What is Soap ?

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Solving Problems
Creating Value
Questions
What is a typical Soaps composition ?
How does it function ?
How is Soap made ?
What parameters are important for its
marketers?
Appreciation of a Formulators work
Implications on perfumes
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What is Soap Bars Chemical Structure ?
Formulation
Soap % Range Typical
TFM : Total Fatty Matter 82-50 78
Sodium Hydroxide 7-4 6
Moisture Content 10-14 12
Superfat 1-2 0.5
Electrolytes (NaCl, Na2CO3) 0.5-1.0 0.7
Fillers 0-25 1.5
Active Surfactants 0-4 0
Speciality Ingredients e.g.
Optical Brighteners max 0.03 0.03
Perfumes ~1.5 1.3
Preservative : Chelating agents max 0.3 0.3
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OLD SYSTEM OF SOAP MANUFACTURING
Oil + Caustic Soap + Glycerine
OIL
Lauric Oils
CNO
CNO Acid Oil
PKFA
Myristic acid
Non Lauric Oils
RBO
HRBO
Karanjia
Neem
Castor Oil
Palm
Cotton seed
Tallow
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NEW SYSTEM OF SOAP MANUFACTURING
Distilled Fatty Acid + Caustic Soap + Water
Lauric Oils-
Fatty Acids
CNO
CNO Acid Oil
PKFA
Myristic acid
Non Lauric Oils- Fatty Acid
Rice Bran Oil
Hydrogenated RBO
Karanjia
Neem
Castor Oil
Palm & Palm Fractions
Cotton seed
Tallow
Fatty Acids
Oil + Water Crude Fatty Acid + Glycerine
Crude Fatty Acids are then Distilled to remove impurities
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CHEMICAL EQNS
Fatty Acid + Caustic Soap + Water
RCOOH NaOH
RCOONa H2O
Oil + Caustic Soap + Glycerine
CH-OR
CH2-OR
CH-OR
3 NaOH
RCOONa
CH-OR
CH2OR
CH-OR
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All Oils = Glycerol + Mixtures of Fatty Acids (organic carboxylic acids)
Organic Carboxlic acids Inorganic acids like HCl etc but like acetic
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IMPORTANT CHARACTERISTICS
For SOAP MAKING
Saturated Fatty Acids
Name Chain
Length
MP
o
C Usefullness
Butyric C4 - 8.0 Not required
Caproic C6 - 2.0 Not required
Caprilic C18 16.5 Lather/Process aid
Capric C10 31.3 Lather/Process aid
Lauric C12 43.6 Lather/Process aid
Myristic C14 53.8 Lather
Palmitic C16 62.8 Body structure
Stearic C18 69.0 Body structure
Arachidic C20 75.3 Not required
Behenic C22 79.8 Not required
Lignoceric C24 84.1 Not required


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UNSATURATED FATTY ACIDS : EFFECTS
Double Bond
One can see the affect of introduction of a unsaturation in fatty acids
Linoleic / Linolenic are useless for dirt removal / lather
Added disadvantage of perfume stability (PUFA bad for Soap stability)
Oleic is most important, attracts equal amount of Laurates/Myristates to form soap
which can go in liquid phase to give excellent lather attributes.
Name Chain
Length
MP
o
C No. of double
bonds
Position
Stearic C18 69.9 0 0
Oleic C18 16.0 1 9 10
Linoleic C18 -5.0 2 0 10, 12 - 13
Linolenic C18 -11.0 3 9-10, 12-13, 15-
16

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HISTORY Vs IDEAL SOAP FAT CHARGE
Universally by accident, good soap was discovered.
Like any other natural resource, related science unfolded after 1900 to
explain properties.
Ideal soap - 60/ 78 TFM made from 20 CNO / 80 Tallow
Gives all soap user attributes.
FA composition % Unsaturation
C8 - C10 2.6 0
C12 Lauric 9.6 0
C14 Myristic 3.8 0
C16 Palmitic 22 0
C18 Stearic 25 0
Oleic 34 1
Linoliec 3 2
Linolenic 0 3
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GOOD SOAP vs SOAP STRUCTURE
Good Lathering Cleaning - dirt removal.
Good feel Good colour
Economy in use Good perfume
Long shelf life Easy to handle shape
Excellent presentation
Last two are aesthetics.
Very difficult to find one single molecule satisfying all these
properties and hence - fat charge selection.
Point proved beyond doubt by 78 TFM -
Laurate/Myristate
- Palmitate / stearate
- Nil Lather / Nil ROW
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VISUALISE SOAP MOLECULE
Water hating
insoluble in water
Water loving
As anion is responsible soap is called anionic detergent.
Na
+
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Micellisation
water
Surface Tension drops with increasing Soap conc, become flat at CMC
Low Surfacre Tension = More penetration of water into cloth fibres or
surface of skin to clean inorganics
Micelles solubilize organic dirt inside and remove
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Formulation Principles
BRICK
Palmitates,
Stearates,
Myristates(50)
MORTAR
Oleates, Laurates,
Myristates(50)
Conventional Soap (78 tfm) :
# 78 tfm , 38-40 IV - 13 mc max (processability issues )
# soluble phase :
* moisture 13
* eutectic mixture of fats 16
Structured Soap :
seeks to replace insoluble brick fat by structurants
total = 29
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Formulation Principle
Formulation
Soap % Range Typical
TFM : Total Fatty Matter 82-50 78
Sodium Hydroxide 7-4 6
Moisture Content 10-14 12
Superfat 1-2 0.5
Electrolytes (NaCl, Na2CO3) 0.5-1.0 0.7
Fillers 0-25 Nil
Active Surfactants 0-4 0
Speciality Ingredients e.g.
Optical Brighteners max 0.03 0.03
Perfumes ~1.5 1.3
Preservative : Chelating agents max 0.3 0.3
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Which Parameters are important?
Formulation
TFM
IV
CNO
Moisture Content
Superfat
Electrolytes
Fillers
Active Surfactants
Speciality Ingredients e.g. Polymers
Environmental
Ageing
Temperature Profile
Humidity
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Parameter mapping

% Wear MVA/MBI Lather PV
TFM

-

CNO -

-
Superfat -

IV

MIV

-

NaCl content

- -


Thumb Rules
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Gross Negatives
Cracking
Efflorescence
Perfume Interaction
due to chemical reactions between different ingredients
viz. aldehydic, ketones and esters, trace metals from
packaging materials and aromatic organic compounds in
printing inks
Grit
Soap grit :due to improper process conditions, detectable
only in cold water
Chemical grit : oversize particulate
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Implications on Perfume
Product Formulation
TFM
Structurant/ inorganic compounds e.g. Soda Ash, Salt, Phosphates etc
Organic compounds e.g. Glycerin, surfactants, starch derivatives, color
Water
Perfume
Outer Packaging
Stiffener
Packaging substrate
Printing inks
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Understanding role of TFM
Major portion of all soaps: Majority of perfume goes in masking
off-odors generated by this component
Fatty Acids <c12have characteristic sharp odor (unpleasant)
Removed during distillation using new structured packing
technology
Improper Distillation op parameters=> unpleasant odor i.e.burnt,
acrid if residence times high => FFR distillation column
Pretreatment of Oilsmust to remove Proteinaceous materials
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Odors in Oils : Understanding them
Influenced by the type and quality (Freshness) of oil
Concept of Natural odors vs. Degradation odors
Natural Odors are characteristic of a particular Oil
For removal of Natural odors identification of characteristic odoriferous
bodies for individual oils a must
Set distillation parameters to ensure separation of these odor bodies
from bulk cut by
Providing adequate number of fractionating stages
Condenser temperatures
Pretreatment of oil
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Natural Odors by Oil type
Characteristic odors of Lauric fractions:
Typical coconut like : Delta Octalactone
Heavy, nutty, oily : Delta Dodecalactone
Oily, old nutty : 2 Tridecanone
Characteristic odors of Palm fractions
Metallic mushroom : 1 Octene-3-one
Germanium metallic: Cis 1,5 Octadiene-3-one
Characteristic Odors of Rice Bran Oil
Husky, Branny, Spicy : Isoeugenol, Eugenol, Guiacol derivatives
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Degradation of TFM
Saturated Fatty Acids are not prone to oxidative degradation however sensitive
to Pyrolysis
Primary cause of degradation is the autoxidation of unsaturated fatty acids
(PUFA)
Rate of autoxidation increases with degree of unsaturation
C18:3 is 30 times faster degrading than
C18:1 and C18:2 is 10 times faster than C18:1
All the above decomposition resultant products are short chain unsaturated
fatty acids, Hydrocarbons, alcohols or carbonyl group compounds viz.
aldehydes & ketones
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Degradation Mechanisms
Free radical Autoxidation of unsaturated fatty acids
(Chain Reaction)
Initiation :
-CH-C=C- => -C*-C=C- + H* (Heat, light, transition metals)
Propagation
R* + O
2
=>ROO*
ROO* + RH => ROOH + R* (ROOH Hydroperoxide)
Termination
R*+R* => R-R
R* + ROO* => ROOR
ROO* +ROO* =>ROOR +O2
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Degradation Mechanisms
Free radical Autoxidation of unsaturated fatty acids
-CH-C=C- => -C*-C=C- + H* (Heat, light, transition metals)
The resultant allyl radical is stabilized due to delocalization of electrons over
3 Carbon atoms for C18:1 and 5 Carbon atoms for C18:2 (Resonance effect)
-C*-C=C <=> -C=C-C* = -C-C-C
-C=C-C*-C=C- <=> -C*-C=C-C=C <=> -C=C-C=C-C*-
=-C-C-C-C-C-
Above explains the different rate of reactions for the three species
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Degradation Mechanisms
Free radical Autoxidation of unsaturated fatty acids
-The different hydroperoxides produced are
C18:1 a mixture of 8-,9-,10-,11 allylic hydroperoxides
C18:2 a mixture of conjugated 9- and 13- hydroperoxides
C18:3 a mixture of diene-triene 9-,12-,13- and 16-
hydroperoxides
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Degradation Mechanisms
Free radical Autoxidation of unsaturated fatty acids
Hydroperoxides are unstable and decompose
1. R-CH(OOH)-R => R-CH(O*)-R +OH*
R-CH(O*)-R => R-CHO +R* and so on
2. R-CH(OOH)-R => R-CH(O*)-R +OH*
R-CH(O*)-R => R-CO-R +H* and so on
Final Degradation products
Oleate : 8-hydroperoxide => 2 Undecanal and decanal
9-hydroperoxide => 2 Decenal & Nonanal
Linoleate: 9-Hydroperoxide => 2,4 decadienal & 3-Nonenal
13-Hydroperoxide=> Hexenal
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Degradation Mechanisms
Singlet Oxygen Mechanism
Singlet oxygen reacts readily with PUFA
generated by exposure to light in the presence of photosensitizes like
Chlorophyll and transition metals etc.
Oxygen added directly across the double bond by ene reaction
Produces allylic hydroperoxides
Effect of Metals
Metals initiate Fatty Acid- Oxygen reactions and form colored
complexes
The anion formed can either lose an electron to give singlet oxygen or
react with a proton to form hydroperoxy radicals
2 O*
M
+
+ O
2
=> M
2+
+ O
2
*
HOO*
H*
e
-
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Antioxidants
Five Categories
Primary antioxidants : Terminate free radical reactions e.g. TBHQ, BHT
etc.
Synergists : Boost activity of primary antioxidant
Oxygen Scavengers e.g. Ascrobic Acid
Biological Antioxidants (natural) e.g. Tocopherols Vitamins
Chelating Agents : Complexes the metal ions and render them inactive
as catalysts e.g. EDTA, EHDP, Citric Acid
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Effect of Temperature
Higher Temperatures = More rapid degradation
Rate of Reaction is that much faster
Longer Exposure to High Temperature = Faster Degradation
DFA tanks Uninsulated
Rapid Cooling of DFA as it leaves the distillation still
Nitrogen blanketing
Citric Acid addition
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Degradation of TFM by Biological
Oxidation
Microbial organic growth in presence of moisture
Two mechanism proposed for this
-Oxidation & -Oxidation
-Oxidation
Terminal Carbon atom attacked by Microbes
Dicarboxylic acids are formed and excreted e.g. Sebacic acids, suberic
acid etc.
Presence of other ketonic bodies has been observed leading to further
complex biological degradation of oils
Some of these compounds will get removed during distillation but some
will co-distill : Rancid Odors
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Role of Structurant and other inorganic materials
Chromatography Principle/Wicking effect of structurants
Mobile Carrier
Substrate
Explained by
Surface adsorption
Relative solubility
Surface Charge
Functional Group
interaction
Substate= Structurant
Mobile Carrier= Solvents/Moisture
Ink = Perfume
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Substrate : inorganic fillers e.g. Talc or Frisis (Hydrated
Magnesium Silicate) or Alumina Hydrate,
Sodium Phosphate, salts etc.
Organic molecules e.g. Glycerin, Surfactants
Perfume
Organics also work by
solubilization and micellar & LC
encapsulation
Why is perfume delivery better
from liquid soaps?
Chromatography Principle applied to Structurants
Surfactant Micelle
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Packaging: Chemical composition
Stiffener : Virgin cellulosic material (Bamboo, Eucalyptus)
extrusion coated with LDPE , Rosin as binder
Outer wrapper :Agricultural Residue (AR:- Bagasse) recycled,
Fungistat :Sodium Salicylanilide (SSA), China clay as binder
Printing inks : Pigments + Solvents
Pigments : Phthalocyanine Blue, Yellow etc.Defined by a
Colour Index number
Solvents : MEBK, MIBK, MEK, Toluene etc.
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Outer Packaging
Stiffener : Paper, resinuous gums, polymer coating, wax etc. In
constant touch with the soap therefore interaction with residual
Chlorine + Transition metals
Outer wrapper : Paper + Printing Inks
Printing inks : Aromatic compounds,
phenols and resins along with solvent carrier.
All have complex reactions with soap
Metal content is specified and controlled
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Q&A
High TFM = Higher Quality of Soap ?
High TFM Higher Quality e.g. Dove
Quality of TFM Quantity
Customers complaining of soap fragrance not lasting after a few bath?
How is it connected to formulation?
Fragrance affected by base odor/ migration due to wicking/micellization
What additives affect fragrance delivery ?
Inorganics like Soda/silicate affect greatly. Talc to some extent.Liquid
crystal disruptors play a part in perfume delivery on skin ( Patent
EP0311343). Shielded Cationics/Shielded Starch Encap will
work/Silicones/ MCT will also work
Mixtures of oils= good formulation ? How to use cheaper oils ?
Cheaper oils can be used without impacting fragrance delivery by using a
good formulator
Even if the oil is cheap Freshness counts! Fresher the oil for the soap
base = better fragrance impact.
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Q&A
What shapes/colours/ textures/ designs are possible ?
Anything is possible. Moulded soaps give more freedom than
extruded soaps (at higher costs)
Can two sides of a soap have different fragrances?
Yes, Both extruded and moulded soaps
What is Virgin base?
Non-recycled. Sometimes it also refers to soaps made from Oils
and not Acid byproducts
What is the best possible base available in India and the world?
40 RBDPS/ 40 Palm Oil/20 CNO euivalent with C12 from CNO is
the best possible base in the world. Available through the
malaysian manufacturers (due to freshness of oil)
What factors affect soap base costs?
Oil/Caustic/location of factory/scale of operation
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Q&A
What is Tallow soap? Why does it have odour?
Tallow is one of the oils from Beef production. It has its own unique
odor due to presence of small amounts of proteins.
Glycerine soaps and winter usage? Which soaps will dry the
skin the least?
Non soaps like Dove. Less lather in the soaps more milder it will
be
Fairness soaps do they work ?
No all. Sunscreen soaps work but Fairness soaps dont at a
consumer level.
Can a shower gel give squeaky clean feel like soap ?
Yes.
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