Presentation to CARB

1. Presentation to CARB Fragrance Materials Association July 24, 2006 William R. Troy, Ph.D. Firmenich, Inc.

2. 2 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

3. 3 The Sense of Smell (cont’d) 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

4. 4 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 chemical’s 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)

5. 5 Fragrances as Volatiles (cont’d) As an example, ethyl alcohol—commonly used in a wide variety of personal care and household products—has 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:

6. 6 Fragrances as Volatiles (cont’d) 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?

7. 7 Fragrances as Volatiles (cont’d) 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 The disconnect between perceived odor of fragrances, and an assumption of concentration, leads to misunderstandings about the contributions of fragranced products to air quality. Many times a strong odor can be produced at a concentration of only parts per million.The disconnect between perceived odor of fragrances, and an assumption of concentration, leads to misunderstandings about the contributions of fragranced products to air quality. Many times a strong odor can be produced at a concentration of only parts per million.

8. 8 Fragrances as Volatiles (cont’d) 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

9. 9 Fragrances as Volatiles (cont’d) 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

10. 10 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

11. 11 Fragrance Materials (cont’d) 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

12. 12 Fragrance Materials (cont’d) 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

13. 13 Fragrance Materials (cont’d) 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

14. 14 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

15. 15 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 synthetics—WRONG!

16. 16 Frag. Ingred. Origins (cont’d) 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

17. 17 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

18. 18 Functions of the Fragrance Entity Principal character material Provides basic smell Modifiers “Decoration” for the fragrance Blenders For “rounding” Fixatives Prolong fragrance life Principle character – rose essence in a Rose perfume Modifier – add style, naturalness, freshness, diffusion; e.g., a banana note in Jasmine. Blender – used to blend sometimes disparate basic and modifying notes; to round, or smooth off Fixative – gives depth, substance and background; holds a fragrance together, preventing too-quick evaporationPrinciple character – rose essence in a Rose perfume Modifier – add style, naturalness, freshness, diffusion; e.g., a banana note in Jasmine. Blender – used to blend sometimes disparate basic and modifying notes; to round, or smooth off Fixative – gives depth, substance and background; holds a fragrance together, preventing too-quick evaporation

19. 19 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

20. 20 Fragrance in Consumer Products Four of the fragranced product areas being reviewed by CARB: Household Cleaning Air Care Laundry Fine Fragrance/Personal Care

21. 21 Frag. in Consumer Prod. (cont’d) 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

22. 22 Frag. in Consumer Prod. (cont’d) 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 Provide consumer test data to support fragrance as a “signal”Provide consumer test data to support fragrance as a “signal”

23. 23 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

24. 24 Consumer Expectations (cont’d) 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 Provide consumer research data to support olfactive expectation statementProvide consumer research data to support olfactive expectation statement

25. 25 Consumer Expectations (cont’d) 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 “Needs more fragrance” – whenever consumers like a fragrance in a panel test, and they are asked what additional characteristics they would like to have in the product, they always respond that they would like to see more fragrance. [Provide consumer test data to support this statement.]“Needs more fragrance” – whenever consumers like a fragrance in a panel test, and they are asked what additional characteristics they would like to have in the product, they always respond that they would like to see more fragrance. [Provide consumer test data to support this statement.]

26. 26 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

27. 27 Prod. Chal. for Frag. (cont’d) 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

28. 28 Why the 2% Fragrance Exemption Must Be Maintained The 2% exemption is already a significant reduction over industry’s original request for 5% The 2% figure was selected in recognition of the fact that consumer products have a very wide range of fragrance concentrations—from Household products containing 5%, to Fine Fragrances with up to 30% 2% also provided for creative flexibility for product marketers in designing future products

29. 29 Why the 2% Fragrance Exemption Must Be Maintained (cont’d) 2% was seen as a “representative” value to be applied across the entire spectrum—not product by product Especially in household products fragrance entity is seen as a “signal” for efficacy Any reduction in fragrance entity—whether to reduce VOC’s or otherwise—will only lead to the consumer using MORE product to achieve the same olfactive impact = efficacy Provide consumer test data to support concept of reduced fragrance--?increased product useProvide consumer test data to support concept of reduced fragrance--?increased product use

30. 30 Why the 2% Fragrance Exemption Must Be Maintained (cont’d) 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

31. 31 Why the 2% Fragrance Exemption Must Be Maintained (cont’d) Increased water also reduces the fragrance “lift” provided by alcohol and other similar ingredients Result: lowered fragrance perception, leading to consumer’s increased product use to achieve olfactive endpoint Increased product use means increased fragrance and increased non-fragrance VOC’s

32. 32 Why the 2% Fragrance Exemption Must Be Maintained (cont’d) 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

33. 33 Why the 2% Fragrance Exemption Must Be Maintained (cont’d) Reduction of fragrance to achieve reduced VOC attacks the very most minute part of the larger subject of VOC’s

34. 34 Thank you!