Formulation Classes and Raw Materials2
Formulation Classes and Raw Materials2
Date Module Focus Speaker Company 11-Sep 18-Sep 25-Sep 2-Oct 9-Oct 16-Oct 23-Oct 30-Oct Introduction to Cosmetics - Trends, Size of Industry, Products, Chemical Classes, Raw Materials Used, Formulation Types Scott Wenzel Tom Schoenberg Perry Romanowski Perry Romanowski Craig Bonda TBD TBD Anna Gripp Kimberly-Clark
6-Nov
Gene Frank
Raani Corporation
13-Nov
Barb Dvoracek
Kimberly-Clark
Jan 2004 Serve a 2nd term as Chair of the Intermountain Chapter of SCC
Sept 2006 Chair-Elect of Midwest Chapter of SCC Sept 2007 Chair of Midwest Chapter of SCC
Cosmetic Overview
Overview of Presentation
How large is the cosmetic industry? What are the trends?
Cosmetic Industry
Size and Growth
Marketing Intensive
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Company Activity: -> Consolidation -> Education -> Mega-Branding -> Cross-Industry Innovation
15 Copyright and database Euromonitor International 2007
Body Sprays
Analytical Chemist
Quality Control Specialist Microbiologist and Life Scientists Perfumers Technical Sales
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Overview
What is a cosmetic and drug?
What is formulating?
Classes/functions of raw materials
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What is a Cosmetic
The Food, Drug, and Cosmetic Act (FD&C Act) defines cosmetics by their intended use, as "articles intended to be rubbed, poured, sprinkled, or sprayed on, introduced into, or otherwise applied to the human body...for cleansing, beautifying, promoting attractiveness, or altering the appearance" [FD&C Act, sec. 201(i)].
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The FD&C Act defines drugs by their intended use, as "(A) articles intended for use in the diagnosis, cure, mitigation, treatment, or prevention of disease..and (B) articles (other than food) intended to affect the structure or any function of the body of man or other animals"
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Formulation Defined
The act, process, or result of formulating or reducing to a formula. Webster's Revised Unabridged Dictionary (1913)
A.K.A Advanced Baking or Bucket Chemistry
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Formulation Defined
Formulating is a: ComplexIterative.Combination of Art and Science
Performance
Aesthetics
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Surfactants
Surfactants Cleansing agents
Used for skin/hair cleansing purposes. In this function, surfactants wet body surfaces, emulsify or solubilize oils, and suspend soil.
It is characteristic, and expected by most consumers that these should contribute foam/lather to cleansing products. Examples: Sodium Lauryl Sulfate (SLS) Ammonium Laureth Sulfate (ALES)
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Surfactants
What is a surfactant? A surface active agent that reduces the surface or interfacial tension by its tendency to adsorb at the surface or interface. How a surfactant functions in a system depends on its HLB (hydrophobic-lipophyllic balance. Surfactants contain a polar and a non-polar region within the same molecule and generally can be characterized via the Head & Tail approach. The elongated hydrophobic end is the tail, while the hydrophilic end is the head
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Micelle Formation
(1) At very low concentrations surfactants aggregate at the surface (2) As the concentration is increased the surfactants aggregate in the solution and form micelles, reducing surface tension
The concentration of surfactant at which micelles first appear is called the critical micelle concentration (CMC)
Surface Tension (N/m) Concentration
Increasing surfactant concentration does not result in in a further decrease of surface tension.
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Surfactants
Surfactants Emulsifying Agents Are employed in cosmetics to prepare emulsions. Their efficacy depends on their ability to: Reduce surface tension Form complex films on the surface of emulsified droplets Create a repulsive barrier on emulsified droplets to prevent their coalescence. Examples: Ceteareth-20 PPG-2 Isoceteth-20 Acetate Glyceryl Stearate SE
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Non-ionic
Ionic
Anionic
GMS-SE TEA-Stearate Sodium Cetearyl Sulfate
Cationic
Amphotheric
Non-Ionic Emulsifiers
Fatty-alcohol ethoxylates dominate but also includes PEG, Glyceryl, Sucrose and Polyglyceryl esters, ether and, in many instances, silicone based compounds Typical alkyl chain for alcohol ethoxylates distributed between C12-18. Broad compatibility Inexpensive Generally organized by hydrophilic/hydrophobic character (HLB) Best stability & effectiveness is achieved through combinations of emulsifiers E.G. Arlacel 165 is a commercial blend of 50% Glyceryl Stearate (HLB 12) and 50% PEG-100 Stearate (HLB 18.8) allow for a broad range or materials to be emulsified. Achieves: smallest droplet size, highest stability, lowest amount of surfactant
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Anionic
Cetyl Phosphate
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Cationic
Consumer Products Using Cationic Emulsifiers
Distearyldimonium chloride
Dry, powdery, smooth skin feel is able to mask high lipophilic content
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Love?
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Surfactants - Emulsifiers
Surfactant = Surface Active Agent
A molecule with a polar head group and a non-polar tail Polar Non-polar
For emulsions, these are usually nonionic surfactants although there are others
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Surfactants - Emulsifiers
Surfactants can have more non-polar character than polar character and vice-versa. These represent different HLB values.
Less polar (low HLB) More Polar (High HLB) Specific oils need specific surfactant polar/non-polar character to be effectively emulsified.
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The HLB System A Time Saving Guide To Surfactant Selection. Uniqema. Presentation to the Midwest Chapter of the Society of Cosmetic Chemists.48 09 March 2004.
Surfactants - Emulsifiers
When added to oil and water, a surfactant will arrange itself such that its non-polar tail is within the oil and its polar heads are exposed to the water. Spherical arrangement of surfactant is known as a micelle. Polar heads Oil Droplet
Non-polar tails
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Emulsion!
An emulsion is a suspension of two immiscible liquids in which one phase is dispersed as small globules within the other. Continuous phase and dispersed phase
The surfactant maintains the small droplet size of the oil, keeps the droplets from aggregating (steric hinderance) and the surfactant/oil complex is soluble in the water.
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Skin Moisturization
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Body Washes
Hand Sanitizers
Hand Soaps
Lip Balms
Sunscreens
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Too Wet
Skin maceration Loss of barrier function Reduced rate of barrier repair Corneocyte swelling Wrinkling
Just Right
Too Dry
Skin flaking Loss of skin barrier Loss of skin elasticity Skin cracks/fissures Painful and/or pruritic skin Skin roughness
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Enhancing barrier function This is generally done with skin conditioning agents
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H2O
Vs.
Normal Skin w/ Normal Barrier Dry Skin w/ Damaged Barrier
Inflammation
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H2O
Apply Lipids
H2O
Irritant
H2O
Formulation Considerations
Most are water insoluble, so must be delivered either in the oil phase of an emulsion system or in an anhydrous system. Too much of a barrier material can result in a formulation that feels greasy, waxy, or heavy. Fatty materials can go rancid over time; preservatives should be used to delay or prevent this.
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Includes primarily hygroscopic agents intended to increase the water content (conductance) of the top layers of skin.
Examples: Glycerin, Propylene Glycol
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Humectants in Formulations
Stratum corneum (dried and cracked)
Relief !!!
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Alpha-hydroxy acids
Urea Pyrrolidone Carboxylic Acid (PCA)
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Formulation Considerations
Most humectants are water-soluble, and can easily be incorporated in water-based formulations. Use in anhydrous formulations is limited.
Many formulations (especially washes, soaps, or hand sanitizers) that state with moisturizers on the label contain glycerin or another humectant.
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Shai, A. et al. Eds. Handbook of Cosmetic Skin Care (2001)
Moisturizing Formulations
Active Ingredients: Dimethicone
Inactive Ingredients: Water, Glycerin, Distearyldimonium Chloride, Petrolatum, Isopropyl Palmitate, Cetyl Alcohol, Oat Flour (Avena Sativa), Benzyl Alcohol, Sodium Chloride
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Additional Ingredients
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Film Formers
Materials which, upon drying, produce a continuous film on skin, hair, or nails Uniform films can enhance the efficacy of an active such as a sunscreen, skin protectant or moisturizer. Can be used to improve the wash off or removal of an active ingredient from the skin surface. Examples: PVP PVA Ethylene Vinyl Acetate Copolymer
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Clays
Magnesium Aluminum Silicate (e.g. VEEGUM) Smectite clay platelets
Hydrates in water
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Clay Platelets
Negatively charged platelet faces and positively charged edges
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Forms Structure
When hydrated, clay assembles a 3D structure
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Preservatives
Ingredients which prevent or retard microbial growth and thus protect products from spoilage. Use is required to prevent rancidity, appearance/odor changes to the product caused by microorganisms Protects activity/functionality of the product Protects from inadvertent contamination by consumer during use or production. The functionality of many classes is determined by the pH, conditions of manufacturing and order of addition. To prevent microbial growth in a product Examples: DMDM Hydantoin Parabens Phenoxyethanol Quaterniary Amines
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Types of preservation
Radiation Heat or cold
Packaging
Chemical and Natural Preservatives
Water activity reducers
Antioxidants
Chelators pH adjusters
Antimicrobials
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Microbial Paradise
Cosmetics contain food numerous food sources for microbes: water, proteins, trace metals, carbon, amino acids. pH of products can enhance microbial growth Most bacteria flourish in pHs between 6.5-7.5, but actual range of growth is 4.5-9.0 Yeasts abound around 4.0-6.5, but can be seen as low as 1.5 and up to 9.6 Molds enjoy a pH between 4.5 and 6.8, but can found between 1.2 (A. niger) and 11. High water activity is preferred Most bacteria need activity above 0.90, S. aureus can go to 0.84 Most yeasts prefer above 0.87, osmophilic yeasts can survive down to 0.60 Most molds are prefer water activity above 0.60
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Things to Consider
What are we concerned with as formulators? Gram negative bacteria Gram positive bacteria Yeast/mold Best preservative system is one that is broad a broad spectrum blend Paragon MEPB (McIntyre) is a blend of phenoxyethanol and parabens Optiphen Plus (ISP) is a blend of phenoxyethanol, caprylyl glycol, and sorbic acid Use preservative boosting techniques Chelating agents such as EDTA pH modification with acids/bases Water activity reducers (glycols,
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Chelating agents are used to help boost preservative efficacy in cosmetic formulations.
Examples: Tetrasodium EDTA Disodium EDTA Gluconic Acid
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Active Ingredients
Exact definition is dependent on desired claims and the associated regulatory status of the claim or ingredient used. Incorporated to alter the structure and function of the skin. Within cosmetics, over-the-counter products (rash creams, sunscreens) are regulated by the FDA under an appropriate monograph. Are all products which change the structure or function of skin regulated by the FDA: No!!! Is there consistent agreement as to what it means to change the function & structure of skin: No!!! Claim language is the fine line to distinguish cosmetic from a drug:
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Skin Protectants
OTC (over the counter) active drug ingredients that temporarily protect injured or exposed skin or mucous membrane surfaces from harmful stimuli, and may help provide relief to such surfaces. Examples:
Allantoin Dimethicone Petrolatum
Zinc Oxide
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Overview
Why are they used in formulations
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Enhance appeal
Enhance the five senses of the consumer (sight, smell, touch, taste, hearing)
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Natural Synthetic
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Aroma Compounds
Chemicals that are somewhat volatile so they can be transported to the upper part of the nose in a high enough concentration to be detected by the olfactory receptors Types of aroma compounds Fragrance A mixture of fragrant essential oils, aroma compounds, solvents, and fixatives Can be extremely complex and contain a top note (perceive immediately upon application), middle note (heart of the fragrance), and base note (perceived after dry down) Essential Oils Hydrophobic portion of a steam distillate Large interest due to the popularity of aromatherapy Examples are Lavender Oil, Peppermint Oil Hydrosols Aqueous phase of a steam distillate and often referred to as essential water, floral water, or herbal distillate Example are Rose Water, Orange Water
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Flavorant
A substance added to impart a pleasant taste to the final formulations
Product Examples
Toothpaste
Mouthwash
Lip Balm Adult novelty products
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Colorants
Materials which impart a visual color to a finished product Types of colorants Dyes Generally soluble and appear to be colored because they absorb some wavelengths of light preferentially Examples are FD&C Yellow No. 5 and D&C Orange No. 4 Pigments Generally insoluble and changes the color of light it reflects as a result of selective color absorption of wavelengths of light. Examples are FD&C Yellow No. 5 Aluminum Lake and D&C Orange No. 4 Aluminum lake Natural Examples are Walnut Extract and Beet Extract
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Marketing Ingredients
Materials which do not add to the end benefit of the product, but help to create the product story and reason to believe Generally these are added in very small amounts Examples: Extracts
Helianthus Annuus (Sunflower) Extract
Moisturizers
Jojoba oil, Aloe
Vitamins
Vitamin A, Vitamin E, Vitamin C
Antioxidants
Green Tea Extract, Vitamin C
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Cooling Agents
Due to volatile evaporation or from a neurosensory response
Examples would be ethanol, menthol, camphor
Tactile Agents
Examples would be powders or silicones to elicit a smooth, powdery finish on the skin
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Exfoliants
Materials added to formulations aimed at improving skin's appearance by removing dead skin cells from the surface of the skin.
Examples: Physical Synthetic
Polyethylene beads
Natural
Walnut shells Rice bran
Chemical
Alpha Hydroxy Acids (AHAs) such as Glycolic Acid, Lactic Acid, Citric Acid Beta Hydroxy Acids (BHAs) such as Salicylic Acid Polyhydroxy Acids (PHAs) such as Gluconolactone, Lactobionic Acid
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Industry Examples
Lavender Aromatherapy
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Formulation Systems
Solutions Oil Based Solutions/Anhydrous Water Based Surfactant Solutions Emulsions Suspensions Powders
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Solutions
Homogeneous mixture of two or more substances.
Examples:
Astringents (Hydro-alcoholic) Anti-septic/microbial Hand Gels
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Anhydrous Formulations
Systems which do not contain water Contains mostly hydrophobic/lipophilic ingredients.
Examples: Ointments, Lip balm/sticks, Vaseline
Advantages: Lipophilic material has direct contact with the skin, best film formation, and film is not water dispersible (water resistant/proof), ease of preservation.
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Shower Gels
Wet Wipe Solutions
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Bubble Bath
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Emulsions
An emulsion is a two phase system consisting of two completely immiscible liquids, one of which is dispersed in the other. Many types of Emulsions:
Oil-in-Water (O/W)
Water-in-Oil (W/O)
Multiple emulsions (O/W/O, W/O/W)
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Oil-in-Water Emulsions
Emulsions with a oil phase dispersed as fine droplets in aqueous external phase (O/W). Advantages: Typically have better Aesthetics, easier to formulate, greater choice of emulsifiers, & lower cost. Disadvantage: Typically does not provide substantivity, water proofing and film formation.
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Example Products
StriVectin-SD Wrinkle and Stretch Mark Cream ($135) Water (Aqua), C12-15 Benzoate, Sesamum Indicum Seed Oil (Sesame), Caprylic/CapricTriglyceride, Prunus Amygdalus Dulcis Oil (Sweet Almond), Cetearyl Olivate, Sorbitan Olivate, Striadril Complex (see product details for ingredients list), Glycerin, Glyceryl Stearate and PEG-100 Stearate, PPG 12/SMDI Copolymer, Stearic Acid, Theobroma Cacao Seed Butter (Cocoa), Butyrospermum Parkii (Shea Butter), Tocopheryl Acetate, Mangifera Indica (Mango), Mentha Piperita Oil (Peppermint), Methylparaben, Xanthan Gum, Triethanolamine, Butylparaben, Ethylparaben, Disodium EDTA, Propylparaben, Retinyl Palmitate, Tetrahexyldecyl Ascorbate Active Ingredients: 4% Octyl Salicylate, 2% Avobenzone, 1% Phenylbenzimidazole Sulfonic Acid, 1% Octocrylene Inactive Ingredients: Water, Glycerin, Dimethicone, Niacinamide (Vitamin B3), Isopropyl Isostearate, Polyacrylamide, Triethanolamine, Titanium Dioxide, C13-14 Isoparaffin, Cetearyl Glucoside, PTFE, Panthenol (Pro-Vitamin B5), Tocopheryl Acetate (Vitamin E), Stearyl Alcohol, Behenyl Alcohol, Cetyl Alcohol, Sucrose Polycottonseedate, Benzyl Alcohol, Dimethiconol, Carbomer, Methylparaben, Ethylparaben, Propylparaben, PEG 100 Stearate, Disodium EDTA, Laureth-7, Stearic Acid
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Example Products
Aveeno Baby Soothing Relief Moisture Cream, Fragrance Free
Water, Glycerin, Petrolatum, Mineral Oil, Cetyl Alcohol, Dimethicone, Avena Sativa (oat) Kernel Flour, Carbomer, Ceteareth 6, Ethylparaben, Sodium Citrate, Stearyl Alcohol, Propylparaben, Methylparaben, Sodium Hydroxide, Tetrasodium EDTA, Benzalkonium Chloride, Citric Acid, Butylparaben, Butylene Glycol, Hydrolyzed Milk Protein, PEG 25 Soy Sterol, Benzaldehyde, Hydrolyzed Oats, Hydroylzed Soy Protein, Isobutylparaben, Phenoxyethanol, Ethyl Alcohol
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Water-in-Oil Emulsion
The inverse is also possible with the oil phase being the continuous phase and the water phase being the internal phase
This is known as a water in oil emulsion (W/O)
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Active Ingredients: Zinc Oxide (10%) Inactive Ingredients: Water, Mineral Oil, Propylene Glycol Dioctanoate, Methyl Glucose Dioleate, Titanium Dioxide, PEG 45 Docecyl Glycol Copolymer, Glycerin, Ceresin, Ethyl Linoleate, Shea Butter, PEG 8, Panthenol, Potassium Sorbate, Fragrance, Magnesium Sulfate, Methylparaben, Caprylyl Glycol, Propylparaben, Sodium Polyacrylate
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Multiple Emulsions
Emulsions formed when a W/O emulsion is emulsified in water or when an O/W emulsion is emusified in oil. Advantages: Good aesthetics and can provide protection of actives within the emulsion. Disadvantage: Can be difficult to stabilize.
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Emulsifying emulsions
With the addition of certain surfactants, an oil in water emulsion can be emulsified within an external oil phase. This is known as an oil in water in oil (O/W/O) emulsion
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Emulsifying Emulsions
With the addition of certain surfactants, a water in oil emulsion can be emulsified within an external water phase This is known as a water in oil in water (W/O/W) emulsion
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Suspensions
A dispersion of solid particles in a liquid medium.
Examples:
Anti-acids
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Powders
Dry solids composed of numerous fine particles
Generally used to absorb moisture and or deliver active ingredients to the skin Examples:
Baby Powder Powder Make-ups Pressed Powders
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Conclusions
Cosmetic industry is extremely large and continues to grow yearly Multiple trends shape the industry and affect consumer buying intent
Multiple product types exist and changes occur due to consumer preference and technology shifts
Vast number of ingredients in the industry each with unique attributes and functionality Numerous formulations are used as delivery vehicles in the industry
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QUESTIONS?
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