Combination Colors – Optical

Properties and Regulatory

Update

PCPC Science Symposium

October 3, 2012

2 BASF Personal Care

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

BASF Personal Care 2

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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

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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.

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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

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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

Dialogue with FDA (2010 - today)

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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

Dialogue with FDA (2010 - today)

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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

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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

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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.

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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

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Points for Discussion

Definitions

Optics

Absorption

Reflection

Interference

Diffraction

Some examples of combination pigments

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Diffuse Reflection off rough surfaces Non-directional

Reflection Types

I = Illumination

Specular Reflection off a smooth surface

Incident = Reflection

(Directional Mirror

Reflection)

S I

I

Aspecular Reflection

(Directional)

S A I

D

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Refractive Index

Light reflects from interfaces

according to:

%R=100 x (n1-n2)2/(n1+n2)

2

Refractive index, (n), of materials

Air 1.0

Water 1.33

Mineral Oil 1.5

SiO2 1.4

Borosilicate 1.52

Mica 1.58

Al2O3 1.73

TiO2 (Rutile, Anatase) 2.5

Fe2O3 2.9

Cr2O3 2.55

BiOCl 2.15

Bases

Media

Materials in media of similar refractive indices have no

interface and therefore disappear.

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.

High RI

Materials

Mica in air

Mica in oil

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Simple Reflection of Light

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

Bases

Borosilicate

Mica

PET

Color Additive

Al

Ag

Reflecting Category II Combination Pigments

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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

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Interference Pigment A simple Category II Combination Pigment structure

Mica 50-200 nm thick TiO2

50-200 nm thick TiO2

300 nm thick mica

Typical Bases

Muscovite Mica

Fluorphlogopite

Borosilicate

Al2O3

SiO2

Cosmetic color additives layered onto a base...an example

2 microns

The base and color

additive retain

their distinct layer

structure

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Examples of Some Common

Category II Bases

BiOCl

Borosilicate Based

Alumina Based

Mica Based

Natural

Mica

Silica Alumina Borosilicate Synthetic

Mica

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Category II Combination Pigments

TiO2 layered onto various bases

BiOCl

Borosilicate Based

Alumina Based

Mica Based

Silica Based

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Iron oxide coated Al Powder Category I Combination pigment

Cornflake type is less

reflective than silver

dollar type

The iron oxide

layer remains a

distinct component

on the Al particle

TEM cross-section

Iron Oxide

Al

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Low refractive index adjunct sandwiched between high refractive index color additives

Examples

Fe2O3/SiO2/Al/SiO2/Fe2O3 Cat. I

TiO2/SiO2/TiO2 Cat. II

Color range determined by refractive index of

materials and thickness of layers

Color Variable Pigment, (CVP)

Color Shifting Combination Pigments

t = 200-400 nm

I

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

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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 (TiO2

on mica) (Category II)

Mica acts as the base

Red absorption color with green interference reflection

color

High transparency

Many combinations are possible

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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

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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. TiO2 on a base

Infinite interference colors

Simple interference or color variable effects

Varying size effects

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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

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Types of Manufacturing Processes

Aqueous deposition of layers

Calcined

Non-calcined

Gas Phase deposition of layers

Physical Vapor Deposition (PVD)

Chemical Vapor Deposition

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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

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Analytical Methods for Combination Pigments

-Particle size distribution Laser beam diffraction

-Particle size and shape Scanning Electron Microscope

-Particle size and shape Transmission Electron

Microscopy

-Color Multi-angle color measurement

-Crystallographic phases Powder X-ray diffraction

-Chemical composition X-ray fluorescence

-Element analysis (heavy metal) ICP-OES, GF-AAS, HR-ICP-MS

-Density Pycnometer method

-Loss of drying ASTM D 280

-Microbiologics Microbiological examination

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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.

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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

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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.

32 BASF Personal Care

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33 BASF Personal Care