABLE 3.7
Common Humectants and Moisturizers
Saccharides

Ethers

Alcohols

Glycols

Miscellaneous
compounds

Fructose
Glucose starch
hydrosylate
Honey
Lactose
Sucrose
Xylitol
Tridecyl
neopentanoate

Methyl gluceth-10
Methyl gluceth-20

Mannitol
Sorbitol

Glycerine
Propylene glycol

Acetamide MEA
Hydrogenated

Diglycerine

PCA
Sodium PCA
Urea

PPG-10 propylene glycol

Dermabrasive/Exfoliating Agents. Dermabrasive agents work in conjunction

with a cleanser to remove the outermost layer of stratum cornea by scrubbing, thus
producing a smoother feel to the skin. Loden et al. (31) describes a method to measure the effects of dermabrasive cleansers and has determined that there is a perception of improving skin smoothness. Natural components, such as bran, loofa,
oatmeal, jojoba beads, and various seeds, are popular since they can be blended to
achieve a desired look in the cleanser and a desired feel on the skin in addition to a
natural claim. Polyethylene beads of various sizes and colors are also used effectively where a natural component is not needed. With some precautions, these
agents can be added to the amalgamator process under normal conditions. When
using refiners, the screen sizes should be large enough to allow the scrub agents to
pass through. Otherwise they will be filtered out. When using mills, the milling
TABLE 3.8
Occlusive Agents
Castor oil
Coconut oil
Dimethicone
Hydrogenated oils
Jojoba oil
Jojoba wax
Mineral oil
Natural and synthetic waxes
Olive oil
Petrolatum
Shea butter
Cocoa butter
Sweet almond oil
Tallow
Wheat germ oil

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action should not break the component down into fines, which will reduce the
scrubbing effect. Proper gapping of the roller mills and the use of low shear mills
will reduce the problem. If this is not possible, then a scrub agent can be added in a
post-milling step or possibly in the finish extruder with no screens. This problem
occurs mostly with the larger size natural components, such as loofa and oatmeal,
and too a much lesser extent with the polyethylene beads. It should be noted that
mild exfoliation could be achieved using spherical exfoliants, such as polyethylene
and jojoba beads, since they tend to roll over the skin. Irregularly shaped material,
such as crushed seeds, leaves, and shells, tend to provide a more aggressive effect.
Drug Components. The most common drug categories that bar soaps are
involved in are antimicrobial and acne. In the U.S., each drug category is governed
by a monograph published by the federal Food and Drug Administration (FDA).
Organizations, such as CTFA, SDA, and others, have been working diligently with
the FDA over the last several years to finalize the antimicrobial monograph to
include personal care antimicrobial cleansers as a separate category. Each monograph sets the conditions under which a product that is claimed in a particular category may be sold. The formulator should consult the monograph to obtain specific
information of a category prior to development work; all of these products should
be manufactured or controlled according to good manufacturing procedures, since
the drugs are subject to FDA auditor inspections.
The antimicrobials, Triclosan and Triclocarban are the two compounds most
widely used in antimicrobial bar soaps. Typical use levels are 0.31% for Triclosan
and 11.5% for Triclocarban. They are incorporated at the amalgamator stage and may
be predispersed or dissolved in a suitable solvent, such as a fragrance, prior to addition.
As with all drug products, the soap line should be validated to ensure that the finished
product is homogenous, and that the proper level of the antimicrobial is in the soap.
The most commonly approved acne ingredients used in bar soap are salicylic
acid, at 0.52%, and sulfur at 310%. They have been formulated both in traditional
and synthetic or combo bases. Sulfur is stable in both alkaline and acid bases.
Salicylic acid however is stable with acid bases but may destabilize traditional alkaline bases. Therefore a mild alkali, such as triethanolamine, is sometimes added to stabilize the salicylic acid. Iron contamination should be avoided, since both ingredients
will remove iron from the equipment. This will result in the iron particles blooming in
the soap. This will cause soap discoloration and can potentially lead to rancidity in traditional soaps. Both of these ingredients are normally added in the amalgamator stage
and processed under normal conditions. As stated previously, good manufacturing
procedures for this product category need to be enforced.
Anti-irritants. There are several ingredients on the market that claim to have antiirritant properties. Among these are sucrose esters, -bisabolol, lactylates, and
ethoxylated vegetable oils. Also, it is known that surfactant mixtures incorporating
such materials as amphoterics, sarcosinates, ethoxylated surfactants, and isethionates

Copyright 2004 AOCS Press

can reduce the overall irritancy of the product. Most of these compounds have been
evaluated in shampoo systems in which skin and eye irritation levels are reportedly
reduced, but it can also be effective in bar soaps.
The overall mechanisms are not fully understood but are believed to involve
several factors, including binding or complexation of irritants, blocking sites that
are prone to irritation, and prophylaxis that covers the skin thus reducing or preventing irritant contact. When adding anti-irritants, a baseline test should be run to
determine the effectiveness on the irritant. This can be achieved by several different methods that are currently on the market. The so-called soap chamber test was
developed by Frosch and Kligman (32); the Zein test, as described by Gotte (33), is
an in vitro method that measures the ability of surfactants to solubilize the vegetable protein Zein. Newer, in vitro methods continue to be developed that utilize
human skin factors in bench-top assays that will benefit the formulator in quickly
screening various additive packages. There does not appear to be one single test
that is an adequate predictor of irritancy potential. Rather, several testing protocols
may be needed to evaluate a product or surfactant.
Secondary Surfactants. Secondary surfactants are often used to increase the performance of the bar resulting in improved skin feel, reduced irritancy from the primary
surfactant, improved solubility, or improved quality and quantity of the foam.
Typically they are added at low levels, under 5%, as an adjunct to the primary surfactant. Theoretically most surfactants found in shampoos and liquid soaps may be used
in bar soap systems as long as they are compatible with the system and are stable
under a given pH. However, most of them are pastes and liquids that tend to make
soap systems tacky and result in increased processing problems. This may be due not
only to their physical state, but also to their tendency to lower the viscosity of the soap
system and soften the system. Furthermore, additives and fragrances may complicate
the formulation.
Table 3.9 lists several of the more common surfactants that are used: acyl
isethionates, amphoterics, sarcosinates, sulfosuccinates, and sulfoacetates. These
ingredients may be added to the amalgamator and processed under normal conditions.
In particular, sodium coco glyceryl sulfonate has good foam boosting, after-feel,
TABLE 3.9
Secondary Surfactants
Type

Example

Chemical type

Form

Acyl isthionates
Amphoterics
Sarcosinates
Sulfosuccinates
Sulfoacetates
Alkyl glyceryl sulfonate

Sodium cocoyl isethionate

Disodium cocoamphodiproprionate
Sodium cocoyl sarcosinate
Disodium lauryl sulfosuccinate
Sodium lauryl sulfoacetates
Sodium cocoglyceryl ether sulfonate

Anionic
Amphoteric
Anionic
Anionic
Anionic
Anionic

Solid
Paste
Liquid-solid
Liquid-solid
Solid
Paste

Copyright 2004 AOCS Press

and processing characteristics. When handling powders, care should be taken to

safely handle dust associated with the surfactants. An alternate method to introduce
these extra surfactants would be to include them in the base-making process so that
they become an integral part of the base. For synthetic and combo bases, these surfactants may be added during the normal compounding process. Additionally,
Rigger (34) has developed an excellent list and overview of surfactant types available to the formulator.
Miscellaneous Compounds. Several miscellaneous compounds are commonly
used in soap formulations. Optical brighteners are sometimes used to shift the
appearance of a product from a yellow tone to a bluer tone. One ingredient, disodium distyrlbiphenyl disulfonate, is particularly effective, requiring approximately
0.3% in traditional soap base for soap products. Currently this compound is viewed
as a noncertified colorant in the U.S. and is not acceptable in products labeled as
cosmetics or drugs. However, it is approved in the EC for use in cosmetics. Color
stabilizers have recently been introduced that help reduce color fading from photolytic effects. Sodium benzotriazolyl sulfonate, sodium benzotriazoyl butylphenol
sulfonate and buteth-3, tributyl citrate, and bumetrizole are a few examples of such
compounds. They can be added to the amalgamator.
Encapsulated products can be useful to the formulator. The challenge of using an
encapsulated product in soap products is capsule survival during processing while having a small enough particle size to minimize drag or grit feel after washing. This
allows the delivery of process- and formula-sensitive materials during washing; this
results in enhanced effectiveness and stability. More recently, U.S. Patent 6,403,543
(35) demonstrates the suspension of microencapsulated beads in clear glycerine soap.
The beads can contain many of the functional materials that have been discussed. This
system not only provides an interesting visual effect, but it also isolates the functional
material from the surrounding soap matrix and offers additional stability.
Herbal extracts have increased in popularity recently due to heightened awareness of the environment and the subsequent natural themes in many product categories. Aromatherapy, spa, and fragrance-free products are included in these categories. Extracts of rosemary, chamomile, sage, and aloe, among others, are often
used as masking agents to replace fragrances while imparting whatever skin benefits they may claim to have. The current CTFA dictionary has an extensive cross
index of botanicals that are powders, oils, and extracts. As with any naturally
derived material, specifications should be developed to ensure acceptable purity
and consistency with every shipment. Many botanicals are offered in a standardized version, giving the formulator some degree of confidence as to the strength of
the material. Since some of the components in a natural product are unknown, adequate stability studies on all formulations need to be performed to determine if
there are any color or fragrance issues. For instance, certain phenols and tannins
may unacceptably discolor the soap. A recent publication (36) outlines many of the
natural and botanical ingredients available today.

Copyright 2004 AOCS Press

Cream soaps and cleansing grains are other types of non-bar cleansing systems
that can be developed. The cream products can be viewed as modified combo bars
that have a paste-like consistency. The formulations include a combination of traditional soap with synthetic detergents, plus structuring agents and benefit additives. Colorants and fragrances can be added as well as special ingredients, such as
clays and botanicals. The resulting product is paste-like generating excellent foaming, cleansing, and after-feel. They can be dispensed from a variety of containers,
and when pressurized will provide an excellent mousse product. Cleansing grains
are formulated with a powdered soap and/or detergent cleanser, benefit additives,
colorants, and fragrances. Liquid additives should be kept at a minimum to ensure
that the product flows and dispenses properly. Encapsulating the liquid material in
a solid matrix whereby the liquid is delivered when the product is used allows
higher amounts of liquids to be used. These products offer an additional way that
the consumer can utilize advances in personal care skin-cleansing additives.
Alternative soap bases can be made from nontraditional oils. These include,
but are not limited to, grapeseed, olive, sweet almond, and rice bran oils. When
saponified, these oils yield a finished soap that can be extruded and pressed. The
resulting soap bars are slightly softer than traditional soap from tallow or palm oil,
but are extremely smooth when used and provide excellent lather and a nice afterfeel. The all vegetable oil components may be attractive for market sectors in spa,
aromatherapy, and natural lines. Standard soap additives, as well as botanicals, can
be incorporated into these bases.

Conclusion
The formulator is urged to take a balanced approach in developing surfactant systems. Consideration must be given to the base type and function; these will dictate
acceptable additives for the product category. In turn, process considerations must
be addressed in order to manufacture a quality product. Surfactant systems can be
overwhelmed trying to achieve higher and higher functionality for a world of everchanging cultures.
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Copyright 2004 AOCS Press

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