Novel Cosmetic Surfactant

Systems
Cosmetic Formulation

Perry Romanowski
Element 44 Inc.
May 3, 2015
Novel Cosmetic Surfactant
Systems
Cosmetic Formulation

Perry Romanowski
Element 44 Inc.
May 3, 2015
 Perry Romanowski
• Element 44 Inc.
• Brains Publishing Inc.
• Cosmetic Chemist
– Formulator
– Inventor
• Writer
• Instructor
• Professional Blogger
http://thebeautybrains.com
http://chemistscorner.com
http://chemistscorner.com/members
 Contact

Vice President Brains Publishing Inc.

Email: Perry.Romanowski@gmail.com

LinkedIn: PerryRomanowski

Phone: 708-207-7642

Twitter: @chemistscorner

Facebook
 Objectives
• Learn about cosmetic technologies
• Understand the raw materials used
• Learn the different formulation forms
• Cover specific formulations
– Cleaning products
– Moisturizing products
 Agenda
• 9:00 – 9:30 Introduction to cosmetics
• 9:30 – 10:30 Cosmetic ingredients
• 10:30 – 10:45 Break
• 10:45 – 11:45 Cosmetic formulations
• 11:45 – 12:30 Formulation process
 My mission

Educate Inspire Entertain

Cosmetics
Purposes of
Cosmetics

• Improve your…

• Appearence
• Skin Feel
• Odor
 What are
Cosmetics?
 Articles intended to be rubbed, poured,
sprinkled or sprayed on or introduced into
or otherwise applied to the human body or
any part thereof for cleansing, beautifying,
or promoting the attractiveness , or
altering the appearance, and articles
intended for use as a component of any
such articles; except that such term shall
not include soap
-FDA CFR
Image of color cosmetics

Color
Cosmetics
Hair Products

Image of hair products

 Skin
Products
Perfume &
Fragrances
Oral care
Products
 Cosmetics aren’t drugs

 Drugs = Treat disease

 Cosmetics = Improve appearance

Can't interfere with metabolism

http://www.fda.gov/Cosmetics
Personal Care Products Council
 International Regulatory bodies

• European Commission
• Health Canada
• Ministry of Health
(Japan)
• Department of Health
& Ageing (Australia)
• CFDA - China
 General Problems
addressed by cosmetics

• Appearance
• Feel
• Smell
 Top 10 skin problems
1. Dry itchy skin
2. Wrinkles
3. Acne
4. Sagging Skin
5. Age spots
6. Skin lightening
7. Tattoo removal
8. Eczema / Dermatitis
9. Psoriasis
10. Cellulite
 Top 10 hair problems
1. Hair Loss
2. Unwanted Hair
3. Gray Hair
4. Hair color change
5. Hair feels bad
6. Frizzy, unruly hair
7. Thinning hair
8. Lack of volume
9. Shine
10. Time needed to style
 Strategies for Improving Appearance
• Remove dirt from surface
– Cleansing products
• Change the surface
– Exfoliating products
• Leave color behind
– Make-up
• Change color of surface
– Self tanning products
 Strategies for Improving Feel

• Materials that make

skin & hair feel better
– Oils and emollients
• Water attracting
compounds
– Moisturizers
• Conditioning products
– Film forming material
 Strategies for Improving Odor
• Clean odor materials
off body
• Cover odors with
fragrance
• Kill microbes that
cause odor
 Lots of interest in
Natural Formulating
Greenwashing
Natural has no legal definition
Natural Standards Groups
 Major US Natural Standards Groups
• USDA
• National Sanitation Foundation
• National Product Association
• OASIS
International Natural Standards
 COSMOS Standards
• Promote organic agriculture
• Use natural resources
• Clean processing and manufacture
• “Precautionary Principle”
• Integrate Green Chemistry principles
Principles of Green Chemistry
 Basic Definition of Natural
• Not Synthetically Derived or
Synthetically processed

• If it’s not from a plant, it’s not

natural

• USDA definition

• Other standards are not as strict

 Common Standards
• Water is natural
• Mineral ingredients are natural
• Physically processed agro-
materials are natural
• Some chemical processing of
agro materials
• Some synthetics allowed
 Some Prohibited Ingredients
• Parabens
• Formaldehyde Donors
• Petrolatum & petroleum derived
• Propylene glycols
• Sodium Lauryl Sulfate
• Ethanolamines
• Synthetic Silicones
• Synthetic Fragrances
• Synthetic Polymers
• EDTA
 Some Chemistry Allowed
• Distillation
• Esterification & Etherification
• Expression
• Extraction
• Fat Splitting
• Fermentation
• Hydrogenation
• Protein Hydrolysis
• Saponification
• Sulfation – (no SLS)
 Cosmetic Science Quiz

• Which ingredient is not in the top 10 most

vilified cosmetic ingredients?

– 1. Methyl Paraben

– 2. Mineral Oil

– 3. Titanium Dioxide

– 4. Sodium Laureth Sulfate

 Most Vilified Ingredients on the Internet

1. Sulfates – SLS / SLES

2. Parabens
3. Talc
4. Petrolatum
5. Mineral Oil
6. Propylene Glycol
7. DEA
8. Formaldehyde
9. Aluminum
10.Fragrance
Cosmetic Raw Materials
Raw Material
Cladistics
 Cosmetic Raw Materials
• Functional – Provide the product benefit

• Aesthetic – Improve the aesthetics of the

functional ingredients

• Claims – Included to help sell the product

 Functional Raw Materials
• Ingredients that make cosmetics work

• Cleansers
• Conditioners
• Film formers
• Drug actives
• Reactants
• Colorants
• Fragrances
 Cleansers
• Ingredients that remove surface dirt / oil
• Some oil based cleansers
• Surfactants
 Surfactants
Hydrophillic Lipophillic

Compatible Compatible
With Water With Oil
 Surfactant Structures

• Structure Factors
• Surfactant type
• Oil type
• Concentration
• Ionic character
 Surfactant Functions
• Cosmetic Benefits
– Cleaning / Detergency
– Conditioning
– Foaming

• Aesthetic benefits
– Emulsification
– Wetting / Dispersing
– Thickening
– Penetration enhancement
– Antimicrobial activity
– Opacification
Types of Surfactants
 Anionic Surfactants
• These are the primary cleansing surfactants
• Alkyl Sulfates
– Examples – SLS and ALS
• Alkyl Ether Sulfates - Ethoxylated
– Example – SLES and ALES
 Anionic Surfactants
• Other types
– Sulfosuccinates – Acyl Isethionates
– Alkylbenzene – Acyl Polypeptide Condensates
Sulfonates – Monoglyceride Sulfates
– Acyl Methyltaurates – Fatty Glyceryl Ether
– Acyl Sarcosinates Sulfonates

Sodium Lauryl Sarcosinate

 Anionics
• Why use them?
– Excellent detergency
– Relatively inexpensive
– Good foaming
– Highly stable

• Drawbacks
– Can be irritating
– Drying to hair
 Sulfates and Naturals
• Unacceptable for cleansing surfactants for
natural products
– Sulfosuccinates
– Sulfonates
– Alkyl sulfates
 What is used instead
• Sultaines
• Mild secondary surfactant, more
stable and better viscosity builder
• e.g. Cocamidopropyl
Hydroxysultaine

• Acyl Sarcosinates
• High foaming secondary
surfactant
• e.g. Sodium Lauryl Sarcosinate
 Natural Surfactant Options
• Alkyl Polyglucoside
• Natural primary surfactant derived from
coconut and sugar
• Does not build viscosity as well
• Does not foam as well
• Higher cost
• e.g. Lauryl Glucoside
 Natural Cleansing Surfactants

• Saponins – Cleansing Surfactants

• Source: plants – marine derived
– Quillaja saponaria Molina
• Difficult to purify
• Too expensive
• Not as effective
• ~40% less foam
• Highly colored
 Commercially Available Saponins
• Bio-Saponins (Bio-Botanica)
– mix of Sarsparilla, Wild Yam, Quillaja and Yucca
extracts.
• Neo Actipone Soap Nutshell (Symrise)
– Soap Nut tree (Sapindus Mukurossi) extract.
• Andean QD Ultra & Ultra Organic (Desert King)
– Chilean soap bark tree (Quillaja Saponaria Molina)
extract.
 Amphoteric Surfactants
• Can have a positive or negative charge
depending on the pH of the solution
• Zwitterionic
• Types
– Cocamidopropyl Betaine Positive Negative
– Sodium Lauraminopropionate
 Amphoteric Surfactants
• Why use them?
– Good Detergency
– Less Irritating than anionics
– Helps thicken system
– Helps improve foam

• Drawbacks
– More expensive
– Do not foam well enough on their own
 Non Ionic Surfactants
• Surfactant molecules with no charge

• Types
– Fatty Alcohol
– Fatty amines
• Lauramide DEA
– Amine Oxides
• Lauramine Oxide
• Polysorbates
 Non Ionic Surfactants
• Why use them?
– Foam enhancer
– Reduce irritation
– Conditioning effect
– Solubilize fragrances
– Emulsifiers

– Gentle Cleansers
• PEG-80 Sorbitan Laurate

• Drawbacks
– More expensive
– Do not foam well on their own
 Functional Raw Materials
Conditioners & Moisturizers
 Functional Raw Materials
Conditioners & Moisturizers

• Defined
– Ingredients that improve condition of hair or skin
– Must be substantive to work
 Moisturizing Ingredients

• Quats
• Cationic Polymers
• Silicones
• Occlusives
• Humectants
• Emollients
 Quats
• Cationic Surfactants
– Hydrophobic tail
– Hydrophilic head

Cetrimonium Chloride
 Quats
• Examples
– Cetrimonium Chloride
– Stearalkonium Chloride
– Dicetyldimonium Chloride
– Behentrimonium Chloride
 Quats
• How do they work?
– Electrostatic Attraction
– More damage = more substantivity
– Longer chain length = more conditioning
 Quats
• Benefits
– Effective
– Easy to work with
– Less expensive

• Drawbacks
– Can be irritating
– Not compatible with anionics

• % Used if formula
– Up to 5%
 Cationic Polymers
• Large molecules with multiple, positively
charged sites
 Cationic Polymers
• Common Examples
– Polyquaternium 4
– Polyquaternium 7
– Polyquaternium 10
– Guar Hydroxypropyltrimonium Chloride
Positive

Negative
Cationic Polymers
 Cationic Polymers
• Benefits
– Effective at low levels
– Compatible with anionics

• Drawbacks
– Can build-up

• % Used if formula
– Up to 5%
– Usually 1% or less
 Silicones
• Compounds containing silicone
Varieties of Silicones

Dimethicone Copolyol
 Silicones
• Benefits
– Increased shine
– Increased lubricity
– Works on undamaged hair
– Synergistic with cationics

• Drawbacks
– Build-up
– Weigh down hair

• % Used if formula
– Up to 2%
 Humectants
• Ingredients that attract water
• Usually water soluble
– Glycerin
– Propylene Glycol
– Sorbitol
– Types of proteins
• Use level
– 0.5% - 15.0%
How Occlusives Work
 Occlusive Agents
• Water-insoluble materials
• Examples
– Petrolatum
– Mineral Oil
– Dimethicone
• Use Level
– 5% to 70%
Emollients
 Emollients
• Light coating on skin
• Used to improve feel
• Examples
– Coconut oils
– Almond oil
– Esters
– Silicones
• Use level
– 5% - 25%
Functional Ingredients
Cosmetic Colorants
 Cosmetic Colorants

 Pigments / Dyes
 Provide color & shine
 Color formulations
 Two main types
 Mineral pigments
 Organic pigments
 Limited by regulations
 Strictly controlled by FDA
 Functional Raw Materials
Active Ingredients

• Proven to have an effect on cells or

fight disease

• Classified as OTC Drugs

– FDA Monograph
– In US & elsewhere
 OTC “cosmetic”
Active Ingredients
• Sunscreens
• Anti-acne
• Anti-perspirants
• Anti-dandruff
• Anti-cavity
• Anti-fungal
• Anti-microbial
• Hair growth
• Skin bleaching
• Wart Remover
 Functional Raw Materials
Film Forming Polymers
• Polymers – Long chain molecules made up of
repeating unit molecules (monomers)

• Wide range of uses

– Thickeners
– Conditioning / moisturizers
– Hair colors
– Styling polymers
 Functional Raw Materials
Reactive Ingredients
• Ingredients that chemically react to produce
an effect

• Hair colorants
• Relaxers
• Perms
• Sunless Tanners
• Depilatories
 Cosmetic Chemistry Quiz
Which ingredient is NOT something you
could possibly find in a cosmetic?

•Whale Vomit

•Sheep placenta

•Cow bone marrow

•Bull Semen
Break
 Aesthetic Raw Materials
• Solvents
• Emulsifiers
• Adjusters
• Preservatives
• Thickeners
• Fragrance
• Fillers
• Delivery Systems
 Solvents
• Ingredients that dilute functional ingredients
• Aid in delivery
• Low cost
• Non-reactive / Compatible
• Most common
– Water
– Alcohol
– Mineral Oil
– Propylene Glycol
 Emulsifiers
• Ingredients that create oil & water mixtures
• Basis for all creams & lotions
• Emulsions consist of
– Internal phase
– External phase
– Emulsifier
• Very few natural emulsifiers
 Standard Emulsifiers to Avoid for
Natural products
Type INCI Name Reason to exclude
Anionic Triethanolamine Stearate TEA (stearic acid may
(Also known as TEA Stearate) be animal derived)
Potassium Cetyl Phosphate Phosphate content
Nonionic PEG-100 Stearate Ethoxylated
Ceteareth-20 Ethoxylated
Steareth-2 Ethoxylated
Bis-PEG/PPG-14/14 Silicone & PEG based
Dimethicone
Polyacrylate-13 Synthetic polymer
Cationic Palmitamidopropyl- Quaternary
trimonium chloride
 Natural Emulsifiers – What To Use
• Esters - glyceryl caprylate
• Lecithin
• Challenging to formulate with
• Beeswax/Borate combination
• Heavy/greasy/unstable
• Soaps
• Saponins
• Polysorbates
 Formulation Aids
• Ingredients that adjust formulation properties
– pH
– Viscosity
– Solubilizers
• Acids, bases or salts
• Chelating agents
• Nonionic surfactants
 Preservatives

• Compounds that prevent contamination

– Bacteria
– Molds
– Psuedomonas

• Sources of contamination
– Equipment
– Ingredients
– Post-manufacture
– Consumer
 Cosmetic Preservatives
• Parabens
– Propylparaben
– Ethylparaben
– Methylparaben
• Formaldehyde donors
• Phenol derivatives
– Phenoxyethanol
• Quats
• Alcohol
• Organic compounds
– Methylchloroisothiazolinone
 “Natural” Preservatives

• Benzoic acid • Perillic acid

• Boraxitrus seed extracts • Salicylic acid
• Salt
• Copper salts
• Silver Chloride
• Fragrance oils • Sodium Gluconate
• Glycerin • Sorbic acid
• Hinokitiol • Sugar
• Honey • Usnic acid
• Wasabi extract
• Japanese Honeysuckle
extracts • Zinc Salts
• Melaleucol (Tea Tree) oil
 Aesthetic Raw Materials
• Thickeners – Ingredients that increase the
thickness of a formula
 Lipid Thickeners

• Composed of lipophilic materials

• Solid at room temperature
• Liquid when heated, solid when cooled

• Examples
– Carnauba wax
– Cetyl Alcohol
– Stearyl Alcohol
 Thickening Technology
• Cellulose & Carbohydrate thickeners

• Examples
– Carrageenan
– Xanthan gum
– Hydroxyethyl Cellulose
 Cellulose & Carbohydrate thickeners
• How they work
– Absorb water
– Internal hydrogen bonding

• Benefits / drawbacks
– High viscosity
– Good spreadability
– Sticky, stringy, cloudy

• Formula use %
– Low levels to prevent stickiness Xanthan Gum
– 1% or less
 Mineral Thickeners

• Mined ingredients that hold water

• Different feeling formula
• Can be used to thicken non-aqueous formulas

• Examples
– Silica
– Bentonite
– Magnesium Aluminum Silicate
 Acrylic Thickeners
• Acrylate thickeners
• Examples
– Carbomer
 Carbomer Thickeners

• How they work

• Polymer freely
moves in solution
(Acidic)
• pH is neutralized
– TEA or AMP
• Cross-linking bonds
 Fragrances
• Used to improve the odor of
formula / surface
• Blend of aromatic compounds.
– Essential oils / naturals
– Synthetics
• Creation requires art and
science
 Fillers
 Used to extend colors
 Choice based on cost & formula needs

 Examples
 Talc
 Mica
 Kaolin
 Bismuth oxychloride
 Calcium Carbonate
 Appearance Modifiers
• Pearling Agents – Opacify formula
• Suspended beads
• Texture modifiers
 Delivery Systems
• Ingredients used to better deliver functional
ingredients to skin & hair
• Cyclodextrins
• Matrix Polymers
• Liposomes
 Marketing Ingredients

• Added to support a marketing story

• Generally have some functionality
• High concentrations are too expensive
• Give a measure of differentiation
• Recognizable by consumers
– Positive reception
– Seem like good ingredients
 Marketing Raw Materials
• Vitamins
• Botanical Extracts
• Proteins
• Anti-Aging

• Used at low levels

• Minimal impact on
performance
 Natural Raw Materials
• Depends on Standards
• Don’t expect them to work
as well
• They will cost more
• Consumers want products
that work
Cosmetic Formulations
Cosmetic Formulation Types

• Solutions
• Emulsions
• Gels
• Sticks
• Powders
• Aerosols
 Solutions
Simplest formulation
Mixture of compounds

Examples
• Shampoo
• Skin oils
• Aftershave
 Solution Technology
• Ingredients in Shampoo formulation

• Functional Ingredients – 10-20%

– Cleansing Surfactants
– Conditioners
• Aesthetic ingredients – 80 – 90%
• Marketing ingredients – 0 – 5%
Example Solution - Shampoo formula
Shampoo

Water 75.60
Sodium Lauryl Sulfate 12.00
Sodium Laureth Sulfate 5.00
Cocamide DEA 3.00
Hydroxyethylcellulose 0.50
Hydrolyzed Keratin 0.50
Hydroxpropyl Guar Trimonium Chloride 0.20
Sodium Chloride 2.00
DMDM Hydantoin 0.20
Fragrance 1.00
Color qs
Natural - Shampoo
 Natural Body Wash
Ingredient Function Wt, %
Sodium Coco Sulfate Primary Surfactant 10.4
Coco Glucoside Secondary surfactant 15.4
Lauryl Glucoside Secondary surfactant 4
Xanthan Gum Thickener 1.6
Apple Juice Marketing ingredient 3
Sodium Benzoate Preservative 0.5
Citric Acid pH adjustment QS
Sodium Chloride Viscosity adjustment QS
Fragrance Fragrance QS
Water Carrier QS to 100

* Meets NaTrue Standard

 Emulsions
Mix of Oil & Water
Held together with
Emulsifier

Examples
• Lotions
• Conditioners
• Moisturizers
 Emulsions Components
• Internal phase
– Discontinuous
phase
• External phase
– Continuous
phase
• Emulsifier
 Emulsions Types
• Configuration
– Oil in Water (O/W)
– Water in Oil (W/O)
– Multiple emulsions (W/O/W)
Multiple Emulsions
 Emulsions Particles
• Classified by particle size
– Solutions <5 nm
– Micelles 5 – 10 nm
– Microemulsions 10 – 100 nm
• Clear
• Stable
– Macroemulsions >100nm
• Opaque
• Unstable
 Emulsions Particles
• Particle size is determined by
– Amount of agitation
– Temperature
– Component concentration
– Type of emulsifier and oil

• Generally, smaller particles are more stable

 General Moisturizing Cream
• Functional ingredients – 10 – 50%
• Aesthetic ingredients – 50 – 90%
• Marketing ingredients – 0 – 5%

• Oil in Water emulsion – O/W

• Water in oil emulsion – W/O
 Creating a formula
• Pick oil phase
• Pick appropriate emulsifier
– HLB method for choosing
• Decide on formula structure
– O/W – less greasy but less effective
– W/O – more effective, more expensive
Moisturizing Cream Formula
 Natural Body Lotion
Ingredient Function %
Water Diluent QS to 100
Glycerin Humectant 3
Sodium Stearoyl Glutamate Emulsifier 0.5
Dehydroacetic Acid (and) Benzyl Preservative 0.8
Alcohol
Xanthan Gum Thickener 1.0
Cetearyl Alcohol Emulsifier 2
Polyglyceryl-2 Dipolyhydroxystearate Secondary emulsifier 2
Glyceryl Stearate Secondary emulsifier 1
Dicaprylyl Ether Emollient 5
Oleyl Erucate Emollient 2
Olive Oil (Organic certified) Emollient 5
 Gel formula

• Thickened solution
or emulsion
 Types of Gel
• Styling Gels
• Normal Hold
• Extra Hold
• Shaving gel
• Hand gels
 Gel formulas
• Ingredients in gel formulas

• Functional Ingredients – 10-30%

– Styling Polymers
– Conditioning Ingredients
• Aesthetic ingredients – 70 – 90%
• Marketing ingredients – 0 – 5%
Example Styling Gel
Natural Styling Gel
 Cosmetic
Chemistry Quiz
Which one is the FAKE beauty gadget?

• Ceramic unipolar magnet that controls acne

• Wand that shoots oxygen into your skin to smooth, tone &
stimulate

• Hand held laser that makes your hair grow

• Electronic headband that relaxes muscles to remove wrinkles

Creating Cosmetic Formulas
 Sources for Starting Formulas
1. Patents
2. Books
1. Harry’s Cosmeticology
3. Chemical suppliers
1. Prospector.com
4. Trade journals
1. Happi.com
5. Colleagues
6. Ingredient lists – LOIs

http://bit.ly/NluE3l
 Getting information from patents
• Google patents
• Sections of patent
• Finding formulas
• Finding testing ideas
• Working around patents
 Relevant Parts of a patent
• Title / Abstract
• Background – good historical info here
• Summary / Description – Good background
• Claims – Most important
– Gives details %, ingredients, etc.
• Examples – The formulas, tests
 Using Ingredient Lists
as Starting Formulas

• Look at the LOI of competitive products

• Sources of LOI and claims information
– http://drugstore.com
– http://ulta.com
• Use the 1% line exercise to guess at formula
 How to read cosmetic ingredient lists
• Ingredient Labeling
• Legal requirement
• Use standardized names (INCI)
• Proper order
– In order above 1%
– Below 1% is mostly arbitrary (colors at the end)
 Ingredient listing tips
• Fragrance is rarely over 1%
• Adjustment ingredients are low
• Natural sounding ingredients are usually
below 1%
• Ingredients over 1% are most important in the
formula
 Ingredient list example
• Identify formula type
• Guess the 1% line
• Identify key ingredients, guess at % levels
• Ignore below 1% ingredients in first formula
efforts
 Ingredient list example
Skin lotion

Water, Safflower Seed Oil, Glyceryl Stearate, Glycerin,

Jojoba Seed Oil, Borage Seed Oil, Cetyl Alcohol, Vitamin E
Acetate, Dimethicone, Aloe Vera Gel, Shea Butter, Sodium
Ascorbyl Phosphate (Vitamin C), Phenoxyethanol, L
Ergothioneine, Ethylhexyl Glycerin
 Possible Starting Formula
• Water 86.0
• Safflower Seed Oil 5.0
• Glyceryl Stearate 3.0
• Glycerin 3.0
• Jojoba Seed Oil 1.0
• Borage Seed Oil 1.0
• Cetyl Alcohol 1.0
• Preservative qs
 Where is the 1% line?

• Hair Shampoo formula

– Water, Ammonium Lauryl Sulfate, Ammonium Laureth Sulfate,

Sodium Chloride, Cocoamide MEA, Glycol Distearate,
Dimethicone, Ammonium Xylenesulfonate, Vanilla Planifolia
Fruit Extract, Cocos Nucifera Milk Coconut, Fragrance, Cetyl
Alcohol, Polyquaternium-10, Sodium Citrate, Sodium
Benzoate, Disodium EDTA, PEG-7M, Citric Acid, Propylene
Glycol, Methylchloroisothiazolinone, Methylisothiazolinone,
Blue No. 1
 Possible Starting Formula
• Water 77.9
• Ammonium Lauryl Sulfate 8.0
• Ammonium Laureth Sulfate 7.0
• Sodium Chloride 1.8
• Cocoamide MEA 1.8
• Glycol Distearate 1.5
• Dimethicone 1.0
• Ammonium Xylenesulfonate 1.0
• Preservative qs
 Where
Where isisthe
the1%
1%line?
line?

• Hair Conditioner formula

– Water (aqua), Cetearyl Alcohol, Glycerin,

Cyclomethicone, Behentrimonium Methosulfate,
Behentrimonium Chloride, Cetyl Alcohol, Wheat Germ
Oil (triticum vulgare), Hydrolyzed Silk, Panthenol,
Tocopheryl Acetate, Jojoba Oil (buxus chinensis), Aloe
Barbadensis Leaf Juice, Fragrance, Propylene Glycol,
Methylparaben, Propylparaben, Diazolidinyl Urea,
Citric Acid, Red 33, Blue 1
 Possible Starting Formula
• Water 87.0
• Cetearyl Alcohol 5.0
• Glycerin 3.0
• Cyclomethicone 2.0
• Behentrimonium Methosulfate 1.0
• Behentrimonium Chloride 1.0
• Cetyl Alcohol 1.0
 Use Knock-out Experiments
• Objective: To figure out the function & effect
of ingredients in a formulation

• Procedure:
– Create a series of formulas substituting main
solvent for one ingredient
– Evaluate effect on specification tests, stability,
performance
Knock-out Example
 Knock-out Experiment shortcuts
• Ingredients you don’t have to knockout
• Dyes
• Feature ingredients
• Preservatives
Knock-out Experiment Example 2
Knock-out Experiment Example 2

15 batches total
Knock-out Experiment Simplified

10 batches total
 Knockout experiment Case Study
• Test a shampoo formula
• See what you can learn from the study
• Things to test
• Specification
– pH
– Viscosity
• Performance
– Foam
– Conditioning
Knockout experiment Case Study
Knockout Results
 Using Knockout Results
• pH is off…
– Too high add SLS or SLMS
– Too low add Cocamide DEA
• Viscosity is off…
– Too high add fragrance
– Too low can try SLS, SLMS, Salt, Cocamide DEA
• Foam is off…
– Too low can try SLS, SLMS, Cocamide DEA
 Knockout Limitations & DOE
• Limitations
– Too many batches to make
– Miss synergistic effects
– Results in unrealistic results
• DOE – Design of Experiment
– More thorough study
– Understand synergies between ingredients
– Not as useful for cosmetics
 Morning Session Summary
• Introduction to cosmetics
• Review of cosmetic ingredients
• Review of cosmetic formulation types
• Beginning steps in creating new formulas

• This afternoon will focus on creating more

optimal formulations
Questions?
Cosmetics
Purposes of
Cosmetics

• Improve your…

• Appearence
• Skin Feel
• Odor
 What are
Cosmetics?
 Articles intended to be rubbed, poured,
sprinkled or sprayed on or introduced into
or otherwise applied to the human body or
any part thereof for cleansing, beautifying,
or promoting the attractiveness , or
altering the appearance, and articles
intended for use as a component of any
such articles; except that such term shall
not include soap
-FDA CFR
 Skin
Products
Perfume &
Fragrances
Oral care
Products
 Cosmetics aren’t drugs

 Drugs = Treat disease

 Cosmetics = Improve appearance

Can't interfere with metabolism

 International Regulatory bodies

• European Commission
• Health Canada
• Ministry of Health
(Japan)
• Department of Health
& Ageing (Australia)
• CFDA - China
 General Problems
addressed by cosmetics

• Appearance
• Feel
• Smell
 Top 10 skin problems
1. Dry itchy skin
2. Wrinkles
3. Acne
4. Sagging Skin
5. Age spots
6. Skin lightening
7. Tattoo removal
8. Eczema / Dermatitis
9. Psoriasis
10. Cellulite
 Strategies for Improving Appearance
• Remove dirt from surface
– Cleansing products
• Change the surface
– Exfoliating products
• Leave color behind
– Make-up
• Change color of surface
– Self tanning products
 Strategies for Improving Feel

• Materials that make

skin & hair feel better
– Oils and emollients
• Water attracting
compounds
– Moisturizers
• Conditioning products
– Film forming material
 Strategies for Improving Odor
• Clean odor materials
off body
• Cover odors with
fragrance
• Kill microbes that
cause odor
Greenwashing
Natural has no legal definition
 Major US Natural Standards Groups
• USDA
• National Sanitation Foundation
• National Product Association
• OASIS
International Natural Standards
 COSMOS Standards
• Promote organic agriculture
• Use natural resources
• Clean processing and manufacture
• “Precautionary Principle”
• Integrate Green Chemistry principles
Principles of Green Chemistry
 Common Standards
• Water is natural
• Mineral ingredients are natural
• Physically processed agro-
materials are natural
• Some chemical processing of
agro materials
• Some synthetics allowed
 Some Prohibited Ingredients
• Parabens
• Formaldehyde Donors
• Petrolatum & petroleum derived
• Propylene glycols
• Sodium Lauryl Sulfate
• Ethanolamines
• Synthetic Silicones
• Synthetic Fragrances
• Synthetic Polymers
• EDTA
 Some Chemistry Allowed
• Distillation
• Esterification & Etherification
• Expression
• Extraction
• Fat Splitting
• Fermentation
• Hydrogenation
• Protein Hydrolysis
• Saponification
• Sulfation – (no SLS)
 Cosmetic Science Quiz

• Which ingredient is not in the top 10 most

vilified cosmetic ingredients?

– 1. Methyl Paraben

– 2. Mineral Oil

– 3. Titanium Dioxide

– 4. Sodium Laureth Sulfate

Cosmetic Raw Materials
Raw Material
Cladistics
 Cosmetic Raw Materials
• Functional – Provide the product benefit

• Aesthetic – Improve the aesthetics of the

functional ingredients

• Claims – Included to help sell the product

 Functional Raw Materials
• Ingredients that make cosmetics work

• Cleansers
• Conditioners
• Film formers
• Drug actives
• Reactants
• Colorants
• Fragrances
 Surfactants
Hydrophillic Lipophillic

Compatible Compatible
With Water With Oil
Types of Surfactants
 Anionic Surfactants
• These are the primary cleansing surfactants
• Alkyl Sulfates
– Examples – SLS and ALS
• Alkyl Ether Sulfates - Ethoxylated
– Example – SLES and ALES
 Anionic Surfactants
• Other types
– Sulfosuccinates – Acyl Isethionates
– Alkylbenzene – Acyl Polypeptide Condensates
Sulfonates – Monoglyceride Sulfates
– Acyl Methyltaurates – Fatty Glyceryl Ether
– Acyl Sarcosinates Sulfonates

Sodium Lauryl Sarcosinate

 Anionics
• Why use them?
– Excellent detergency
– Relatively inexpensive
– Good foaming
– Highly stable

• Drawbacks
– Can be irritating
– Drying to hair
 Sulfates and Naturals
• Unacceptable for cleansing surfactants for
natural products
– Sulfosuccinates
– Sulfonates
– Alkyl sulfates
 What is used instead
• Sultaines
• Mild secondary surfactant, more
stable and better viscosity builder
• e.g. Cocamidopropyl
Hydroxysultaine

• Acyl Sarcosinates
• High foaming secondary
surfactant
• e.g. Sodium Lauryl Sarcosinate
 Natural Surfactant Options
• Alkyl Polyglucoside
• Natural primary surfactant derived from
coconut and sugar
• Does not build viscosity as well
• Does not foam as well
• Higher cost
• e.g. Lauryl Glucoside
 Natural Cleansing Surfactants

• Saponins – Cleansing Surfactants

• Source: plants – marine derived
– Quillaja saponaria Molina
• Difficult to purify
• Too expensive
• Not as effective
• ~40% less foam
• Highly colored
 Amphoteric Surfactants
• Can have a positive or negative charge
depending on the pH of the solution
• Zwitterionic
• Types
– Cocamidopropyl Betaine Positive Negative
– Sodium Lauraminopropionate
 Non Ionic Surfactants
• Surfactant molecules with no charge

• Types
– Fatty Alcohol
– Fatty amines
• Lauramide DEA
– Amine Oxides
• Lauramine Oxide
• Polysorbates
 Non Ionic Surfactants
• Why use them?
– Foam enhancer
– Reduce irritation
– Conditioning effect
– Solubilize fragrances
– Emulsifiers

– Gentle Cleansers
• PEG-80 Sorbitan Laurate

• Drawbacks
– More expensive
– Do not foam well on their own
 Functional Raw Materials
Conditioners & Moisturizers
 Moisturizing Ingredients

• Quats
• Cationic Polymers
• Silicones
• Occlusives
• Humectants
• Emollients
 Quats
• How do they work?
– Electrostatic Attraction
– More damage = more substantivity
– Longer chain length = more conditioning
 Cationic Polymers
• Common Examples
– Polyquaternium 4
– Polyquaternium 7
– Polyquaternium 10
– Guar Hydroxypropyltrimonium Chloride
Positive

Negative
Cationic Polymers
 Cationic Polymers
• Benefits
– Effective at low levels
– Compatible with anionics

• Drawbacks
– Can build-up

• % Used if formula
– Up to 5%
– Usually 1% or less
 Silicones
• Benefits
– Increased shine
– Increased lubricity
– Works on undamaged hair
– Synergistic with cationics

• Drawbacks
– Build-up
– Weigh down hair

• % Used if formula
– Up to 2%
 Humectants
• Ingredients that attract water
• Usually water soluble
– Glycerin
– Propylene Glycol
– Sorbitol
– Types of proteins
• Use level
– 0.5% - 15.0%
How Occlusives Work
 Occlusive Agents
• Water-insoluble materials
• Examples
– Petrolatum
– Mineral Oil
– Dimethicone
• Use Level
– 5% to 70%
Emollients
 Emollients
• Light coating on skin
• Used to improve feel
• Examples
– Coconut oils
– Almond oil
– Esters
– Silicones
• Use level
– 5% - 25%
 Functional Raw Materials
Active Ingredients

• Proven to have an effect on cells or

fight disease

• Classified as OTC Drugs

– FDA Monograph
– In US & elsewhere
 OTC “cosmetic”
Active Ingredients
• Sunscreens
• Anti-acne
• Anti-perspirants
• Anti-dandruff
• Anti-cavity
• Anti-fungal
• Anti-microbial
• Hair growth
• Skin bleaching
• Wart Remover
 Functional Raw Materials
Film Forming Polymers
• Polymers – Long chain molecules made up of
repeating unit molecules (monomers)

• Wide range of uses

– Thickeners
– Conditioning / moisturizers
– Hair colors
– Styling polymers
 Functional Raw Materials
Reactive Ingredients
• Ingredients that chemically react to produce
an effect

• Hair colorants
• Relaxers
• Perms
• Sunless Tanners
• Depilatories
 Cosmetic Chemistry Quiz
Which ingredient is NOT something you
could possibly find in a cosmetic?

•Whale Vomit

•Sheep placenta

•Cow bone marrow

•Bull Semen
 Aesthetic Raw Materials
• Solvents
• Emulsifiers
• Adjusters
• Preservatives
• Thickeners
• Fragrance
• Fillers
• Delivery Systems
 Solvents
• Ingredients that dilute functional ingredients
• Aid in delivery
• Low cost
• Non-reactive / Compatible
• Most common
– Water
– Alcohol
– Mineral Oil
– Propylene Glycol
 Emulsifiers
• Ingredients that create oil & water mixtures
• Basis for all creams & lotions
• Emulsions consist of
– Internal phase
– External phase
– Emulsifier
• Very few natural emulsifiers
 Formulation Aids
• Ingredients that adjust formulation properties
– pH
– Viscosity
– Solubilizers
• Acids, bases or salts
• Chelating agents
• Nonionic surfactants
 Cosmetic Preservatives
• Parabens
– Propylparaben
– Ethylparaben
– Methylparaben
• Formaldehyde donors
• Phenol derivatives
– Phenoxyethanol
• Quats
• Alcohol
• Organic compounds
– Methylchloroisothiazolinone
 Aesthetic Raw Materials
• Thickeners – Ingredients that increase the
thickness of a formula
 Lipid Thickeners

• Composed of lipophilic materials

• Solid at room temperature
• Liquid when heated, solid when cooled

• Examples
– Carnauba wax
– Cetyl Alcohol
– Stearyl Alcohol
 Appearance Modifiers
• Pearling Agents – Opacify formula
• Suspended beads
• Texture modifiers
 Delivery Systems
• Ingredients used to better deliver functional
ingredients to skin & hair
• Cyclodextrins
• Matrix Polymers
• Liposomes
 Marketing Raw Materials
• Vitamins
• Botanical Extracts
• Proteins
• Anti-Aging

• Used at low levels

• Minimal impact on
performance
 Natural Raw Materials
• Depends on Standards
• Don’t expect them to work
as well
• They will cost more
• Consumers want products
that work
 Solutions
Simplest formulation
Mixture of compounds

Examples
• Shampoo
• Skin oils
• Aftershave
Natural - Shampoo
 Emulsions
Mix of Oil & Water
Held together with
Emulsifier

Examples
• Lotions
• Conditioners
• Moisturizers
 Emulsions Components
• Internal phase
– Discontinuous
phase
• External phase
– Continuous
phase
• Emulsifier
 Emulsions Types
• Configuration
– Oil in Water (O/W)
– Water in Oil (W/O)
– Multiple emulsions (W/O/W)
Multiple Emulsions
 Gel formula

• Thickened solution
or emulsion
 Types of Gel
• Styling Gels
• Normal Hold
• Extra Hold
• Shaving gel
• Hand gels
Natural Styling Gel
 Cosmetic
Chemistry Quiz
Which one is the FAKE beauty gadget?

• Ceramic unipolar magnet that controls acne

• Wand that shoots oxygen into your skin to smooth, tone &
stimulate

• Hand held laser that makes your hair grow

• Electronic headband that relaxes muscles to remove wrinkles

Creating Cosmetic Formulas
 Sources for Starting Formulas
1. Patents
2. Books
1. Harry’s Cosmeticology
3. Chemical suppliers
1. Prospector.com
4. Trade journals
1. Happi.com
5. Colleagues
6. Ingredient lists – LOIs

http://bit.ly/NluE3l
 Getting information from patents
• Google patents
• Sections of patent
• Finding formulas
• Finding testing ideas
• Working around patents
Knockout Results