4-2011

English Edition International Journal for Applied Science Personal Care Detergents Specialties

E. Endlein K.-H. Peleikis

Natural Waxes Properties, Compositions and Applications

CO S M ET I C S
N AT U R A L WA X E S

E. Endlein, K.-H. Peleikis*

Natural Waxes Properties, Compositions and Applications

General Properties of Waxes

Waxes exist in form of natural and synthetic substances (Fig. 1). The natural ones can be divided into renewable and nonrenewable. The renewable waxes are regrowing and can be either chemically unmodified vegetable and animal based or can be chemically modified like f.i. hydrogenated or re-esterified types. The non-renewable fossil waxes are divided into crude or refined montan resp. petroleum waxes. Synthetic waxes exist as homo-polymers (f.i. PE, PP, PAO, FT, Oxidates) and copolymers (f.i. EAS). Due to the difficulty to find a common chemistry for all kind of waxes it is necessary to come up with an accepted general definition. As such a general definition, waxes can be defined according DGF (German Society for Fat Sciences) as a mixture of more or less hydrophobic substances of medium chain length with the following properties:

Abstract

n general waxes are always a mixture of more or less hydrophobic organic substances of medium chain length. At 20 C plastic up to hard and brittle, waxes will melt higher than 40 C up to 140 C without decomposition and will re-solidify unchanged. Solubility and consistency of waxes are strongly temperature depending. Natural waxes are derived by biogenesis in a sustainable process and are physically refined without any chemical transformation. Hence natural waxes can be considered truly as natural resp. even organic (bio) in particular cases. Natural waxes show unrivaled well-balanced compositions leading to great performances for all kind of applications and offer exceptional properties in diverse systems in cosmetic, pharmaceutical, food and household consumer goods. Especially properties refer to oil gelling and retention as well as to viscosity build-up and structuring. An array of different sensory profiles and textures can be achieved and surface gloss can be altered as well.

from soft and tacky to hard and plastic or breakable at 20 C melting points from 40 to 140 C, approx. re-solidifying unchanged after melting mostly relatively low melt viscosities sometimes buffable strong temperature dependence of solubility and consistence.

Real natural waxes according to our understanding are re-growing, derived by biogenesis in a sustainable process and

Fig. 1 Diversification of waxes

SOFW-Journal | 137 | 4-2011

CO S M ET I C S
N AT U R A L WA X E S

will be truly natural (e.g. acc. certification standards like Ecocert). In case of organic farming or certified wildflower collection they are conforming to European Directives 834/2007 resp. 2092/ 91 and USDA/NOP as well as Natrue Class 1. Natural waxes show unrivalled well-balanced compositions leading to great performances for all kind of applications. They offer exceptional properties in diverse systems in cosmetic, pharmaceutical, food and household consumer goods. Special properties refer to oil gelling and oil retention as well as to viscosity buildup and structuring. An array of different sensory profiles and textures can be achieved and surface gloss can be altered as well. Natural waxes are composed around a basic principle which is a unique mix of long-chain, linear and even-numbered aliphatic mono-esters. Partially varying amounts of linear hydrocarbons (candelilla and bees wax), free wax acids (bees wax), free wax alcohols resp. polycosanoles (shellac and carnauba wax) and other ingredients like phytosterols, natural resins etc. are also enclosed. For cosmetic applications in particular berry wax and some further more exotic waxes (myrtle, mimosa, green tea, jasmin, rose, lotus and orange blossom wax) are also of interest.

A lot of very specific characteristics arise from the usage of waxes in very different applications. Examples are the ability of

oil binding in shoe polish and lipsticks water repellency in dragees and industrial coatings release performance in bakery and plastics scratch resistance in car polish and inks platicizing in hot-melts and chewing gum lubrication in pencils and metal working dispersing in mascara and toners retard release in agriculture and pharma matrices binding properties in ceramic and cosmetic powders.

melting point (MP), often as drop melting point solidification as congealing point hardness as penetration number at 25 C acid and saponification value (AV and SV) iodine value (IV) and peroxide value (POV) differential scanning calorimetry (DSC-analysis).

Characterization
For the characterization of waxes the following properties are typical:

Using the DSC curves waxes can be classified very well by their thermal properties. These graphes give an information about the beginning and ending of the softening of the material. In Fig. 2 the DSC curves of several natural waxes (Candelilla Wax/Kahlwax 2039, Beeswax/ Kahlwax 8108 and Carnauba Wax/Kahlwax 2442L) are shown. Candelilla wax (green broken line) shows a little broader but a similar curve like carnauba wax (black unbroken line) where as candelilla wax melts somewhat lower than carnauba wax. Candelilla wax is still quite hard but much more amorphous when compared with carnauba wax. Hence tendency to break is less pronounced with candelilla wax.

Field of Applications
For applications the main properties of waxes refer to oil gelling, viscosity increasing and texturing. A lot of gellifiers (hydrocolloids) for water based systems are well known but not for oils. More or less just waxes serve this required performance. Other oil gellifiers like polymers or sugar esters will form non true crystalline gels. In mixtures of oils and waxes a special kind of crystalline structure is formed during solidification these structured oil gels are not real gels according a more narrow definition. When these structures of oil-wax-gels will be pressed or rubbed the crystals will break and melt so that as a result a smooth distribution of the oil gel on f.i. skin and hair is achieved.

Fig. 2 DSC curves of several natural waxes

SOFW-Journal | 137 | 4-2011

CO S M ET I C S
N AT U R A L WA X E S

Bees wax has a more complex melting curve (red dotted line). The softening starts already at about 35 C that means around skin temperature. Hence beeswax is quite soft and pliable. In contrast to beeswax the curve of carnauba wax shows the beginning of softening only at about 55 C but the majority of the composition melts even at much higher temperatures. Also the curve is quite narrow. Hence carnauba wax is a very hard high melting wax with a high degree of crystallinity.

Natural Waxes
In nature waxes are effective protectors against mechanical stress, water-loss, UVradiation and parasites. The permeability for gas and water vapor of the thin waxy films is essential for plants. Incorporated into cosmetics or as coatings for fruits permeability is an important factor as well. The biogenesis of natural waxes is a sustainable process. Refining of crude natural waxes is carried out in a multi-stage process. At the beginning the crude material will be molten under steam heating and cleaned by specific filtration processes to receive a so-called pre-cleaned wax. After the addition of different kind of refining additives the mixture is cleaned a second time to obtain the final fully refined wax. This process requires an in-depth knowhow which will be reflected in the very special quality products from Kahl Wax Refinery, Trittau (Germany) which are offered as Kahlwax. The basic principle of the cleaning and refining process is schematically shown in the flow chart of Fig. 3.

Fig. 3 Cleaning and refining of crude natural waxes

Fig. 4 Typical particle distribution in Kahlwax emulsions

Shapes of waxes from the range of Kahlwaxes Depending of the processing or application Kahlwaxes can be applied in the form of pellets, prills, powders and emulsions with different particle sizes. The emulsions typically contain particles with mean diameters of about 100 nm. In Fig. 4 the very narrow distribution of particles from two typical Kahlwax emulsions are shown.

Fig. 5 Prill waxes consist of beads (100-fold magnification)

(Source: Fraunhofer Institut, Oberhausen, Germany)

SOFW-Journal | 137 | 4-2011

CO S M ET I C S
N AT U R A L WA X E S

The prill waxes consist of perfectly round-shaped beads with particle sizes in the micrometer range. The picture in Fig. 5 shows a 100-fold magnification of such particles. The powdery types of the Kahlwaxes have the form of either spherical beads or are particles with finely grained fracture pattern in the lower micrometer range (Fig. 6). The renewable natural waxes can be animal derived like bees wax and shellac wax or plant derived like carnauba, candelilla, rice brain and sunflower seed wax as well as berry, fruit and flower waxes. Natural waxes can be divided into first and second generation. First generation waxes are beeswax, carnauba wax and candelilla wax. Natural waxes do not fall under REACh registration (excempted according to REACh Annex 5).

Fig. 6 Typical powdered Kahlwaxes (type P100): REM pictures with magnifications
of 250-fold (left) and 500-fold (right) (Source: Fraunhofer Institut, Oberhausen, Germany)

Genesis of Natural Waxes

Carnauba wax, candelilla wax, sunflower wax and rice bran wax are leaf and hull waxes, resp. Examples for fruit and flower waxes are berry wax and japan wax, harvested from rhus verniciflua and rhus succedanea trees in Asia, and f.i. mimosa wax. Animal derived waxes are bees wax and shellac wax.

1 kg of honey, ca. 100.000 flights over 240.000 km with the contact of roughly 15 million blossoms by the bees (apis mellifera) are necessary. From a colony with 30-70.000 bees ca. 30 kg honey p.a. and about 1 kg wax can be harvest. Organic bees wax (Kahlwax 8139) is obtained from organic honey production under strictly controlled and protocolled conditions. Organic bees wax is obtained mainly from capping wax. The product is ecocertified as Organic Food Additive according to EC 834/2007 and USDA NOP. The main cultivated bees races are showing only little differences in the composition of the bees waxes and contain:

10-15% C24-C32 free wax acids (C26 and C30 = cerin dominating) approx. 1% C34-C36 free wax alcohols 0.5-1% myristolacton.

Bees wax when freshly exuded is white and colourless but will become coloured mainly by picking up and storing pollen and honey. The crude wax is refined by an absorption technology to receive white Kahlwax 8104 (Fig. 7). The cosmetic definitions are cera flava for the yellow grade and cera alba for the white grade. The INCI name is Bees wax/Cera Alba. The properties of bees wax are:

Animal Waxes Insect Waxes

Bees wax Cera alba and Cera flava Bees wax is an exudation of the abdominal glands of the honeybee. To gather

approx. 70% C40-C52 esters of C24C34 long-chain alcohols with C16C18 fatty acids (C46, Myricylpalmitate dominating) 13-18% mainly C25-C35 hydrocarbons (C27 dominating)

relatively low melting point (drop melting point 61-65 C) moderately hard and a bit sticky plastic and kneadable at body temperature

Beeswax Crude

Beeswax Yellow

Beeswax White

Fig. 7 Bees wax in crude, yellow (Cera flava) and white (Cera alba) quality

SOFW-Journal | 137 | 4-2011

CO S M ET I C S
N AT U R A L WA X E S

non crystalline, finely grained fracture pattern excellent retention of oils with different polarities provides matt surfaces.

Plant Waxes
Carnauba Wax Copernicia Cerifera Cera Carnauba wax is an exudation of the Brazilian palm Copernicia cerifera (Fig. 8). The palm produces the wax in the cuticula of the fronds. The leaves are harvested from the wild growing trees by cutting the leaves, trying in the sun and threshing. The crude wax is refined to Kahlwax 2442 in different variations. For cosmetics several grades of carnauba wax are available as Kahlwax 2442, 2442L (food-grade) and 2442P5. Carnauba wax is available from organic harvesting as well. Refined organic carnauba wax (Kahlwax 6642) is certified according to EC-Directive 834/2007 for organic food. Fig. 9 shows the crude wax in comparison to different refined grades. In Fig. 10 the REM picture of Kahlwax 2442P5 is shown; a very fine powder with an average particle size of 5 micron. Carnauba wax has an extremely narrow melting curve with a melting point of approx. 84C. The wax is of high cristallinity and of high contraction, very hard and brittle. Carnauba wax consists of:

3-6% free wax acids 10-15% free wax alcohols 2-3% lactides 1-2% hydrocarbons 4-6% resins.

Bees wax is one of the best oil binding waxes known. Therefore bees wax is used in considerable amounts for lip stick and lip balm preparations to provide creamy textures, good adhesion to skin and well consumer accepted films. The oil gelling is also helpful to stabilise water-in-oil emulsions for skin and hair applications and to give texture build-up effects. The wax will be used for texture enhancement and volume build-up in mascara and make-up as well. Bees wax is applied in creams and ointments for viscosity build-up, in oil-based capsules and as a glazing agent in combination with carnauba wax. Bees wax is the most universal suitable wax of all natural waxes. For applications in pharma and food, bees wax is subject to different regulations and monographs: Ph.Eur. and Food Directive 95/2 as E901, US-Regulations for food (FDA 21 CFR), GRAS 184.1973 (Generally Recognized As Safe) and FCC (Food Chemical Codex).

75-85% aliphatic & aromatic (cinnamic acid based) mono- and di-esters

Fig. 8 Brazilian palm Copernicia cerifera

Shellac wax Shellac Cera Shellac is an exudation of the insect Laccifer lacca (Kerr), parasitic on certain trees. Shellac wax is mainly harvested in India and Thailand and is collected as a by-product of shellac. It is removed from the shellac to improve the clarity of alcoholic solutions of shellac. The crude wax is refined by a special absorption technology to the light coloured Kahlwax 7302L. Shellac wax consists of long- chain esters of monovalent alcohols and acids. Typical for this wax is the content of more than 30% of free wax alcohols with a chain length of C28C32. Due to the content of these alcohols it becomes very much suitable for stick preparations and emulsions, in particular mascara where amongst others it helps to disperse pigments.

CrudeT1

2442

2442K

2442L

Fig. 9 Crude carnauba wax in comparison to the cosmetic grade types Kahlwax
2442, 2442K and 2442L

SOFW-Journal | 137 | 4-2011

CO S M ET I C S
N AT U R A L WA X E S

Carnauba wax has very good emulsification properties and an excellent oil binding capacity for ester oils as well as for mineral oil. Carnauba wax raises the melting point of oil gels. Therefore it is a preferred additive in lipsticks, lipbalms and very well suitable for mascaras. It provides glossy and slippy surfaces. For pharma and food applications the types of Kahlwax 2442L, 2442P100 and 2442P5 are used as glazing agents (alone or in combination with bees wax) and as release agents (as a technical aid). It is added also to chewing gums, fruit coatings, bakery (wafer) coatings and retard tablets. For applications in pharma and food industries carnauba wax is subject to different regulations and monographs: Phar.Eu. and Food Directive 95/2 as E903, US-Regulations for food (FDA 21 CFR), GRAS184.1978 (Generally Recognized As Safe) and FCC (Food Chemical Codex). Organic carnauba wax, Kahlwax 6642, is obtained by just melting and filtration of crude untreated carnauba wax of highest quality. Its very light coloured and of a faint pleasant smell. It shows outstanding oil binding properties. Kahlwax 6642 is ecocertified as Organic Food Additive according to EC 834/2007 and USDA NOP.

Fig. 10 Particle structure of carnauba wax: REM picture of Kahlwax 2442P5

(Source: Fraunhofer Institut, Oberhausen)

tion, important for the demoulding of lipsticks. Kahlwax 2039L is peroxide-free, gives a fully transparent melt without any resinous residues. Kahlwax 2039L en-

hances oil binding and provides excellent sensory properties. As an additive in food and pharma it is a glazing agent for chiclets, used in chewing gums and in pharmaceutical tablets. It is regulated acc. Ph.Eur. and as direct food additive according to EU Regulation Food-Additive (95/2) as E902 and acc. US-Regulation (FDA 21 CFR): GRAS 184.1976 and FCC (Food Chemical Codex)

Candelilla wax Candelilla Cera Candelilla wax is an exudation of the wild plant euphorbia cerifera (antisiphilitica) which is located in the northern Mexican desert (Fig. 11). The wax is obtained from the upper earth part of the plant. The weed is dried, boiled with water and the wax is then skimmed off by decanting. The dark brown crude candelilla wax is refined to a pale yellow wax to the type Kahlwax 2039 and 2039 L, resp. (Fig. 12). Candelilla wax has a remarkable hardness but little crystallinity. It shows some tackiness at higher temperatures. The melting point of about 72 C is in between bees and carnauba wax. The content of resins and sitosterols together with the esters are responsible for the excellent oil binding for ester oils (in particular Kahlwax 2039 L). The wax provides high surface gloss when applied in lipsticks and serves sufficient contrac-

Fig. 11 Mexican plant euphorbia cerifera

Sunflower wax Helianthus Annuus Seed Cera The wax is obtained from Sunflower oil by a special winterisation technology. The crude wax is refined to Kahlwax 6607 L. It is a non chemically treated, saturat-

Crude

2039

2039 L

Fig. 12 Crude candelilla wax in comparison to the refined types Kahlwax 2039 and
2039L

SOFW-Journal | 137 | 4-2011

CO S M ET I C S
N AT U R A L WA X E S

ed, high melting and light coloured wax. By chemistry it is a long chain (about C60) wax ester from monovalent alcohols and acids mainly. Minor components like alcohols are not important. The melting point is about 80 C. Sunflower wax forms hard and very homogen thermally stable oil gels and is therefore excellent suitable for lightcoloured, practically odourless and tasteless lipbalms, lipsticks and other oil gels. Sunflower wax shows a narrow melting curve with no molten contents below 55 C. Therefore the oil gels are very well heat resistant.

Rice bran wax Oryza Sativa Cera By winterisation of rice oil the crude rice bran wax is obtained. Like sunflower wax the main components are long-chain wax esters. The chain lengths of the esters are also around C60. Although it is by chemistry very similar to sunflower wax, applications are quite different. Refined Rice bran wax has a very hydrophobic character. It forms soft oil gels and is therefore highly preferred for emulsions like mascaras and skincare products. It serves a much less sticky texture than bees wax in W/O-emulsions.

Fig. 14 Improvement of the texture of O/W emulsions with berry wax

Berry wax contains:

90% glycerolesters of C16-C18 fatty acids 2-5% glycerolesters of C20-C22 dicarboxylic acids (so-called Japonic Acids) 5% free fatty acids and alcohols.

Berry wax from Rhus Verniciflua Peel Cera Berry wax, Kahlwax 6290, is extracted from an Asian fruit of the tree rhus verniciflua (Fig. 13). The wax consists mainly of saturated triglycerides. The specific performance of Kahlwax 6290 results from the content of glycerol esters of a C20-C22 dicarboxylic acid.

Fig. 13 Fruits and leaves of the Asian

tree Rhus verniciflua

Kahlwax 6290 is of off-white colour and 100% vegetable based. A significant part of berry wax already melts below 30 C and gives therefore a very silky and soft feeling to the skin like a classical emollient. On the other hand berry wax shows very little to almost no crystallinity leading to very soft but significant textures in creams (whipped cream like). Kahlwax 6290 is the preferred additive for skincare emulsions to improve significantly texture and sensory behaviour of O/W emulsions (Fig. 14). Berry wax is an excellent additive for oil gels to be used in lipsticks (pay-off enhancer), mascaras and similar products and is well suited for lipgloss formulations as well. The content of relatively high molecular weight glycerol esters from the so called Japonic Acids makes Kahlwax 6290 to the preferred ingredient of pencil formulations, e.g. lipliner or eyebrow pencils. Although soft it improves the break resistance of pencils.

Excotic waxes From the range of exotic natural waxes the following types from Kahlwax are available on demand: myrtle wax (6269), mimosa wax (6602), green tea wax (6640), jasmin wax (6684), rose wax (6692), lotus wax (6694) and orange blossom wax (6699). All these flower and leaf waxes are showing very special performances but are only of limited availability.

* Authors address: Dr. Edgar Endlein K.-H. Peleikis Kahl GmbH & Co. KG 22946 Trittau Germany Email: e.endlein@kahlwax.de

SOFW-Journal | 137 | 4-2011