Emollient W3 Nov 21-09-hanout - Mae Fah Luang University

MFU 1

Raw Materials For Skin Care ProductsRaw Materials For Skin Care Products

Ampa Jimtaisong, PhD1702702 Advanced Cosmetic Science for Skin (2/2009)School of Cosmetic Science-Mae Fah Luang University

Outline

1. Oils and oil-miscible materials (emollient)2. Humectants3. Surfactants4 Thickening agents (polymers)

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4. Thickening agents (polymers) 5. Water6. Anti-aging and antioxidants7. Whitening agents, Sunscreens, Anti-acne8. Other additives, preservatives

Raw Materials For Skin Care ProductsRaw Materials For Skin Care Products

Creams, lotions ==> EmulsionOils and oil-miscible materials

Emollients: oily materials (esters, fatty acids, silicone oils)Wax materialsEmulsifiers

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Water and water miscible materialsHumectantsThickening agent (Water-soluble polymers)

PreservativesAdditives

Active ingredientsAntioxidants, fragrances, coloring agents

Oily MaterialsOily Materials

Emollient Esters and Oils

Oils & OilOils & Oil--miscible Materialsmiscible MaterialsEmollient Esters and Oils

Oils and fatsWax esters

Wax materials

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Wax materialsHydrocarbonsHigher fatty acidsHigher alcoholsSilicones

EstersEstersEstersEstersR' C

O

O R

6

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EstersEsters1. Naturally Occurring Esters

2. Simple Esters

3. Complex Esters

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O C

O

DOA

IPM

Naturally Occurring EstersNaturally Occurring Esters

The first used and still in wide use today

Perform well and has the properties closely mimic the lipids components

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occurring naturally in skin and hair.

1. Triglycerides2. Lanolin and Lanolin Derivatives

TriglyceridesTriglycerides: Naturally Occurring Esters: Naturally Occurring Esters

Three fatty acid radicals are united by oxygen (in an ester linkage) to glycerin

H2C

HC

H2C

O C

O

R

O C

O

R'

O C

O

R''

9


Fat splitting==> Alkaline hydrolysis (sponification)

H2C OHH2C O C

O

RO

R C

O

ONa

ONaOHH2C OH

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HC

H2C

OH

OH

HC

H2C

O C R'

O C

O

R''

R' C ONa

R'' C

O

ONa

+H2O, Heat

Triglyceride(Fat / oil)

Glycerol Mixture of fatty acid soaps

HC

H2C

OH

OH


Acid hydrolysis

R C

O

ONa

O Acid (HCl)R C

O

OH

O

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R' C

O

ONa

R'' C

O

ONa

+( )

H2O

Mixture of fatty acidsMixture of fatty acid soaps

R' C

O

OH

R'' C

O

OH

NaCl


Triglycerides compose the largest group of oils and fats found in both vegetables and animals.

Triglycerides are differentiated by their fatty acid

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composition

H2C

HC

H2C

O C

O

R

O C

O

R'

O C

O

R''

Handout Table 1

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1. Vegetable Triglycerides

2. Animal Triglycerides

3. Marine Triglycerides

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1. Vegetable TriglyceridesVegetable triglycerides are called oilsAnimal triglycerides are referred to as fats

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Olive oil: original emollients

Vegetable oils: fluid at room temperature

H2C

HC

H2C

O C

O

R

O C

O

R'

O C

O

R''



Composition and nature of fatty acid composition

Vegetable oils contain a high proportion of

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unsaturated fatty acid triglyceride esters.

C=C bond: a kink in the fatty acid chain

H2C

HC

H2C

O C

O

R

O C

O

R'

O C

O

R''


1. Vegetable TriglyceridesA kink make it more difficult for the molecule to form an ordered structure ≠> solidification

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H3CCOOH

H3CCOOH

Stearic acid

Oleic acid


Cis – and Trans-isomersTrans- Oleic acid =Elaidic acid

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•cis-Δ9-octadecenoic acid•Oleic acid; C18:1,cis-, Δ9


1. Vegetable TriglyceridesVegetable oils: important role as emollients

Vegetable oils: lack of stability to oxidation

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Oxidation reaction = rancidity unpleasant odor and taste.

Vegetable oils => soften skin but oily feelH2C

HC

H2C

O C

O

R

O C

O

R'

O C

O

R''

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Vegetable oils: large size (three fatty acids)

Easier to emulsify the smaller molecule

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Use large emulsifier to emulsify the oils

H2C

HC

H2C

O C

O

R

O C

O

R'

O C

O

R''


1. Vegetable TriglyceridesVegetable oils: trace compounds

Oxidation of trace compounds aldehydes,

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ketones

Potential irritants or degradation

H2C

HC

H2C

O C

O

R

O C

O

R'

O C

O

R''Handout Table 2

Vegetable TriglyceridesVegetable TriglyceridesOlive oil (Olive oil (OleaOlea europaeaeuropaea LinnLinnéé))Fruit of olive tree

Oleic acid (C18:1) 65-85%Palmitic acid (C16) 7-16%Linoleic acid (C18:2)4-15%

Naturally O

ccN

aturally Occ

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Linoleic acid (C18:2)4 15%

H3CCOOH

Oleic acid

curring Esterscurring Esters

H3CCOOH

Palmitic acid

HO

O

Linolenic acid

Vegetable TriglyceridesVegetable TriglyceridesOlive oilOlive oil

Naturally O

ccN

aturally Occ

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H2C

HC

H2C

O C

O

O C

O

O C

O

H2C

HC

H2C

O C

O

O C

O

O C

O

Vegetable TriglyceridesVegetable Triglycerides

Caster oilCaster oilSeed of caster plant (Ricinus communis)Ricinolic acid as the hydroxy acid (85-95%)

Naturally O

ccN

aturally Occ

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Hydrophilic, viscous and soluble in ethanol



Sesame oilSesame oilPalmitic acid C16:0 7-12 %Palmitoleic C16:1 ~0.5 %St i id C18 0 3 5 6 %

Naturally O

ccN

aturally Occ

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Stearic acid C18:0 3.5-6 %Oleic acid C18:1 35-50%Linoleic acid C18:2 35-50%Linolenic acid(C18:3)Eicosenoic(C20:1)

Penetrate the skin easily


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Jojoba oilJojoba oilLiquid wax ester from seed of wild jojoba plant (Simmondsia chinensis

d Si d i lif i )

Naturally O

ccurN

aturally Occur

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and Simmondsia californica )Unsaturated higher alcohols and

unsaturated fatty acids (C36-C46)

Pleasant touch to the skin

ring ring W

axW

axEstersEsters


2. Animal Triglycerides

HC chain length of component fatty acids

Degree of unsaturation of component fatty acids

H2C

HC

H2C

O C

O

R

O C

O

R'

O C

O

R''

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Degree of unsaturation of component fatty acids

Presence of trace components


2. Animal TriglyceridesAnimal fats : the subcutaneous fat layer (mostly)

Animal fats : other sources-- egg oil and milk fat

H2C

HC

H2C

O C

O

R

O C

O

R'

O C

O

R''

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(butter)

Animal fats : high content of saturated fatty acid

Handout Table 3

Naturally Occurring Esters2. Animal Triglycerides

Animal fats : beef tallow and lard Soft solids except mink oil.

H2C

HC

H2C

O C

O

R

O C

O

R'

O C

O

R''

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Animal TriglyceridesAnimal Triglycerides

Tallow and lardTallow is a rendered form of beef or mutton fat, processed from suet. Lard refers to pig fat in both its rendered and

Naturally O

ccN

aturally Occ

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Lard refers to pig fat in both its rendered and unrendered forms.Traditionally, soap is made by the reaction between a fat and a strong alkali such as NaOH, KOH, NaHCO3



Soap is a salt of a fatty acid. Fat (Triglyceride) + a strong alkali

Naturally O

ccN

aturally Occ

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Mink oilMink oil is a source of palmitoleic acid which possesses physical properties similar to human sebum

Naturally O

ccN

aturally Occ

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human sebum. Botanical alternatives to mink oil as a source of palmitoleic acid include macadamia nut oil which contain a larger percentage of palmitoleic acid (22%) than does mink oil (17%).




Emollients & aiding the biological functioning of the skin due to the highly polyunsaturated oils.

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Cold-water fish: salmon, anchovy, menhaden

TriglyceridesTriglycerides: Naturally Occurring Esters: Naturally Occurring Esters3. Marine Triglycerides

Polyunsaturated Fatty Acid (PUFA):EPA, DHAEPA : Eicosapentaenoic acid (C20:5)DHA: Docosahexaenoic acid (C22:6)H t iti d bi h i l

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Human nutrition and biophysiologyExtreme sensitivity to oxidationFishy odorRancidity--> paint-like smell

COOH

CH3 CH3

COOHEPA DHA

LanolinLanolin : Naturally Occurring Esters: Naturally Occurring Esters

2. Lanolin and Lanolin Derivatives

Alcohol fraction of triglycerides: glycerin

Al h l f ti f l li di

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Alcohol fraction of lanolin: very diverse

Two classes of alcohol fraction :

Aliphatic alcohols

Steroidal alcohols



Cholesterol, Lanosterol

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Cholesterol

Lanosterol



Lanolin: the purified form of wool wax, or

wool grease (lipid in fleece of sheep)

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wool grease (lipid in fleece of sheep).

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Lanolin: a soft, tenacious solid, Mp ~ 40°C

U d lli t d ili l ifi

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Used as emollient and auxiliary emulsifier

of the W/O type

Lanolin : Lanolin : Naturally Occurring EstersNaturally Occurring Esters


2.1 Lanolin Oil

Mi ibl ith i l il i ll ti

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Miscible with mineral oil in all proportions

2.2 Lanolin Derivatives

Physical form and solubility characteristics

EstersEsters1. Naturally Occurring Esters

2. Simple Esters

3. Complex Esters

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O C

O

DOA

IPM

Simple EstersSimple EstersEsterification reaction

Alcohols + Acids Esters

R O H O C R'+ R O C

O

R'

O

+ H OH

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R O H O C R'+ R O C R' + H2OH

alcohol carboxylic acid ester water


R O H O C R'+ R O C

O

R'

O

+ H2OH

alcohol carboxylic acid ester t

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Properties of Esters1. HC chain length of the component acid and alcohol2. Degree of unsaturation 3. Presence of brancing4. Presence of multiple acid or alcohol fractions5. Presence of trace components


R O H O C R'+ R O C

O

R'

O

+ H2OH


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y

Alcohol Carboxylic acid EsterMethanol Benzoic acid Methyl benzoateLinalool Linalyl acetate

Propyl phenylacetateMethyl salicylate

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Simple EstersSimple EstersIsopropyl myristate

O H O C+

O

H

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O C

O

Isopropyl Myristate : IPM

+ H2O

Acid, Heat

Simple EstersSimple Esters

Isopropyl myristate is a fluid emollient ester

O C

O


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Isopropyl myristate is a fluid emollient esterNo unsaturation of fatty component—fluid?Branching helps interrupt the orderly association

Changes in the alcohol fraction can substitute for variations in the acid fractionBranching can be substitution for unsaturation with regard to fluidity

Simple EstersSimple Esters1. Straight-Chain Esters

Straight HC chain fatty acidStraight HC chain fatty alcohol

2 Branched-Chain Esters

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2. Branched Chain Esters

O C

O


Simple EstersSimple EstersStraight-Chain Esters

1. Acid Component VariationsKeeping the alcohol the same

H O C

O

n

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As the n increase, - the Mp of the resulting ester increase- the fluidity decrease- the hydrophobicity increase- oilier-feeling ester (or waxier feeling if MW up)


1. Acid Component VariationsSimple straight-chain emollient esters used in

H O C

O

n

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Simple straight chain emollient esters used in cosmetics: Lauric (C12:0) to Stearic (C18:0)Shorter HC chains: NOT capable of delivering non-greasy, lubricating emollient feelHigher HC chains: esters with Mp well above skin temperature==> Wax Esters


1. Acid Component VariationsSimple straight-chain esters can be based on unsaturated fatty acids: Oleic (C ) Linoleic

H O C

O

n

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unsaturated fatty acids: Oleic (C18:1), Linoleic (C18:2) and the less common palmitoleic (C16:1)

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2. Fatty Alcohol Component VariationsWith the n increase, the Mp and Bp of the resulting esters increase

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resulting esters increase.

H O n


1. Straight-Chain Esters2. Branched-Chain Esters

Short Branched-Chain Alcohols

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Branched-Chain Fatty Alcohols


2. Branched-Chain EstersBranched chain molecules remain fluid over a much greater temperature range

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Higher spreading factor on skinLess oily-feelingLow irritationSkin feeling- “cushiony”


Examples:

1. Isopropyl myristate (IPM)

2. Isopropyl stearate (Cetiol 868)

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3. Isopropyl palmitate

4. Butyl stearate

Complex EstersComplex Esters

Complex Esters: multifunctional acids and alcoholsEconomic, Very fluid, light-feeling, extreme non greasy

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extreme non-greasyDioctyl sebacate, Dioctyl adipate, Dioctylmaleate


Dioctyl sebacate

Dioctyl adipate (DOA)

2-ethylhexanol

sebacic acid

Octanol

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Dioctylmaleate (DOM)

Octanol

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MFU 10

Complex EstersComplex EstersStearate ester: stearic acid + ethylene glycol HOCH2CH2OHGlycol monostearate ester, Glycol distearate esterGlycols: diethylene or triethylene

HOOH

ethylene glycol

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In emulsion: Low HLB emulsifierIn surfactant: opacity and pearlescence

HOO

OH

diethylene glycolstearic acid

HOO

OOH

triethylene glycol


PEG-150 distearate (or PEG-6000 distearate)Synonym: Polyethylene glycol distearate

CAS:9005-08-7

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PEG 6000 distearate

Viscosity-building agent

Formula:(C2H4O)nC36H70O3

CH3(CH2)16CO(OCH2CH2)nO2C(CH2)16CH3


Caprylic/capric estersEmollient, pigment-wetting agent

A mixed triester of caprylic and capric acids, is

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a highly refined medium chain triglyceride (MCT) oil possessing excellent oxidation stability with an almost indefinite shelf life.


Caprylic/capric estersCCT is a desirable emollient with quick skin penetration and has no color, odor or taste.

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Great as a dispersing agent and useful as a solvent for vitamins and actives.

Excellent as a superfatting oil in soapmaking and improves spreading of skin care formulas.



Wax materials

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Carnauba wax

Canauba palms

INCI name is Copernicia Cerifera (carnauba) wax

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Ester of C20-C32 fatty acids and C28-C34 alcohols

Mp 80-86 °C

Improve gross

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Candelilla waxCandelilla plant (Euphorbia cerifera, Euphorbia antisyphilitica)45 % Hydrocarbon(C31H64)30% C16-C34 fatty acid esters

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30% C16 C34 fatty acid esters25% free alcohols (e.g. myricyl alcoholResins, etc.Mp 70 oCImprove gross

Hives of honeybees of the genus ApisCeryl 16-hydroxypalmitate

Beeswax

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(C15H30(OH)COOC26H35)Ceryl palmitate (C15H31COOC26H53)Miricyl palmitate (C15H31COOC31H63)



Wax materials

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HydrocarbonsHydrocarbonsHydrocarbonsHydrocarbons

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HydrocarbonsHydrocarbons

ParaffinMineral oilPetrolatumMineral wax (solid paraffin)

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Mineral wax (solid paraffin)Squalene, squalene


Paraffin or Paraffin HydrocarbonIn chemistry, paraffin is the common name for the alkane hydrocarbons with the general formula C H

66

formula CnH2n+2

The simplest paraffin molecule: Methane, CH4

Heavier members of the series: Octane C8H18,

The solid forms of paraffin: paraffin wax, C20H42

to C40H82

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Paraffin or Paraffin HydrocarbonTechnical name for a linear, or normalalkane

67

Branched alkane, or isoalkanes: isoparaffins

Non-polar and very unreactive.


Mineral oilor liquid petrolatum: by-product in the distillation of petroleum to produce gasoline

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Mixture of heavier alkanes (typically 15 to 40 Cs)

Transparent, colorless oil, density of ~ 0.8 g/cm3

Low value, produced in very large quantities

Mineral oil : light and heavy grades

HydrocarbonsHydrocarbonsNames: Mineral oilNujol, adepsine oil, alboline, glymol, medicinal paraffin, saxol, USP mineral oilBaby Oil Liquid paraffin Paraffin oil

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Baby Oil, Liquid paraffin, Paraffin oil, Liquid petroleumWhite oil Cable oil Lignite oil Mineral Seal Oil Synthetic (Motor) Oil


Petrolatum

Petroleum jelly or soft paraffin

Semi-solid mixture of HCs (with C >25 atoms)

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Topical ointment for its healing properties. Its folkloric medicinal value as a "cure-all" has since been limited by better scientific understanding of appropriate and inappropriate uses

HydrocarbonsHydrocarbonsMineral wax (solid paraffin)

Macro-crystalline waxes (normal alkanes)Relatively large brittle crystals (Macrocrystalline) Generally have little affinity for oilParaffin wax

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Paraffin waxMicrocrystalline waxes (branched and cyclic saturated hydrocarbons, in addition to normal alkanes)

have very minute crystals (Micro Crystals) flexible, with a greater affinity for oil, which is held tightly in the crystal lattice and does not migrate to the surface.Ozokerite, ceresine (refine grade of ozokerite)

HydrocarbonsHydrocarbonsTypical Properties of Mineral wax

Property WaxMacrocrystalline Microcrystalline

Flash point closed cup, C 204 260

Viscosity at 98.90C, mm-9/s 4 2-7 4 10 2-25

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Viscosity at 98.90C, mm 9/s 4.2 7.4 10.2 25

Melting range, ~C 46-68 60-93

Refractive index at 98.9~C 1.430-1.433 1.435-1.445

Number average molecular weight 350-420 600-800

Carbon atoms per molecule 20-36 30-75

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HydrocarbonsHydrocarbonsParaffin wax (Macrocrystalline wax)Solid alkane hydrocarbons with n=20–40 (C20H42, C40H82)Brittle solid40-90 wt % normal alkanes

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40 90 wt % normal alkanesC18-C36 isoalkanes and cycloalkanes. Paraffin wax has little affinity for oil content: fully refined paraffin has less than 1 wt %; crude scale, 1-2 wt %. Within these classes, the melting point of the wax determines the actual grade, with a range of about 46-71ºC

HydrocarbonsHydrocarbonsOzokerite & Ceresine (refine grade of ozokerite)a product of Poland, Austria, and in the former USSR where it was mined. True ozokerite no longer seems to be an article of commerce and has been replaced ith blends of

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commerce, and has been replaced with blends of petroleum-derived paraffin and microcrystalline waxes.

Ceresin wax [8001-75-0] originally was a refined and bleached ozokerite wax.

HydrocarbonsHydrocarbonsSqualene, squaleneSqualene is a natural organic compound originally obtained for commercial purposes primarily from shark liver oil, though there are

Squalene

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botanic sources as well, including rice bran, wheat germ, and olives. All higher organisms produce squalene, including humans. It is a hydrocarbon and a triterpene.

Squalane (C30H62)Squalene (C30H50)

HydrocarbonsHydrocarbonsSqualene, squaleneSqualane is a light and stable version of squalene with a long shelf life. It is extremely useful (and widely used) as an

Squalane (C30H62)

Squalene (C30H50)

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y ( y )emollient, skin conditioner and carrier oil in cosmetic applications and hair care. Easy to emulsify, Squalane is soluble in most cosmetic oils including Cyclomethicone. Often referred to as “mother nature’s face lift”, Squalane is found in human sebum at 12 %


squalene

Squalane (C30H62)

Squalene (C30H50)

77squalane



Wax materials

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Higher Fatty AcidsHigher Fatty Acids

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Higher Fatty AcidsHigher Fatty AcidsRCOOH, R= saturated alkyl group or unsaturated alkenyl groupMix with caustic soda and TEA –emulsifier

R C

O

O H

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Lauric acidMyristic acidPalmitic acidStearic acidIsostearic acid

Triethanolamine stearateC17H35COOH•N(CH2CH2OH)3

HO

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N

OH OHO O

H

triethanolamine stearate


Palmitic acid: CH3(CH2)14COOH

One of the most common saturated fatty acids found in

animals and plants.

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As its name indicates, it is a major component of the oil

from palm trees (palm oil and palm kernel oil).


Stearic acid, CH3(CH2)16COOH

Common stearic acid is actually a mix of stearic acid and

palmitic acid, although purified stearic acid is available

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separately.

Used in cream to modify the cream consistency and

hardness.


Isostearic acid

The C18-saturated fatty acid with a branched

structure

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structure

Liquid ingredient

Heat stability

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Wax materials

85


Higher AlcoholsHigher Alcohols

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Higher Alcohols (Fatty alcohols)Higher Alcohols (Fatty alcohols)Monovalent alcohols with C6 or moreOily material and emulsion stabilizerCetyl alcoholStearyl alcohol

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Stearyl alcoholCetostearyl alcoholCetearyl alcohol Oleyl alcoholMyristyl alcohol

Higher Alcohols (Fatty alcohols)Higher Alcohols (Fatty alcohols)Cetyl alcohol, CH3(CH2)15OHknown as Cetanol, 1-hexadecanol and palmityl alcoholAt room temperature: waxy white solid or flakes

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At room temperature: waxy white solid or flakes. The name cetyl derives from the whale oil (Latin: cetus) from which it was first isolated.OH group-no emulsifying properties itselfThickening agent

Higher Alcohols (Fatty alcohols)Higher Alcohols (Fatty alcohols)

Stearyl alcohol, CH3(CH2)17OHOctadecyl alcohol Waxy white solid or flakes

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Melting point of 61°CIt is used as an emollient, and thickener in ointments of various sorts

ReferencesReferences

1. Mitsui,T., New Cosmetic Science, Elsevier Science B.V, Tokyo,

Japan, 1997.

2. Schueller, R., Romanowski, P., Conditioning Agents for Hair and

Skin, Marcel Dekker, Inc., New York, NY, USA, 1999.

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Documents

Emollient W3 Nov 21-09-hanout - Mae Fah Luang University