2006 ANNUAL SCIENTIFIC MEETING 73
Investigating and Identifying Factors Affecting Emulsion Quality
Precise control of chemical composition in the production batch is crucial, as inaccurate weighing or
the use of the wrong raw materials can certainly cause variations in many important chemical/physical
properties related to product quaJity and shelf life. Equally important, however, are "Process Variables,"
which can also exert strong influence on perceived product quality. Most cosmetic emulsions on the
market are processed by a batch process, using kettles and mixers. By nature, batch processing is
accompanied by numerous process variables which are difficult to control precisely, and which may affect
emulsion quality. Process variables are those variables introduced during the manufacturing process
including emulsification temperature, mixing speed, the rate and the order in which the two phases are
combined, cooling rate and even filling speed. Depending on the type of product and formulation, some
process variables can be very important while others may be insignificant. Better control of process
variables can often be attained by adopting a continuous process, but this method is not often used in
cosmetic production because of the high engineering and equipment costs and the lack offlexibility.
Understanding the Nature of Emulsion Products
One reason why so many emu1sion products are tricky to manufacture and pose difficu1ty in controlling
the quality of every batch is that most emulsions, except microemulsions, are non-equilibrium systems.
As such, they are subject to the Second Law of thermodynamics and there is a strong tendency for the oil
phase to become separated from the water phase, even when surfactants and polymers are used to retard
this process. In general, a non-equilibrium product such as an 0/W cream, consisting of incompatible oil
and water phases, is much more susceptible to process variables and more troublesome to process than is a
single phase product like a toning lotion consisting mainly of water and ethanol in an equilibrium state.
Many process variables, such as shear stress from mixing and even the speed of adding one phase to
another, if not carefully controlled, can affect emu1sion properties and shelf life. Thus, a 1000 gram
sample of a new cream made in a beaker in the product development laboratory may have a shelf life of 3
years while the first production batch from the same formula, produced in a I 000 gallon tank, may end up
having only a 6-month shelf life. If the shortened shelf life is not detected before shipment, a costly
product recall could result. Scaling-up of a new product from the laboratory to production is a very
important step in prudent emulsion product development and carefully controlled piJot batch experiments
go a long way in preventing production disasters.
Manufacturing Trouble Prevention Program
To avoid problems in manufacturing a new emulsion formulation, it is essential for the development
chemists, quality control staff and process engineers to work together to develop an effective trouble
prevention program. Early detection and identification of potential manufacturing problems is crucial.
The product development chemists in charge of the new product should be alert to communicating
potential processing problems to the QC and engineering staff. Since each emulsion formulation is
unique and may be affected differently by different process variables, it is often advisable to carry out pilot
process experiments to determine the best way of processing and scaling up a new emulsion.
The importance of staff training cannot be overemphasized in our fast-changing industry. Companies
are expanding production by installing larger kettles and bigger mixers. Changing batch size often means
introduction of many process variables which can affect product quality and stability. It is not surprising
that some emulsions made in a new larger kettle can often produce batches having lower quality or
shortened shelf life. An experienced staff may be able to detect signs pending trouble from the appearance
of a batch sample and take corrective, or at least cautionary action. Proper staff training and open
communication among manufacturing staff, QC and development chemists are very important in
formulating a sound strategy for trouble-free manufacturing of cosmetic emulsions.
References
(1) T. J. Lin, Rheology Fundamentals and Applications in Cosmetics Formulation, Manufacturing and
Quality Control, The Chemistry and Manufacture of Cosmetics, M. L. Schlossman, editor, Allured
Publishing Corp. volumel, pp 341-371 (2000)
74 JOURNAL OF COSMETIC SCIENCE
OPTIMIZING PERFORMANCE WHEN USING POLYMERS
IN SURFACTANT·8ASED CLEANSING PRODUCTS
Alan Suares, Patrick McCoy, Michael Myers, Steven Smith,
Julie Castner, Daniel Hasman and Julie Shlepr
Noveon., Inc., a wholly owned subsidiary of The Lubrizol Corporation
9911 Brecksville Road, Brecksville, OH 44141
Introduction
Acrylate polymers are widely used in surfactant cleansing systems for rheology modification,
suspension and stabilization. These polymers can enhance sensory properties, such as product appearance,
te.1ure. pourability and flow. ease of spreading and distribution and skin feel -propertiescriticaltosuccess
in the marketplace. Further. they offer advantages vs. salt thickening and other rheology modifiers in
improved flow (smooth vs. stringy or sticky) and appearance, suspension and stabilization.
Staying ahead in today's marketplace requires focus on creating the best formulations and on efficient
production, especially for high volume, high throughput products like shampoos, body washes and liquid
soaps. Critical decision points include total surfactant actives concentration and the type of surfactants to
be used desired pH: desired viscosity and flow characteristics the need for suspension of insoluble
particles whether the finished product is to be clear or opaque anticipated processing conditions and
storage and handling capabilities.
The objective of this work is to assist formulators and process engineers in the scale-up and
manufacturing of surfactant-based cleansing products which employ polymeric rheology modifiers.
Polymer properties. thickening mechanisms, formulating conditions and processing parameters most
critical to optimizing perfonnance and throughput are presented for:
TraditionaL highly crossJinked polyacrylic acid (PAA) polymers
Hydrophobically-modified. crosslinked acrylate copolymers such as Accylates/Cl0-30 Alkyl
Acrylate Crosspolymer
Liquid rheology modifiers such as Acrylates Copolymer
Liquid, hydrophobically-modified. amine functional and crosslinked Polyacrylate-1 Crosspolymer
General Polymer Properties
General polymer properties in formulations are presented in Table I, showing physical form, flo�
profile. relative viscosity. relative yield value, clarity, relative ion tolerance and relative shear tolerance.
Thickening and stabilization mccban" in rfactaat sy ems
Traditional crosslinked PAA polymers build viscosity through charge-ihdua;d polyelectrolyte chain
expansion and hydrogen bonding. This creates a network of swollen, microgels
tightly packed in close contact ('"space-filling mechanism"). It is well known
through the literature• that dri\ing forces in polymer-surfactant interactions
include hydrophobic modification and electrostatic interaction. In cleansing
formulations. microge1 interactions are influenced by the presence of surfactant
micelles which also occupy space in the solution. Anionic surfactant micelles
repel anionic polymer microgels. thus reducing contact and viscosity. A high
relative viscosity and yield value profile can deliver adequate thickeningandstabilization. 1bese polymers
can form hydrogen bonds with formulation ingredients such as EO and/or PO nonionic surfactants, fatty
acids and polyols. Thickening occurs over time through the fonoation of large, cooperative structures, but
rarely affects final formulation.
With Acrylates/C 10-:-30 Alkyl Acrylate Crosspolymer, thickening occurs upon neutralization due to
charge repulsion (hydrodynamic volume expansion). Again, ii is primarily the physical packing of polymer
microgels which provides viscosity and suspending capabilities. This polymer has moderately high ion
tolerance and thus. maintains good integrity in the presence of electrolytes.
Though not associative by chemistry. Acrylates Copo]ymer shows unique behavior.·Itinteracts with
surfactant systems in a way that is pH dependent. Thickening occurs via hydrodynamic volume expansion
and through interaction with surfactant micelles. The resulting three-dimensional networlc. enables
viscosity to be maintained in the presence of higher electrolyte content. The polymer builds viscosity at pH
6. but in the presence of typical anionic and amphoteric surfactaJ ts, a patented ""back-.acid thickening"
mechanism enables viscosity and suspension to be increased through the addition of an acid, like citric
acid. The polymer offers synergistic thickening with surfactants and salt.
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