Lecture Notes on Waxes and Humectants

Waxes

  • Definition: Natural waxes are natural esters consisting of a fatty acid attached to a long-chain fatty alcohol.

    • The alcohol component has a hydroxyl group (alcohol functional group).
    • Long hydrocarbon chains, generally 16-30 carbon atoms in length.
    • Joined by an ester linkage via dehydration synthesis.
    • Lack a glycerol backbone, unlike triglycerides.
    • Essentially fatty acids and fatty alcohols joined.
  • Properties:

    • Often saturated and have long chains, making them harder, less greasy, and more brittle.

    • Typically solid at room temperature.

    • Melting points generally above 45°C.

    • Exception:

    • Jojoba oil is a liquid wax.

    • Melting Points:

    • Different waxes have different melting points.

    • Lipstick formulation example: Waxes must be solid in the stick but melt upon skin contact.

    • Microbial Resistance:

    • Waxes are resistant to microbial attack; microbes generally don't use them as a food source.

    • Preservatives:

    • Solid waxy formulas (e.g., lip balms) may not require preservatives.

    • Considerations:

    • Resistant to moisture and oxidation.

    • Can alter product thickness and melting point.

    • May add heaviness, requiring adjustments to the formula.

  • Sources:

    • Animal Waxes:
    • Beeswax (solid at room temperature).
    • Lanolin (from sheep's wool).
      • Historically used as a moisturizer but can be comedogenic and contain contaminants.
      • Modern lanolin is often chemically modified and purified to remove undesirable qualities.
    • Plant Waxes:
    • Produced by plants to prevent water evaporation.
    • Examples: carnauba, candelilla, jojoba.
    • Often come in flake form.
    • Used in color cosmetics.
    • Modifications:
    • PEG modifications (adding hydroxyl groups).
    • Examples: PEG oils, PEG waxes, PEG six, PEG eight beeswax, peg six, peg 20 sorbitum beeswax, silicone and beeswax.
    • Mineral Waxes:
    • From soils and petroleum byproducts.
    • Examples: ozokerite, paraffin, microcrystalline, ceresin.
    • Synthetic Waxes:
    • Paraffin wax is a basic synthetic wax.
    • Polyethylene and carbo waxes.
    • Paraffin wax is often used in candles.
    • Can add brittleness to products.

Humectants

  • Definition: Polar substances that absorb water vapor and draw water to themselves.

  • Function:

    • Part of the water phase of an emulsion.
    • Hygroscopic/hydrophilic: attract and hold onto water via hydrogen bonds.
    • Typical concentration: 1-5% in a formula (can be higher in serums).
  • Benefits in Emulsions:

    • Hydrating Effect: Retain water to reduce transepidermal water loss (TEWL).
    • Prevent Product Dehydration: Maintain product hydration over its lifespan.
    • Reduce Free Water:
    • Humectants bind water molecules, reducing free water.
    • Free water is the first to evaporate and can be used by microbes for replication.
  • Mechanism: Ability to form hydrogen bonds due to hydroxyl groups (-OH) or oxygen atoms.

  • Examples:

    • Glycerin:
    • Benchmark humectant.
    • Has a hydrocarbon backbone with a hydroxyl group attached to each carbon.
    • Can modify aquaporin channels in the epidermis to enhance water delivery, and is considered a cosmeceutical.
    • May feel tacky at concentrations above 5%.
    • Sorbitol:
    • Similar to glycerin, with hydroxyl groups on each carbon.
    • Common in toothpaste due to its humectancy and slight sweetness.
    • Hyaluronic Acid:
    • Large molecule with hydrocarbon structures and numerous oxygen-containing functional groups.
    • Binds 10001000 times its weight in water.
  • Sources of Water:

    • Water within the formulation.
    • Water from the viable epidermal and dermal layers.
    • Water from the surrounding air (in high humidity).
  • Water Binding and TEWL:

    • Humectants pull water from within the skin to the stratum corneum, preventing TEWL.
    • May increase TEWL if not combined with occlusive ingredients (e.g., ceramides, dimethicone, silicas).
  • Aquaporins/Aquaglyceroporins:

    • Protein channels in keratinocyte plasma membranes that transport water and glycerin.
    • Present from the basal layer to the granular layer.
    • Non-functional in stratum corneum to prevent rapid water loss.
  • Environmental Factors:

    • High humidity (>70%) allows skin to absorb water from the air.
    • Steam facials provide a high-humidity environment to hydrate skin.
    • Moisturizing creams are crucial after facials to prevent water loss.
  • Common Humectant Ingredients:

    • Glycerin, sorbitol, urea.

    • Components of natural moisturizing factors (NMF) in the stratum corneum.

    • Examples: pyrrolidone carboxylic acid (PCA), sodium lactate, alpha hydroxy acids (AHAs), lactic acid, urea.

    • Alternatives to glycerin: hexylene glycol, butylene glycol, propylene glycol, MP diol.

    • Glycerin Detailed:

    • Still one of the most commonly used humectants in products.

    • Measure for how humid something is.

    • Has a reservoir effect in the skin.

    • Exhibiting action on the skin that makes it a cosmeceutical.

    • Can modify aquaporin channels within the epidermis to enhance the delivery of water.

    • Sorbitol Detailed:

    • Longer hydrocarbon chain than glycerin, with hydroxyl groups.

    • Usually in powder form or a 70% aqueous solution.

    • Hexylene, Butylene, and Propylene Glycol Detailed:

    • Common in facial emulsions.

    • Do not have the sticky after-feel of glycerin.

    • Used in foundations to help spread pigment without streaking.

    • Also can be used as a penetration enhancer, but with limitations on its use because of its ability to potentially enhance the delivery of less desirable things.

    • MPDIOL:

    • Similar, but cheaper in formulas.

    • Natural Moisturizing Factor (NMF) Ingredients:

    • Hydroxyl groups or oxygen creates polar qualities.

    • Alpha Hydroxy Acids (AHAs):

    • Also known as peeling agent; used for skin peels, chemical skin peels.

    • AHAs + urea both have a crashlytic and desmolytic effect, but can also both have humectant qualities to them.

    • $<10$%

      • humectant with 0.1% 3% concentration
    • $>10$%

      • caratolitic or desmolitic properties
    • Hyaluronic Acid (HA):

    • High molecular weight polymer that is made from subunits.

    • Huge water-binding capacity due to polar areas.

    • High Molecular Weight ( > 500,000 Daltons):

      • Forms a moisturizing viscoelastic film on the skin surface and is an occluded