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Productos Claros: formulación Transparente de Aceite

en Dispersión de Agua
Posted on May 26, 2017 by George Deckner — Leave a Comment

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Copyright: naphotos / 123RF Stock Photo

Formulación transparente de aceite en dispersiones de agua puede ser una de las


áreas más desafiantes en la ciencia cosmética. También es un área que
probablemente haya tenido más interés y preguntas de seguimiento de cualquier
artículo que haya publicado en los últimos tres años.1

Técnicamente, hay dos tipos de dispersiones que se conocen como "soluciones" de


acuerdo a los químicos cosméticos: isótropos y micelulares.

Las soluciones isotrópicas son mezclas homogéneas de dos o más ingredientes


en los que las partículas del aceite o soluto se solubilizan en un disolvente sin el uso
de tensoactivos.

Las soluciones micelulares transparentes son dispersiones acuosas que usan


tensoactivos y / o disolventes para reducir el tamaño de gota de aceite a <50
nanómetros.

Las micelas son estructuras organizadas que los surfactantes forman en el agua.
Este punto se conoce como concentración crítica de micelas o CMC.

Concentración crítica de micelas (CMC), estas estructuras rodean los ingredientes


hidrófobos, como fragancias y aceites, y pueden formar dispersiones claras si se usa
el tensoactivo correcto y a una concentración lo suficientemente alta.

Estas emulsiones típicamente tienen un tamaño de partícula de aproximadamente 5-


10 nanómetros y solo deben usarse cuando se emulsiona una fase oleosa altamente
polar como una fragancia.
Las dispersiones micelulares también se pueden formular usando niveles más bajos
de surfactante, si se usa energía mecánica de alto cizallamiento para reducir el
tamaño de partícula. Sin embargo, normalmente tienen un tamaño de partícula más
grande.

Las microemulsiones son un tercer tipo de dispersión micelular que requiere


concentraciones más altas de surfactante versus las soluciones micelares típicas. 2

Las microemulsiones, a diferencia de las soluciones micelulares típicas, son


dispersiones termodinámicamente estables con un tamaño de partícula de <50
nanómetros que se forman instantáneamente con una mezcla simple.

Son sistemas de baja viscosidad que contienen una fase acuosa, fase oleosa, agente
tensoactivo y un cotensioactivo. El cotensioactivo, típicamente es un poliol o alcanol
insoluble en agua, ayuda a reducir la tensión interfacial que disminuye el tamaño de
las gotitas dispersadas.

Otras formas de formular emulsiones claras de aceite en agua incluyen ajustar el


índice de refracción del aceite con el de la fase acuosa y la encapsulación molecular
usando ciclodextrina (CD). La comparación del índice de refracción normalmente
requiere un emulsionante y el uso de altas concentraciones de poliol. Esto solo
funciona bien con ciertos tipos de aceites que tienen un índice de refracción cercano
al del agua.

Estas emulsiones también requieren un espesante para ayudar a mejorar la


estabilidad ya que su tamaño de partícula es típicamente> 100 nanómetros. Los
complejos claros de CD solubles en agua requieren el uso CD altamente solubles en
agua de formas como alfa, gamma o hidroxipropilo CD y solo funcionan para
ingredientes que se unirán dentro de la estructura. La proporción típica de CD a
ingrediente complejo es de 5-10 partes de CD por cada 1% de ingrediente complejo,
dependiendo del tipo de ingrediente utilizado y el peso molecular.

Factores principales que influyen en la formación / estabilidad de la emulsión

 Los aceites de polaridad alta como la polaridad del petróleo como las
fragancias son mucho más fáciles de solubilizar que los emolientes. Por
ejemplo, 10 gramos de tensoactivo pueden solubilizar de dos a tres gramos de
aceites de fragancia y solo de 0,2 a 0,5 gramos de aceites no polares.
 Al solubilizar aceites, comience con una proporción de 20 partes de
solubilizante por una parte de aceite.
 Para las fragancias, comience con cinco partes de solubilizante por una
parte de aceite de fragancia y reduzca el solubilizante hasta que la
emulsión se vuelva turbia.
 Pruebe soluciones claras hechas usando varias proporciones de
solubilizante a aceite a 4 ° C y 45 ° C para determinar la estabilidad óptima.
 Tipo y concentración de surfactante: use combinaciones de surfactantes para
una mejor eficiencia.
 Los solventes-solventes como etanol, propanodiol y PEG 8 a menudo pueden
reducir la cantidad de surfactante que se necesita.
 Maduración de Ostwald describe el crecimiento del tamaño de partícula a lo
largo del tiempo y es una de las principales causas de la inestabilidad de la
emulsión clara de aceite en agua. Típicamente, la emulsión comienza clara y
se vuelve turbia con el tiempo. Este fenómeno es el resultado de la diferencia
en la solubilidad del aceite inmediatamente fuera de las micelas pequeñas y
grandes.
 Para reducir la maduración de Ostwald, se requiere una distribución de
tamaño de partícula estrecha. A medida que las micelas se someten a la
maduración de Ostwald, la concentración del aceite insoluble aumenta a
medida que el aceite más soluble migra de la micela.
 El equilibrio se alcanza en algún punto, deteniendo la maduración adicional
de Ostwald. Típicamente, la adición de una pequeña cantidad de aceite no
polar es suficiente para limitar la maduración de Ostwald.
 Los polímeros modificados hidrófobamente también pueden ser útiles para
estabilizar la interfaz contra la maduración de Ostwald.

Solubilizadores recomendados para fragancias

 El principal solubilizador histórico de referencia es el aceite de ricino


hidrogenado PEG 40 (Cremophor RH 40-BASF)
 Eumulgin HPS (PEG-40 Aceite de ricino hidrogenado, PPG-1-PEG-9 Lauril
Glicol Éter-BASF, Coceth 7-BASF)
 COSMACOL N II-9 (C12-C13 Pareth 9-Sasol)
 Brij IC20 (Isoceteth 20-Croda)

Opciones Verdes Recomendadas

Los siguientes no contienen surfactantes basados en óxido de etileno para


fragancias.

 TEGO Solve 61 (Polyglyceryl-6 Caprylate, Polyglyceryl-4 Caprylate,


Polyglyceryl-4 Cocoate, Polyglyceryl-6 Ricinoleate-Evonik)
 TEGO Solve 55 (Polyglyceryl-3 Caprylate / Caprate / Succinate, Propylene
Glycol-Evonik)
 Sepiclear G7 (Heptyl Glucoside, 70% sólidos-Seppic)
 Poly Suga Mulse D9 (Polímero Cruzado de Decylglucoside Oleate Sorbitan,
64% sólidos-Colonial Chemical)
Enfoques de microemulsión
 Caprol Micro Express (PEG 6 Caprylic / Capric Glycerides, Polyglyceryl-6
Dioleate, Glyceryl Caprylate / Caprate-Abitec): solo agregue su emoliente y
agua para formar una microemulsión.
 Formulación de microemulsión base - agua DI 16%, glicerina 15%, emoliente
47%, poliglicerilo 10 diisoestearato 12%, poliglicerilo 10 diisoestearato 10%
(formulación base Dr Straetmans)
 30% de laurato de sucrosa (Ryoto Sugar Ester L-1695-Mitsubishi Kagaku
Foods), 20% de glicerol, 50% de aceite forma una microemulsión
transparente.

Referencias:

1. Solubilizing Oils into Water


2. Microemulsions Explained

The views, opinions and technical analyses presented here are those of the author,
and are not necessarily those of UL, ULProspector.com or
Knowledge.ULProspector.com. While the editors of this site make every effort to
verify the accuracy of its content, we assume no responsibility for errors made by the
author, editorial staff or any other contributor. All content is subject to copyright and
may not be reproduced without prior authorization from Prospector.
Solubilización de aceites en el agua
Posted on January 23, 2014 by George Deckner — 65 comments

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Creé la siguiente guía para solubilizar aceites en agua para ayudarlo en sus formulaciones. Aquí,
cubro los conceptos básicos y le doy sugerencias de formulación y producto.

Las dispersiones micelares son el tipo más común de dispersiones transparentes de aceite en
agua que usan surfactantes y / o solventes. Si el tamaño de partícula de la fase dispersa es <100
nm, la dispersión normalmente aparece clara. Típicamente, estas dispersiones se usan para
solubilizar aceites de fragancia en productos basados en agua y tienen un tamaño de partícula de
~ 5 nm.

Consejos de Formulación:

 Generalmente, los aceites más polares son más fáciles de solubilizar en agua y
requieren menos surfactante. Por ejemplo, 10 gramos de polisorbato 20 pueden
solubilizar ~ 1-3 gramos de aceites de fragancia y solo 0,1-0,3 g de aceites no
polares.(UE: polisorbato 20)
 Al solubilizar la mayoría de los aceites, comience con una proporción de 10 partes de
solubilizante por 1 de aceite y disminuya la titulación. Para las fragancias, comience
con 5 partes de solubilizante por 1 parte de aceite de fragancia.
 Los solubilizadores líquidos son preferidos frente a los tipos sólidos debido a la
facilidad de procesamiento.(UE: solubilizadores líquidos)
 Los solventes solubles en agua, en los que se disuelve el aceite, pueden ayudar a
reducir la cantidad de solubilizante que se necesita.
 Los solventes generalmente pueden ayudar a reducir la cantidad de solubilizante que
se necesita. 1, 2 hexanodiol es de lejos el mejor, seguido de 1, 2 pentanodiol,
dietilenglicol mono etil éter y dimetil isosorbida. (EU: 1, 2 hexanodiol | 1, 2 pentanodiol
| dimetil isosorbida)
 Use combinaciones de solubilizantes para una mejor eficiencia. Muchos de los más
eficientes son mezclas de surfactantes.
 Supervise los cambios en la distribución del tamaño de partícula (analizador de
tamaño de partícula submicrónico) a lo largo del tiempo utilizando pérdida de claridad
o cambios en el tamaño de partícula como puntos finales.
 Generalmente, Maduración de Ostwald puede causar una pérdida de claridad o un
cambio de tamaño de partícula a lo largo del tiempo. Agregar una pequeña cantidad
de aceite no polar o un surfactante polimérico puede ser útil para minimizar el
problema.

Solubilizadores Recomendados:

 El principal solubilizante histórico de referencia es PEG 40 aceite de ricino


hidrogenado (Cremophor RH 40 - BASF) (UE: PEG 40 aceite de ricino hidrogenado)
 Eumulgin HPS (PEG-40 aceite de ricino hidrogenado, PPG-1-PEG-9 lauril glicol éter -
BASF, Coceth 7 - BASF) (EU: Eumulgin HPS)
 Cosmacol N119 (C12-C13 Pareth 9-Sasol) Opciones verdes recomendadas que no
contienen tensioactivos a base de óxido de etileno
 Sophogreen (agua, glucosa, ácido graso de semilla de colza)
 Sepiclear G7 (Heptyl Glucoside-Seppic)

The views, opinions and technical analyses presented here are those of the author, and are not
necessarily those of UL, ULProspector.com or Knowledge.ULProspector.com. While the editors of
this site make every effort to verify the accuracy of its content, we assume no responsibility for
errors made by the author, editorial staff or any other contributor. All content is subject to
copyright and may not be reproduced without prior authorization from Prospector.
Oil in Water Nano-emulsions
Posted on July 11, 2014 by George Deckner — 6 comments

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Typically characterized by their clear or bluish/translucent appearance, oil in water nano-


emulsions are water continuous colloidal dispersions that have a particle size distribution of
around 20-200 nm. These nano-emulsions are very stable to creaming due to Brownian motion.

Nano-emulsions can be formed by using either low or high energy processes. The phase
inversion temperature (PIT) method is a low-energy process based on the changes in solubility
of polyoxyethylene (EU) type of nonionic surfactants with temperature. These surfactants become
lipophilic with increasing temperature because of dehydration of the polyoxyethylene chains. PIT
emulsification takes advantage of the extremely low interfacial tensions achieved at inversion
temperature. Above this temperature, a water in oil emulsion is formed which becomes a
bicontinuous emulsion at the inversion temperature and an oil in water nano-emulsion below.

D phase emulsification is a low-energy process to make nano-emulsions that involves mixing a


surfactant with a polyol (EU) or with a polyol and a small amount of water. Oil is then added and a
gel is typically formed (oil in polyol-water emulsion). When additional water is added, an oil in
water nano-emulsion is formed. Heating both phases prior to mixing helps promote a smaller
particle size due to a lowering of the interfacial tension. The likely mechanism is the formation
before dilution of a lamellar liquid crystalline phase.

High-energy approaches use equipment capable of generating intense disruptive forces to break
up the oil phases. The most widely used include high-pressure valve homogenizers, micro-
fluidizers, and sonication methods. Generally, conventional high-pressure homogenizers work in a
range of pressures between 50 and 100 MPa.

Applications

 Stable thin emulsions for sprays or wipes


 Improved active skin penetration
 Improved deposition of emollients in rinse off products

Commercial technologies

 Nanocream (15%-Potassium Lauroyl Wheat Amino Acids, 25%-Palm Glycerides, 20%-


Capryloyl Glycine, 40%-Water-Sinerga)
o Using 10% different oils and 5% Nanocream emulsions with a particle size of 120-
320nm were produced.
o Using 10% Coco Caprylate/Caprate and 2.5-10% Nanocream the particle size ranged
between 120-250nm.
o Cold mix 5% Nanocream and 10% oil and heat to 40-45C. Start heating until the mixture
forms a homogeneous clear phase. Heat 25-30% (w/w) of water to the same temperature.
Slowly add small increments of water phase to the mixture until a viscous gel is obtained.
The formation of bluish color is typical of the nano particle size droplets and must be
obtained in this step. Mix at least for 5 minutes again. Add the remaining water phase and
continue stirring for 5-6 minutes.
 Sucrose C1215L (Sucrose Laurate-Mitsubishi-Kagaku Foods)
o 20% C1215L is dissolved using 30% glycerin and heated to 75C. 50% oil is heated to
75C and is slowly added to the glycerin/surfactant. A nano emulsion will form on water
dilution.
 Tego Wipe DE PF (EU) (Diethylhexyl Carbonate; Polyglyceryl-4 Laurate; Phenoxyethanol,
Dilauryl Citrate-Evonik (EU))
o Forms a nano-emulsion when diluted with water.
 Expired patent US 5362418 (Kao-11/8/94) claims a gel-like oil in water concentrated
emulsion can be prepared by adding an oil to a mixture of a monoalkyl phosphate salt,
polyhydric alcohol and water. Very fine oil in water emulsions can be formed with very little
surfactant and without high shear by diluting the gel (50nm particle size-3 to1 ratio oil to
surfactant, 265 nm-350 to 1 ratio) with water. The lead surfactant was a high mono
myristyl phosphate neutralized using arginine dissolved in glycerin/water. This is a very
useful technology for making nano emulsions. High mono alkyl phosphates are
commercially available.

The views, opinions and technical analyses presented here are those of the author, and are not
necessarily those of UL, ULProspector.com or Knowledge.ULProspector.com. While the editors of
this site make every effort to verify the accuracy of its content, we assume no responsibility for
errors made by the author, editorial staff or any other contributor. All content is subject to
copyright and may not be reproduced without prior authorization from Prospector.
Water: An Important, Unusual, Personal Care
Ingredient
Posted on January 27, 2017 by George Deckner — 5 comments

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Copyright: zven0 / 123RF Stock Photo

Water is the most important, unusual, and underappreciated ingredient used in personal care. It is
also one of the most peculiar materials found in nature with over 74 reported scientific anomalies1.
Many these anomalies are due to the ability water to form short-lived hydrogen bond connections.

Water is a colorless, odorless, liquid with an exceptionally high boiling and freezing point for its
molecular weight. It has a molecular weight of 18 and is comprised of Oxygen covalently bonded
to two Hydrogen atoms. It is the only known material that can co-exist in a solid, liquid, and
gaseous state.

Physicists have also demonstrated that somewhere between 40 and 60°C, liquid water can
change states, exhibiting different properties depending on what form it switches to2. The
crossover temperatures were approximately 64°C for thermal conductivity, 50°C for refractive
index, 53°C for conductivity, and 57°C for surface tension.

A research team led by Gerald Pollack from the University of Washington in 2010 discovered what
they referred to as exclusion zone (EZ) water3. Molecules of liquid water near hydrophilic surfaces
are arranged in a hexagonal crystal lattice and have properties dramatically different then
conventional water. These include having a UV absorption at 270 nm, more viscosity, and a
different refractive index. It is believed that all water found in living cells is in the form of EZ water.
This form promotes protein conformation/folding and many of the redox reactions critical for life to
exist4.

Recently scientists at MIT discovered that if you confine water in a Carbon nanotube, its freezing
point can be dramatically increased to over 105°C7.

A recent controversial phenomenon is the reported ability of water to retain a memory of objects
placed in it. When flowers are placed in water and removed and the water is flash cooled, it
exhibits a unique crystal pattern dependent on the type of flower used5. Several researchers have
made similar memory claims but their experiments often can’t be reproduced6.

Apart from Mercury, water has the highest surface tension of all liquids1 and is one of few known
substances that expands when frozen and can float on top of its liquid state. Water reaches its
maximum density at 4°C, causing water to freeze from the top down. If water froze from the
bottom to the top, most aquatic life could not survive on Earth.

More than 100 years ago Michael Faraday discovered that a thin film of liquid-like water is present
at the surface of frozen ice that is well below 0°C. This water has very different properties than
normal water. This film also makes ice slippery and is crucial for the motion of glaciers8.

Water in personal care formulations

Water is an ideal carrier for personal care formulations, as it is inexpensive, safe, and readily
available. It also is one of the best known solvents, dissolving a wide range of materials due to its
high polarity (dielectric constant), and low molecular weight.

Deionized or USP purified are the most common grades of personal care water and are typically
tested for total organic carbon (TOC), conductivity, pH, and microbiological count. This type of
water is normally produced either by distillation or using a mixed bed ion exchange column.
Additional processing such as UV irradiation is also normally employed to insure a low
microorganism count.

The top 10 water anomalies1

 Water co-exists in the solid, liquid, and gaseous state and can sublime under pressure
from the solid to the gas state (freeze drying).
 Water has an unusually high melting/freezing point and expands on freezing.
 Water has an unusually high boiling point.
 Water has a very high surface tension.
 Water is most dense at 4°C and frozen water floats on top of liquid water
 Water has an exceptionally high specific heat capacity which means it requires a lot of
energy to raise its temperature by a given amount.
 Water has very low compressibility.
 The speed of sound in water increases with temperature up to 74°C, after which it starts to
fall again.
 Water molecules diffuse more easily, not less easily, at higher pressures.
 Water becomes less viscous, not more viscous, at higher pressures.

References

1. “Anomalous properties of water”


2. “Physicists just discovered a second state of liquid water”
3. The Fourth Phase of Water: Beyond Solid, Liquid, and Vapor by Gerald Pollack
4. Cells, Gels, and the Engines of Life by Gerald Pollack
5. “Water Theory”
6. “’Water memory’ – a myth that wouldn’t die”
7. “Researchers discover astonishing behavior of water confined in carbon nanotubes”
8. “How does water melt? Layer by layer!”

The views, opinions and technical analyses presented here are those of the author, and are not
necessarily those of UL, ULProspector.com or Knowledge.ULProspector.com. While the editors of
this site make every effort to verify the accuracy of its content, we assume no responsibility for
errors made by the author, editorial staff or any other contributor. All content is subject to
copyright and may not be reproduced without prior authorization from Prospector
Beyond H2O: Defining Different Types of
Water
Posted on January 19, 2018 by Perry Romanowski — Leave a Comment

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When formulating at my previous company, the


type of water used was never something I thought about much. In the lab, we had a benchtop
water deionizer and used it whenever making aqueous formulas. Of course, not everyone has one
of these devices and there are other water options you should know about. The different types of
water used in formulating cosmetics include tap, distilled, deionized, and purified) water. Here are
some water type definitions.

Looking for water for your personal care formulations?


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Tap water
Tap water comes from municipalities and is suitable for many types of cosmetic products. But
when you get the water right from the city water supply, it’s filled with a small amount of metal and
mineral ions. Often this will not have any effect on your cosmetic formula, but it can be a problem
especially if you are using any soap-based ingredient. Since this type of water doesn't allow you
to control the level of ions in the formula, it’s best to use something that is more purified.

Distilled water
Distilling is the oldest method for purifying water. In this process water is boiled in a still. The
vapor is collected in a condenser and cooled to reform the water. Theoretically, it removes all
traces of contaminants except those that boil at a temperature lower than water, such as some
alcohols. It also will absorb Carbon Dioxide from the air so the pH will typically be lower (pH 4.5 –
5.0). This is suitable for most any type of formulation but can be inconvenient if you have to
produce it.
Deionized water
This is water in which the non-water related ions have been removed. Tap water is usually filled
with ions from the soil including sodium, calcium & magnesium plus metal ions from the pipes
such as iron and copper. It is deionized by sending it through an ion exchange column, which is a
tube that contains a resin that selectively binds with ions in water. Ionized water goes in and
deionized water comes out. This process doesn’t remove organic contaminants, viruses or
bacteria. This water is suitable for most any formulation and can be produced quickly.

Demineralized water
This water is sent through an ion exchange process and is pretty much the same as deionized
water. From a formulation standpoint, there is no difference.

Ultrapure water
When you want just pure H2O, this is what you want. The water is first demineralized, then sent
through an electrodeionization process. This is great for electronics and pharmaceuticals. It’s
probably over-kill for cosmetics.

There you have it, all the different water types you might use when making cosmetic formulas.
One final note: no matter which type of water you use when making a cosmetic, the only proper
way to list it is on the ingredient list is WATER or AQUA.

Further reading:
 Water: An Important, Unusual, Personal Care Ingredient
 Formulating Clear Oil in Water Dispersions
 Oil in Water Nano-emulsions
 Solubilizing Oils into Water

The views, opinions and technical analyses presented here are those of the author, and are not
necessarily those of UL, ULProspector.com or Knowledge.ULProspector.com. While the editors of
this site make every effort to verify the accuracy of its content, we assume no responsibility for
errors made by the author, editorial staff or any other contributor. All content is subject to
copyright and may not be reproduced without prior authorization from Prospector.

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