Combination Colors Optical Properties and Regulatory Update PCPC Science Symposium October 3, 2012 Outline 1 History leading to current FDA dialogue on Combination Pigments 2 Optical and Physical Properties of Combination (Effect) Pigments 3 Next Steps and Summary 2 BASF Personal Care 21 CFR listing of Mica-Based Pearlescent Pigments A petition was filed and approved by FDA for the use of some combination pigments in direct food and pharma applications 2005-06: In the 21 CFR Part 73 listing of Mica-Based Pearlescent Pigments for use in food and drugs, FDA: Treated pearlescent pigments as a composite, not a mixture of color additives and other ingredients Established approval for this composite for food & drugs, but not cosmetics 3 1
February 5, 2007 untitled letter by FDA Alleges that effect pigments are adulterated in that they are unapproved color additives for cosmetics Contends that FDA approved similar composite pigments made from iron oxide, titanium dioxide and mica as separate color additives for food and drugs (but not cosmetics) Based on Agency experience, manufacture of these pigments whereby the color is formed in situ on a substrate results in other chemical residues that must be assessed. 4 Industry dialogue with FDA (2007-2009) BASF/Merck comments to FDA in 2007 meeting: Effect pigments have been used safely in cosmetics for over 40 years in hundreds of thousands of products. Manufacturers and industry have long considered these products to be mixtures of approved color additives (and no regulatory authority treats them otherwise). International labeling nomenclature is based on this mixture principle. BASF/Merck to provide a study plan to FDA that would demonstrate effect pigments as mixtures BASF/Merck submitted effect pigment study plan to FDA in February 2008 The mixture nature of effect pigments was demonstrated, but not accepted by FDA 5 Dialogue with FDA (2010 - today) An effect pigment working group (EPWG), composed of major effect pigment manufacturers working in conjunction with the PCPC, was formed to discuss with FDA: The variety and composition of effect pigments in the cosmetic marketplace (categorization) Manufacturing/safety information Possible framework for proposed regulation changes A consensus was reached that the term combination pigments best described effect pigments 6 2
Dialogue with FDA (2010 - today) More Recent Events (2011) After some import detentions of cosmetic products containing effect pigments in mid- 2011, the PCPC and EPWG put together a proposed straw regulation and requested a meeting with FDA. The straw regulation proposed two basic groupings of combination pigments: Combination pigments are formed by binding one or more safe and suitable cosmetic color additives with i. a safe and suitable cosmetic color additive that serves as a base, with or without one or more safe and suitable coloring adjuncts, or ii. a safe and suitable cosmetic ingredient that serves as a base, with or without one or more safe and suitable coloring adjuncts. Note: safe and suitable is defined as color additives listed in Part 73,74, and 82 7 Recent EPWG/PCPC/FDA Activities PCPC March 2012 letter submitted to FDA: Provided written responses to the October 2011 questions FDA emailed to PCPC Proposed three 90-minute technical meetings with the agency to allow the EPWG/PCPC an opportunity to better describe the identity and manufacture of combination pigments FDA answered favorably, and 3 meetings were scheduled for April-June 8 April 13, 2012 EPWG/PCPC/FDA Meeting The intent of the first meeting was to educate FDA on the optical and physical properties of combination pigments Presented by EPWG/PCPC: Combination Pigment Optics (with a glossary of terms provided to FDA) Important topics presented Combinations of bases, color additives, and coloring adjuncts produce a wide variety of coloring effects Bases provide structure but not necessarily color Mixture best describes the relationship between a base, coloring adjunct, and the color additive coating Bases and coloring adjuncts serve to modify the shape, structure and shading of combination pigments while different particle sizes produce different effects. Thus one cosmetic color additive, with or without coloring adjuncts, can generate many colors and effects when combined with a base 9 3
Concepts Presented Existing color additives develop color by physics Combinations of bases, adjuncts, and a limited number of color additives produce a wide variety of coloring effects Bases provide structure but not necessarily color Mixture best describes the physicochemical relationship between a base and a coating. 10 Combination Pigments Color additives with structure Color additives in a platy form Thin layers on a base Interacting with light in different ways Infinite colors with varying color travel Many sizes and shapes 11 Points for Discussion Definitions Optics Absorption Reflection Interference Diffraction Some examples of combination pigments 12 4
Reflection Types I = Illumination I D I S Diffuse Reflection off rough surfaces Non-directional I A S Specular Reflection off a smooth surface Incident = Reflection (Directional Mirror Reflection) 13 Aspecular Reflection (Directional) Refractive Index A dimensionless number that describes how light, or any other radiation, propagates through a medium. Relates speed of light in medium to that in a vacuum. Media Refractive index, (n), of materials Air 1.0 Water 1.33 Mineral Oil1.5 Light reflects from interfaces according to: %R=100 x (n 1 -n 2 ) 2 /(n 1 +n 2 ) 2 Bases SiO 2 1.4 Borosilicate 1.52 Mica 1.58 Al 2O 3 1.73 Materials in media of similar refractive indices have no interface and therefore disappear. High RI Materials TiO 2 (Rutile, Anatase) 2.5 Fe 2O 3 2.9 Cr 2O 3 2.55 BiOCl 2.15 Mica in air Mica in oil 14 Simple Reflection of Light Reflecting Category II Combination Pigments Light interacting with a smooth reflective surface Typically a metallic cosmetic color additive like Al on a base Total specular, mirror-like, reflection Sizes from 6-70 microns, but thin Bases do not impart color Color Additive Al Ag Bases Borosilicate Mica PET θ θ 15 5
Interference Color is Defined by Thickness of the Metal Oxide Layer ( e.g. TiO2) on the Base 40-60 nm 60-80 nm 80-100 nm 100-140 nm 120-160 nm 16 Interference Pigment A simple Category II Combination Pigment structure Cosmetic color additives layered onto a base...an example Mica 50-200 nm thick TiO2 300 nm thick mica 50-200 nm thick TiO2 Typical Bases Muscovite Mica Fluorphlogopite Borosilicate Al2O3 SiO2 2 microns The base and color additive retain their distinct layer structure 17 Examples of Some Common Category II Bases Alumina Based Mica Based Natural Mica Synthetic Mica Silica Alumina Borosilicate Borosilicate Based BiOCl 18 6
Category II Combination Pigments TiO 2 layered onto various bases Silica Based Mica Based Alumina Based 19 BiOCl Borosilicate Based Iron oxide coated Al Powder Category I Combination pigment The iron oxide layer remains a distinct component on the Al particle Al Iron Oxide Cornflake type is less reflective than silver dollar type TEM cross-section 20 Color Variable Pigment, (CVP) Color Shifting Combination Pigments I Color variable or optically variable pigments have a high degree of color change with changing illumination and viewing angles due to structure and materials Low refractive index adjunct sandwiched between high refractive index color additives Examples Fe 2 O 3 /SiO 2 /Al/SiO 2 /Fe 2 O 3 Cat. I TiO 2 /SiO 2 /TiO 2 Cat. II Color range determined by refractive index of materials and thickness of layers I t = 200-400 nm 21 7
Multilayer Combination Pigments Two cosmetic color additives on one base resulting in a mixture of colors and effects Carmine layered onto a green combination pigment (TiO 2 on mica) (Category II) Mica acts as the base Red absorption color with green interference reflection color High transparency Many combinations are possible 22 Spatial Reflections The impact of size Large Sizes Large particles, (>35 microns), appear as glints or sparkles Pigment color blends seen as discrete pinpoints of confetti-like color Small Sizes More edges produce more scattering of light Color blends seen as sum of colors Blue + Gold = Silver (White) Green + Red = Silver (White) Less sparkle, more uniform color 23 Conclusions Physics Describes Optical Behavior Interference, reflection, absorption, diffraction create different effects Bases and adjuncts serve to modify the shape and structure of the combination pigments Different sizes generate additional effects One cosmetic color additive can generate multiple colors and effects when combined with a base and/or adjunct, i.e. TiO 2 on a base Infinite interference colors Simple interference or color variable effects Varying size effects 24 8
April 30, 2012 EPWG/PCPC/FDA Meeting The intent of the second meeting was to describe the various manufacturing processes used to product combination pigments, as well as the role of adjuncts. Presented by EPWG/PCPC: Combination Pigment Manufacturing Processes and Role of Adjuncts Some of the topics presented: Four general types of manufacturing processes are used to produce combination pigments Combination pigments are prepared by layering the various components to create the desired optical properties. They may be as simple as 2 layers (color additive on a base) or several layers with adjuncts The layers of a combination pigment are not bonded together by covalent bonding, but are better characterized as attraction of physisorption Tin oxide is a common coloring adjunct, used primarily as a color enhancer and stabilizer 25 Types of Manufacturing Processes Aqueous deposition of layers Calcined Non-calcined Gas Phase deposition of layers Physical Vapor Deposition (PVD) Chemical Vapor Deposition 26 June 5, 2012 EPWG/PCPC/FDA Meeting The intent of the third meeting was to cover current combination pigment specifications and control points. Presented by EPWG/PCPC: Current Industry Specifications for Combination Pigments and Analytics of Combination Pigments Some of the topics presented: Combination pigment manufacturers, through the use of the qualified raw materials of appropriate composition, manufacture safe and suitable cosmetic ingredients. QA/QC requirements are established to ensure combination pigments meet the applicable 21 CFR requirements for the color additives used (i.e. heavy metal purity) A variety of physical, optical, and elemental analytical instrumentation are used by combination pigment manufacturers in the analysis and characterization of these pigments 27 9
Analytical Methods for Combination Pigments -Particle size distribution -Particle size and shape -Particle size and shape -Color -Crystallographic phases -Chemical composition -Element analysis (heavy metal) -Density Laser beam diffraction Scanning Electron Microscope Transmission Electron Microscopy Multi-angle color measurement Powder X-ray diffraction X-ray fluorescence ICP-OES, GF-AAS, HR-ICP-MS Pycnometer method -Loss of drying ASTM D 280 -Microbiologics Microbiological examination 28 Next Planned Meeting with FDA Discussion of EPWG/PCPC s proposed regulation for combination pigments (originally submitted to FDA on September 2011) Combination pigments are formed by binding one or more safe and suitable cosmetic color additives with: A safe and suitable cosmetic color additive that serves as a base, with or without one or more safe and suitable coloring adjuncts, or A safe and suitable cosmetic ingredient that serves as a base, with or without more or more safe and suitable coloring adjuncts Safe and suitable cosmetic color additives - A color additive that is listed in parts 73,74, or 82 for use in cosmetics, is either exempt from certification or is from a batch that has previously been certified. A color additive must conform to applicable specifications in parts 73, 74, and 82. 29 Next Planned Meeting with FDA (cont.) Discussion of EPWG/PCPC s proposed regulation for combination pigments Safe and suitable cosmetic ingredients provide safe and suitable functional components to facilitate use of the combination pigments to color the human body. Safe and suitable cosmetic coloring adjuncts are substances used to preserve or enhance the color or shading of combination pigments. Examples include, but are not limited to, color stabilizers, fixatives, retention agents, and synergists Labeling: Each ingredient comprising the combination pigment shall be declared on the label of the finished cosmetic product. Solicit FDA acceptance of proposed regulation and define path forward 30 10
Summary Three technical meetings were held with FDA during the first half of 2012. The meetings covered three aspects of combination pigments: 1. physical and optical properties 2. manufacturing processes and role of adjuncts 3. analytical methods and specifications The information presented supports the position that combination pigments should continue to be considered mixtures. 31 DISCLAIMER This document, or any answers or information provided herein by BASF, does not constitute a legally binding obligation of BASF. While the descriptions, designs, data and information contained herein are presented in good faith and believed to be accurate, they are provided for your guidance only. Because many factors may affect processing or application/use, we recommend that you make tests to determine the suitability of a product for your particular purpose prior to use. It does not relieve our customers of the obligation to perform a full inspection of the products upon delivery or any other obligation. The claims and supporting data provided in this publication have not been evaluated for compliance with any jurisdiction s regulatory requirements and the results reported may not be generally true under other conditions or in other matrices. Users must evaluate what claims and information are appropriate and comply with a jurisdiction s regulatory requirements. NO WARRANTIES OF ANY KIND, EITHER EXPRESS OR IMPLIED, INCLUDING WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE, ARE MADE REGARDING PRODUCTS DESCRIBED OR DESIGNS, DATA OR INFORMATION SET FORTH, OR THAT THE PRODUCTS, DESIGNS, DATA, OR INFORMATION MAY BE USED WITHOUT INFRINGING THE INTELLECTUAL PROPERTY RIGHTS OF OTHERS. IN NO CASE SHALL THE DESCRIPTIONS, INFORMATION, DATA, OR DESIGNS PROVIDED BE CONSIDERED A PART OF OUR TERM SAND CONDITIONS OF SALE. 32 BASF Personal Care 33 BASF Personal Care 11