Presentation to CARB

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Presentation to CARB

• Fragrance Materials Association
• July 24, 2006
• William R. Troy, Ph.D.
• Firmenich, Inc.

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The Sense of Smell

• Odorant molecules are conveyed via the air to a
  thin layer of mucus overlying the receptor sites
  in the nasal epithelium
• About 50 million such receptors in the human
  nose, and tens of thousands of discrete odors
  which can be distinguished
• The latter may explain the profusion of scented
  products in the marketplace

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The Sense of Smell (contd)

• In order for odor to be detected by the human
  olfactory system it must be, by definition,
  volatile
• Non-volatile material no odor
• Two components to odor perception
• Chemical volatility
• Odor threshold

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Fragrances as Volatiles

• A fragrance is a mixture of volatile materials
  that are so interdependent that it must be
  considered as a single entity
• Volatility expressed in physical terms as vapor
  pressure
• V.P. a function of a chemicals structure and
  molecular weight
• In general, very large molecules less volatile
  (i.e., lower v.p.)
• Vapor pressure measured in millimeters (mm) of
  mercury (Hg)

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Fragrances as Volatiles (contd)

• As an example, ethyl alcoholcommonly used in a
  wide variety of personal care and household
  productshas a v.p. of about 50 mm Hg
• Many fragrance materials have a v.p. less than 2
  mm Hg
• The v.p. of a mixture of fragrance materials
  (i.e., a perfume) can be estimated by

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Fragrances as Volatiles (contd)

• Summing the partial pressures of each fragrance
  material based on
• individual v.p.s
• mole fraction of each
• Question if the v.p. of many individual
  fragrance materials, and mixtures of these, is
  less than 2 mm Hg, how do they function
  effectively as complete fragrances?

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Fragrances as Volatiles (contd)

• Answer odor threshold
• The odor threshold of a typical fragrance
  material can be thousands of times lower than,
  e.g., ethyl alcohol
• Therefore, perceived odor is not always directly
  indicative of mass concentration of an odorant in
  air

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Fragrances as Volatiles (contd)

• While the v.p. of a fragrance can be estimated,
  it is impossible to know precisely because
• In a mixture the relative volatility of each
  component is influenced by the volatility (i.e.,
  v.p.) of the other components, and

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Fragrances as Volatiles (contd)

• There can be chemical interactions among
  fragrance ingredients
• Therefore, because of the interdependency of its
  components, a fragrance must be considered as a
  single entity when making decisions about vapor
  pressure

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Fragrance Materials

• There are about 2,500 individual fragrance
  materials in current use in perfumery
• Fragrance mixtures of these materials may contain
  as few as 50, or as many as 300, individual
  chemical entities
• Fragrance raw materials may contain as few as 5
  carbon atoms, or as many as 18, with attached
  hydrogen, oxygen, etc., atoms

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Fragrance Materials (contd)

• About 80 of all fragrance materials have between
  9- and 15-carbon atom structures
• Lower weight (i.e., fewer carbons) materials are
  typically used in low concentrations in mixtures
  due to their high v.p. and powerful olfactory
  effects ( odor threshold)
• Lower weight materials are those that usually
  contribute to the top of the fragrance, or that
  portion that is perceived immediately after use

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Fragrance Materials (contd)

• Higher weight materials usually constitute the
  bottom notes of the fragrance, or those that
  remain for long periods after initial dry-down
• The mid-notes of the fragrance are represented by
  a mixture of materials of varying sizes and vapor
  pressures

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Fragrance Materials (contd)

• Fragrances intended for different product
  applications (e.g., fine fragrance, air
  freshener, laundry) will have differing ratios of
  top/mid/bottom notes within the same single
  entity
• In general, fine fragrances will discretely
  display all 3 olfactive segments during dry-down,
  while some functional and household products may
  have a more linear odor rendition

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Fragrance Families

• Aromatic Herbal
• E.g., pine, eucalyptus, lavender
• Chypre
• E.g., mosses
• Citrus
• E.g., lemon, orange
• Floral
• E.g., jasmine, rose, muguet

• Fougere
• E.g., geranium, coumarin
• Fruity
• E.g., peach, apricot, melon
• Oriental
• E.g., balsamic, vanilla
• Woody
• E.g., sandalwood, patchouli

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Fragrance Ingredient Origins

• Naturally derived directly from plant materials,
  distilled or extracted from flowers, leaves,
  woods or grasses
• Synthetic originate via organic synthesis
• Natural materials are mistakenly thought to be
  superior to syntheticsWRONG!

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Frag. Ingred. Origins (contd)

• In fact, the only difference between natural and
  synthetic fragrance materials is their origin and
  method of preparation
• Additionally, no differences in reactivity of
  natural vs. synthetic fragrance materials

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Functions of the Fragrance Entity

• While there may be hundreds of fragrance
  materials in a single formula, each one is there
  for a specific purpose
• Think of a musical chord, played on an organ, but
  instead of 3-4 simultaneous notes there are
  hundreds, all blending together
• Removal of an ingredient usually results in a
  dischord

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Functions of the Fragrance Entity

• Principal character material
• Provides basic smell
• Modifiers
• Decoration for the fragrance
• Blenders
• For rounding
• Fixatives
• Prolong fragrance life

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Functions of the Fragrance Entity

• Solvents used in fragrances are typically diethyl
  phthalate (DEP) or dipropylene glycol (DIPG)
• Small amounts of ethyl alcohol used occasionally
• V.P. of DEP reported as negligible
• V.P. of DIPG is 0.38 mm Hg

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Fragrance in Consumer Products

• Four of the fragranced product areas being
  reviewed by CARB
• Household Cleaning
• Air Care
• Laundry
• Fine Fragrance/Personal Care

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Frag. in Consumer Prod. (contd)

• Household Cleaning may contain as much as 5
  fragrance
• Laundry as much as 4 (Dryer Sheets)
• Air Care pump sprays have 5 fragrance
• Personal Care such as body lotion, typically
  about 2 fragrance
• Fine Fragrance may have up to 30 fragrance

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Frag. in Consumer Prod. (contd)

• It should be remembered here that the original
  CARB decision to adopt a 2 exemption for
  fragrance-containing products was based on the
  very wide range of fragrance use levels in
  various product types (i.e., Household Cleaning
  5 Fine Fragrance 30), and the recognition
  that fragrance is a very critical signal
  ingredient in consumer products

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Consumer Expectations

• For Fine Fragrance/Personal Care, fragrance is
  the product, for the most part, even when present
  in small amounts
• Deodorants, shampoos do have other functionality,
  but fragrance preference still plays a large role
  in product selection
• For functional products, performance is key but
  fragrance guides consumer preferences when
  performance is perceived to be equivalent

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Consumer Expectations (contd)

• Market research has shown that consumers have
  olfactive expectations for the odor of the
  functional product(s) they use, and for the
  residual odor after product use
• E.g.
• Laundry detergent clean smell
• Fabric softener fresh smell

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Consumer Expectations (contd)

• Toilet cleaner disinfectant
• All purpose cleaner citrus fresh
• In addition to qualitative expectations,
  consumers who like the fragrance say, in every
  single market test, needs more fragrance!
• Product marketers, therefore, need to retain
  flexibility for future product design

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Product Challenges for Fragrance

• Practically all functional products contain base
  ingredients with significant malodor value, which
  must be covered by fragrance for consumer
  acceptance
• Many functional products contain aggressive
  ingredients such as bleach, ammonia, etc., which
  adversely affect the fragrance

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Prod. Chal. for Frag. (contd)

• Fragrances are, by nature, hydrophobic, while the
  majority of consumer products are water-based
• This can result in product stability issues
• This also reduces the selection of fragrance
  materials that can be used

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Why the 2 Fragrance Exemption Must Be Maintained

• The 2 exemption is already a significant
  reduction over industrys original request for 5
• The 2 figure was selected in recognition of the
  fact that consumer products have a very wide
  range of fragrance concentrationsfrom Household
  products containing 5, to Fine Fragrances with
  up to 30
• 2 also provided for creative flexibility for
  product marketers in designing future products

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Why the 2 Fragrance Exemption Must Be Maintained
(contd)

• 2 was seen as a representative value to be
  applied across the entire spectrumnot product by
  product
• Especially in household products fragrance entity
  is seen as a signal for efficacy
• Any reduction in fragrance entitywhether to
  reduce VOCs or otherwisewill only lead to the
  consumer using MORE product to achieve the same
  olfactive impact efficacy

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Why the 2 Fragrance Exemption Must Be Maintained
(contd)

• Any increase in water content of the product base
  (e.g., to reduce VOC content) will upset the
  solubility of the fragrance entity, and hence
  adversely affect the stability of the product
• Increasing surfactant level to force fragrance
  solubility may lead to a need for additional
  safety testing

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Why the 2 Fragrance Exemption Must Be Maintained
(contd)

• Increased water also reduces the fragrance lift
  provided by alcohol and other similar ingredients
• Result lowered fragrance perception, leading to
  consumers increased product use to achieve
  olfactive endpoint
• Increased product use means increased fragrance
  and increased non-fragrance VOCs

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Why the 2 Fragrance Exemption Must Be Maintained
(contd)

• Damages the consumer products and upsets product
  consumers
• Will have questionable end benefit because
  consumer will titrate product use to achieve
  same level of fragrance perception, which they
  equate with product efficacy

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Why the 2 Fragrance Exemption Must Be Maintained
(contd)

• Reduction of fragrance to achieve reduced VOC
  attacks the very most minute part of the larger
  subject of VOCs

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Thank you!