THE FUNCTIONAL ADVANTAGES OF

NATURAL WAXES IN TRADITIONAL SOAPS

Originally Published by SOFW Journal April 2023 - English

 THE FUNCTIONAL ADVANTAGES OF
NATURAL WAXES IN TRADITIONAL SOAPS
Alexandra G. McMahon, B.S., Research & Development Chemist, Koster Kuenen, Inc.
Belén M. Lemieux, M.S., Research & Development Laboratory Manager, Koster Keunen, Inc., [email protected]

ABSTRACT
Humans have been manufacturing soap since at least 2800 B.C., modifying and perfecting their recipes
over the centuries. Today’s traditional soap bars are made via saponification of triglycerides: the alkaline
hydrolysis of fatty ester bonds, leading to mainly C16-C18 fatty acid soaps and glycerol. In this paper, we
explore the use of Natural Waxes from Koster Keunen, Inc. as starting raw materials in soap formulations,
both alone and as additives to traditional triglycerides. Twelve Natural Waxes were blended with olive oil
at 50/50 ratios, each blend was fully saponified, and the reaction products were evaluated for different
properties and compared to a standard olive oil soap bar. It was determined through experimentation that
each Saponified Natural Wax or Saponified Natural Wax Blend made a chemically complex finished soap,
with different properties from the control and from each other. Some of the benefits encountered included
improved bar hardness, a longer lifespan, more hydrophobicity, and innovative INCI declarations.

Introduction and Background global hand soap market is forecasted to grow by 6.7% from 2020
to 2030, with the household segment accounting for over 70% of
Few personal care products can have their history traced as far back
the market share [6]. Although it is not clear what percentage of
as soap. While the historical accounts on soap and soapmaking
said growth refers to traditional soap bars (versus “syndet” bars
are rife with legend, experts agree that the earliest evidence dates
or liquid detergents), current consumer trends, such as natural
back to 2800 BC in Ancient Babylon, when a soap-like substance
ingredient demand, small business support, and plastic reduction
was discovered during an archaeological dig [1].
seem to support the persistence of traditional soaps [7], [8].
Other records show ancient Egyptians, Greeks and Romans
Soap Chemistry and The Role of Waxes
also made and used soap for thousands of years, perfecting the
technique over time. By 1100 AD, soap making was an established All soaps have in common one core recipe: Lipid + Alkali = Soap +
practice in Mediterranean countries with easy access to olive oil, a By-product.
key ingredient in Castille Soap, which was widely traded at the
time [2]. The chemical reaction that takes place is called saponification
and can be defined as the alkaline hydrolysis of fatty ester bonds,
Soap was introduced to the Americas in the 17th century, when resulting in fatty acid salts -the soaps- and a by-product (typically
soap makers arrived in Jamestown, VA [1]. Over the next 200 glycerol) [9].
years, as the United States industrialized, soapmaking evolved into
one of the fastest growing businesses, with P&G’s Ivory being one Most commercial soaps (and also DIY versions) are variations
of the first to gain national distribution [3]. However, food and fat of “tried and true” recipes, based on well-known saponification
shortages during World War I led German engineers to introduce reactions of well-known lipids, like tallow or palm oil [10], with the
synthetic replacements for soap, now known as detergents [4]. only variations being in fragrance, color, and claim ingredients. This
American consumers quickly embraced detergents due to their work is meant to encourage chemists and soap makers looking
efficiency, availability, and low price; moving traditional soaps for innovation to vary the lipid source. This can be done by trying
over time to niche market segments, particularly “Indie” brands, new ingredients, trying new combinations of known ingredients, or
artisanal soap makers, and crafters [5]. varying the ratios of these combinations. This will lead to new and
innovative soap products, as well as by-products (often overlooked
In recent years, and specifically at the onset of the COVID-19 but important as well), which will affect the product performance,
Pandemic, the demand for hand soap has escalated. In fact, the sensory aspects, and ingredient listing.

PAGE 02
The Lipid Source Waxes as Lipids

Lipids are a diverse group of organic compounds, characterized by Waxes are a class of lipids with varying definitions and
their hydrophobicity and their biological importance. They present classification options. In a strict sense, waxes are comprised of
either as linear alkyl chains, saturated or with unsaturations, or as long chain monoesters: long chain fatty acids esterified onto long
isoprene units in varying structures. These molecules may contain chain alcohols with similar chain lengths, mainly saturated. A more
oxygenated substituents, such as carboxylic acids or hydroxyl practical description of waxes should include that they are blends
groups [11]. of many components, including monoesters, hydrocarbons, sterol
esters, and fatty alcohols [14].
Traditional soapmaking would not be possible without a specific
class of lipids, known as fatty acids. Fatty acids are linear alkyl Many natural waxes are biosynthesized by living organisms to
chains, typically C12 - C22, saturated or with unsaturations, and provide a protective barrier against environmental stresses. Due
a terminal carboxyl group [12]. In nature, fatty acids are typically to their protective nature, waxes are widely used in personal care
found linked by ester bonds to glycerol, called triacylglycerols or and OTC drugs to provide a barrier to human skin, and are staple
triglycerides [11]. Due to this richness in fatty acids and widespread ingredients in lip balms, hand salves, and body creams [15]. In this
availability, triglycerides are the most prevalent starting raw paper, we explore the use of natural waxes as starting materials
materials in soapmaking. Some examples of lipid sources rich in for traditional soaps.
triglycerides are tallow, palm oil, or olive oil [13].

WE ARE ALL
NE HIVE
TM
Waxes Make Complex Soaps
Major Natural Wax Saponifiable? By-Product Natural Wax Example
Component
Traditional lipid sources used in soap making, like
Monoesters Yes Fatty alcohols Sunflower Wax, Rice Bran Wax
animal fats (very high triglyceride content, usually
Hydrocarbons No N/A Candelilla Wax
centered around C16 - C18 saturated fatty acids)
or plant oils (very high triglyceride content, usually Fatty alcohols No N/A Orange Wax

centered around C18 unsaturated fatty acids) Free fatty acids Yes Water (likely evaporates) Beeswax

[13], will yield almost exclusively combinations of Triglycerides Yes Glycerol Bayberry Wax, Cocoa Butter

saturated and unsaturated C16 –C18 fatty acid

Mono- and Diglycerides Yes Glycerol
soaps, and glycerol as a by-product. While these
Triterpenes / Derivatives Possibly Various
small differences in carbon number and degree of
Other Possibly Various
unsaturation can translate to subtle differences
in a finished soap bar, the chemical richness and Table 1. Saponifiable Materials Found in Natural Waxes.

complexity of each natural wax will create soap bars with vastly different chemical compositions. In addition to the C16-C18 soaps and
glycerol described above, waxes can also yield very high molecular weight soaps (from C24 up to C38) and a broad molecular weight
range of fatty alcohols as reaction by-products, while keeping their unsaponifiable materials intact. These higher molecular weight
soaps are more hydrophobic than their traditional counterparts, resulting in harder finished bars with a longer lifespan. In addition, both
the newly generated higher molecular weight fatty alcohols, as well as the existing unsaponifiables will also contribute to the overall
hydrophobicity of the soap bar, improving the film –forming and skin protecting qualities of the bar [15].

The reaction products obtained from the saponification of each major natural wax component are summarized in Table 1.

Objective Experimental
The objectives of this paper are as follows: MATERIALS: The following materials were used to conduct this experiment:
• Saponify multiple natural waxes and determine the • Natural Waxes as described in Table 2, all provided by Koster Keunen, Inc.
properties of the reaction products.
• Olive oil (INCI: Olea Europaea (Olive) Fruit Oil) as the control and standard,
• Determine the effects of adding different percentag- provided by Columbus Vegetable Oils.
es of natural waxes to traditional soap recipes.
• Sodium hydroxide, purchased from Fischer Scientific, from which a 30%
solution was prepared for use in all the saponification reactions.

Wax Name INCI Name Source Broad Chemical Average Sap Melt Point Appearance State at Room
Composition Value (mg (°C) Temperature
NaOH/g)
Bayberry Wax Myrica Cerifera (Bayberry) Bayberry Fruit Triglycerides, C16 155 40-55 Light Brown to Solid
Fruit Wax Olive Green

Cocoa Butter Theobroma Cacao (Cocoa) Cocoa Beans Triglycerides, C16, C18:0, 138 29-35 White to Off Solid
Seed Butter C18:1 White

Soy Wax Hydrogenated Soybean Oil Crude Soybean Oil Triglycerides, C18 135 62-72 White to Off Solid
White

Castor Wax Hydrogenated Castor Oil Crude Castor Oil Triglycerides, C18:OH 128 85-89 Off White Solid

Kester Wax K-24 Lauryl Laurate Crude Coconut and Low Molecular Weight 104 23-30 Off White to Liquid
Palm Oils Monoesters Light Yellow

Kester Wax K-48 Cetyl Palmitate Crude Coconut and Medium Molecular 104 45-53 White to Off Solid
Palm Oils Weight Monoesters White

Orange Wax Citrus Aurantanium Dulcis Orange Peels Fatty Acids, Phytosterols, 73 35-45 Orange to Brown Liquid
(Orange) Wax Fatty Alcohols

Rice Bran Wax Oryza Sativa (Rice) Bran Crude Rice Bran Oil High Molecular Weight 70 77-82 Yellow to Light Solid
Wax Monoesters Brown

Beeswax Beeswax Bee Secretion Esters, Hydrocarbons, 66 62-65 White to Yellow Solid
Free Fatty Acids/Alcohols

Sunflower Wax Helianthus Annuus Crude Sunflower High Molecular Weight 63 74-77 Light Yellow Solid
(Sunflower) Seed Wax Oil Monoesters

Carnauba Wax Copernicia Cerifera Carnauba Palm Esters, Free Fatty Acids, 62 80-86 Dull Yellow to Solid
(Carnauba) Wax Leaves Hydrocarbons Light Brown

Candelilla Wax Euphorbia Cerifera Candelilla Shrub Hydrocarbons, Esters, 43 68-73 Yellow to Brown Solid
(Candelilla) Wax Leaves Free Fatty Acids, Resins

Table 2. Chemical and Physical Properties of Natural Waxes.

PAGE 04
Methods and Procedures In some cases, Natural Waxes did not make a commercially
acceptable soap at 100% usage, as the bars were composed of
• 
Saponification values for each Natural Wax in Table 2 were a high level of unsaponifiables. To continue the experiment, each
either obtained from the specification sheet provided by Koster Natural Wax was blended with olive oil at 50% ratios, saponified,
Keunen, Inc. or calculated using the USP 401 Method [16]. and the reaction products were evaluated and compared to 100%
The saponification values were then used to determine the olive oil (control). We will refer to these blends as “saponified
amount of the 30% sodium hydroxide solution required for blends” for the remainder of this paper, and each one was
each saponification reaction. evaluated within the following categories:

• 
The saponification reactions were carried out as follows: Quantitative Evaluation: Effect on Bar Rigidity.
o Each Wax or Wax/olive oil blend was heated to approximately
80 °C as Phase A and allowed to cool below 60 °C. Penetration values were measured on a Koehler K19500
o The appropriate amount of 30% Sodium hydroxide solution penetrometer. The penetration of 100% saponified olive oil
was also heated to 60 °C as Phase B. was recorded at 57 dmm (needle, 50g). The saponified blends
o Phase B was added to Phase A with sufficient mixing using measuring below 57 dmm proved to harden the bar, increasing
a propeller mixer, while maintaining the temperature at 60 bar rigidity, while the saponified blends measuring above 57 dmm
°C for approximately 25 minutes. The saponified blend was proved to soften the bar, decreasing bar rigidity.
then immediately poured into a silicone mold and allowed to
Tactile Evaluation: Effect on Bar Cleansing Properties and

cure for 48 hours.
Lather
o After the 48-hour cure time, a pH testing at or below 10
confirmed the reaction was complete. In a sensory panel performed internally (N=20); individuals were
Experimentation given specific hand washing instructions and asked to evaluate
both the lather on the hands and the cleansing properties of each
Each Natural Wax, as well as the olive oil control, was saponified saponified blend against the olive oil control. Panelists rated each
individually (100%) and the reaction products were evaluated. saponified blend as “increases,” “decreases,” or “no change.”

No matter what
the product…

“We’ve got a
wax for that.”

Kosterkeunen.com
Sensory Evaluation: Effect on Bar Color and Odor

The same sensory panel was asked to describe the finished bar colors and odor. These subjective observations were determined by
comparing each saponified blend to the olive oil control.

Practical Evaluations: Trace Level, Recommended Use Level, Recommended Applications

Trace Level was determined by a skilled soap maker based on how fast/slow each saponification reaction took place. The Recommended
Use Level and Recommended Applications for commercial soapmaking were also determined for each Natural Wax.

Results

All results are presented in Table 3.

Quantitative Tactile Sensory Practical

Evaluation Evaluation Evaluation Evaluation

Wax Name Effect on Bar Effect on Bar Effect on Effect on Effect on Trace Level at Recommended Recommended
Rigidity Cleansing Bar Lather Bar Color Bar Odor 50°C Usage Level Applications
Properties
Bayberry Wax Hardens Increases No Change Green Yes Very Fast 100% Artisanal

Cocoa Butter Softens Decreases No Change Light Yellow Yes Slow 100% Layering, Pours

Soy Wax Hardens Decreases Decreases White/Off No Slow 15% Molds

White

Castor Wax Hardens Decreases No Change Off White No Slow 15% Molds

Kester K-24 Softens Decreases Decreases Ivory No Slow 50% Drop Swirls

Kester K-48 Hardens Decreases Decreases White No Average 15% Molds

Orange Wax Softens No Change Increases Dark Orange Yes Average 50% Layering, Swirls

Rice Bran Wax Hardens No Change No Change Light Brown Slight Fast 15% Layering, Designs

Beeswax Hardens Increases No Change Ivory Slight Average 50% Textured Top

Sunflower Wax Hardens Decreases Decreases Light Brown No Fast 15% Molds

Carnauba Wax Hardens Increases Increases Orange Yes Very Fast 50% Artisanal

Candelilla Wax Hardens No Change Increases Tan Yes Average 50% Embedding

Table 3. Properties of Saponified Natural Wax/Olive Oil blends. 50% of Each Natural Wax was saponified with 50% Olive Oil and evaluated.

Discussion

The results in Table 3 indicate each Natural Wax tested brought forth very distinct characteristics and attributes in traditional soapmaking.
It was also determined that certain waxes are not always a suitable addition to these traditional techniques. Specifically, Natural Waxes
with high melt points, higher molecular weight components or hydrogenated triglycerides can pose some challenges in processing
techniques and are therefore recommended as hardening additives at ≤ 15% use level. Despite these few specific challenges, we
were able to conclude that the following Natural Waxes offer numerous advantages in soap making, whether at 100% usage or as an
addition to traditional triglyceride formulations.

PAGE 06
Bayberry Wax Candelilla Wax

Due to its high triglyceride content, Bayberry Wax is fully Although Candelilla Wax is composed of 50% natural
saponifiable and can be used alone to make textured, artisanal hydrocarbons, the free fatty acids present saponify readily,
bars, or as an additive to impart a rustic texture, color, and odor. especially when combined with other triglycerides. Candelilla Wax
also produces an excellent lather and an overall hard bar of soap.
Cocoa Butter
The natural color and odor are preserved.

Presenting a high triglyceride content and a relatively low melt

Rice Bran Wax
point, Cocoa Butter can also be used at 100% to make a naturally
moisturizing soap. As an additive, Cocoa Butter can slow trace, Rice Bran Wax contains mostly high molecular weight monoesters
allowing soap makers to achieve swirls and designs, or soften and is an effective and inexpensive hardening agent in soap
existing bars. systems with no real effect on color, texture, or odor. Also high in
palmitic acid, Rice Bran Wax also raises the possibility of replacing
Lauryl Laurate
palm oil in low percentages.

The saponification of Lauryl Laurate yields sodium laurate, which

aids in a stable, fast acting lather. This, combined with the lauryl
alcohol generated, allows for soft formulas and unique, jelly-like
textures in higher percentages.

Orange Wax

Only partially saponifiable with a high phytosterol content, Orange

Wax is recommended as a natural orange colorant (both in the bar
and the lather it produces), fragrance additive, and bar softener.

Beeswax

Beeswax is useful in all soap formulations at different usage levels

due to its free fatty acids and its ratio of saponifiable/unsaponifiable
components. Beeswax adds tack and is primarily a hardening
additive, while also maintaining the original soap characteristics
like odor, color, or lather.

Carnauba Wax

The hardening properties of saponified free fatty acids and high

molecular weight monoesters present in Carnauba Wax helps
to impart a firmer, long-lasting bar of soap with a dense, stable
lather. Saponification also occurs much faster due to the higher
percentage of unsaponifiables.

CONCLUSIONS
Although there is minimal information in current literature regarding the use and effects of Natural Waxes in soapmaking, possibly
due to a very triglyceride-focused soap industry, the results of these experiments indicate the beginning of a relationship between
the two. The uniqueness of each Natural Wax can be leveraged to create improvements in appearance, performance, and stability,
setting the soap maker apart from the competition. In conclusion, incorporating Natural Waxes into traditional soap recipes allows
for new formulas and more creativity, while keeping in alignment with a sustainable, natural future.

PAGE 07
References 9. Ashenhurst, J. (n.d.). Basic Hydrolysis of Esters –
Saponification. Retrieved January 5, 2023, from https://www.
1. 
American Cleaning Institute (n.d.). Soaps & Detergents masterorganicchemistry.com/2022/10/27/saponification-of-
History. Retrieved December 12, 2022, from https://www. esters/
cleaninginstitute.org/understanding-products/why-clean/
soaps-detergents-history 10. Mintel (n.d.). Untitled. Retrieved December 13, 2022, from
https://mintel.com
2. 
BearMoon Soap (2020, September 15). The Origins of
Soap. Retrieved December 28, 2022, from https://www. 11. Christie, W. W. (n.d.). Lipids: Definitions, Classification and
bearmoonsoap.com/blogs/news/the-history-of-soap Nomenclature. Retrieved December 29, 2022, from https://
lipidmaps.org/resources/lipidweb/lipidweb_html/lipids/basics/
3. Koeppel, D. (2020, April 15). The History of Soap. Wirecutter. Nomen/index.htm
Retrieved December 21, 2022, from https://www.nytimes.com/
wirecutter/blog/history-of-soap/ 12. Rustan, A. C., & Drevon, C. A. (2005). Fatty Acids: Structures
and Properties. In eLS (Ed.). John Wiley & Sons, Ltd. https://doi.
4. Davidson, A. S. (n.d.). Early Synthetic Detergents. Britannica. org/10.1038/npg.els.0003894
Retrieved December 28, 2022, from https://www.britannica.
com/science/soap/Early-synthetic-detergents 13. Coiffard, L., & Couteau, C. (2019). Soap and syndets: Differences
and analogies, sources of great confusion. Eur Rev Med
5. Stephenson (2014, September 12). Soap vs. Syndet. Retrieved Pharmacol Sci, 24, 11432-11439. https://doi.org/10.26355/
January 5, 2023, from https://www.stephensonpersonalcare. eurrev_202011_23637
com/blog/2014-12-09-soap-vs-syndet
14. 
Christie, W. W. (n.d.). Waxes. The Lipid Web. Retrieved
6. Fact.MR (n.d.). Hand Soap Market. Retrieved January 11, 2023, December 29, 2022, from https://lipidmaps.org/resources/
from https://www.factmr.com/report/4718/hand-soap-market lipidweb/lipidweb_html/lipids/simple/waxes/index.htm

7. Moriarty, S. (2022, October 26). Mintel’s Global Annual Trends 15. Eberting, C. L., Coman, G., & Blickenstaff, N. (2014). Repairing
2023. Retrieved January 13, 2023, from https://clients.mintel. a Compromised Skin Barrier in Dermatitis: Leveraging the
com/content/trend/mintel-s-global-annual-trends-2023 Skin’s Ability to Heal Itself. J Allergy Ther, 5(5). https://doi.
org/10.4172/2155-6121.1000187
8. Prieto Vidal, N., Adeseun Adigun, O., Pham, T.H., Mumtaz, A.,
Manful, C., Callahan, G., Stewart, P., Keough, D., & Thomas, R.H. 16. General Chapter: USP. Fats and Fixed Oils – Chemical Tests
(2018). The Effects of Cold Saponification on the Unsaponified and Assays <401>. In: USP-NF. (2022, May 1) DOI: https://doi.
Fatty Acid Composition and Sensory Perception of Commercial org/10.31003/USPNF_M99160_04_01
Natural Herbal Soaps. Molecules, 23(9), 2356. https://doi.
org/10.3390/molecules23092356

www.kosterkeunen.com