Colloids and Surface Phenomena

Aspects of Makeup and Lipstick

Group 6

CHAIN, KOK KEONG

LE, DIEUHANH THI

MCLAUGHLIN, KELLY E

VAN NATTER, RAINEE M

Date: 9^th April 2002

Introduction

In recent years, the rise of the worldwide living standard has created a path for the increasing use of cosmetic products. The featured article by the R & D in the Cosmetic Age has reported that the global personal care market that includes skin care, makeup, hair care and fragrance products is estimated to be $125 million. The consumer demands that cosmetic products be high quality, safe for daily application without creating any long or short term side effects to skin, reasonably priced to be affordable by the working class, containing ingredients that have multiple abilities and two in one formulations, and long-wearing by resisting moisture. In order to meet these challenges, application of polymers and surfactants play an important role in modern cosmetic products. The functions involve the encapsulation of the active ingredients for later release, lowering the surface tension between the materials and skin, aiding in firm distribution of the cosmetics ingredients, promoting adhesiveness, and reducing allergic reaction with skin. Cosmetics vary greatly in formulation and this creates differences in texture, color, and physical and chemistry properties. In general, cosmetics ingredients are classified into vehicle group and active ingredients. Vehicles are spreading agents but do not alter the appearance of the skin. Active ingredients including emollients, humectants, binders and surfactants cause changes in the physical appearance such as smooth finish (R&D, J.Mufti and R.Macchio).

A polymer is a chemically manufactured gel like, long chain carbon with cross-linked conformation. The active ingredients such as emollients and vitamins are loaded during the polymerization processes. The spherical bead has high internal surface areas, from 200 to 500 m²/g, created an ideal sorption and desorption mechanism to serve as carriers for the oil soluble active ingredients (R&D, J.Mufti and R.Macchio). The positively charged surface of the polymeric membrane make it favorably adhered to the mildly negatively charged skin surface. Consequently, it helps in distributing the ingredients evenly on skin.

Surfactant or surface-active agents possess a chemical structure that consists of head and tail components. The hydrophilic head group has strong attraction to solvent or bulk material, while the hydrophobic tail with long chain hydrocarbon behaves oppositely. Distortion of the water structure by surfactant in aggregation or micellation process helps to lower the energy of the system, thus improving the interfacial adsorption. Micelle formation is important due to the thermodynamic stabilization in solution behaving as dispersed species. Suitable solvent environments will determine the best chemical structure for use in a given cosmetic system. Emollients, wetting agents, and emulsifying agents are typical surfactants that are used to promote lubrication, adhesiveness, slip and covering. Emulsifiers include an anionic, cationic or nonionic surfactant. This ingredient has made the union of water and oil possible. Emollients are used to soften and smoothen the skin. Humectant has the ability to hold and retain the moisture respirated from the skin. Both the liquid and solid binder is used to provide cohesion. Cosmetic colorant is essential to give color to the cosmetic so it is pleasing to consumer and to impart suitable color appearance on the skin (Happi, J.Mufti). In the following report, the discussion will concentrate on efficiency of the application of surfactant and polymer in four types of cosmetics that are widely used. They are lipstick, eye shadow and blush, face powder for both dark and pale skin, and liquid creams.

Lipsticks

Lipstick in some shape or form has been around for a long time and has always been a part of the fashion statement. Lipstick is a true icon of the feminine mystique.  Its allure and seduction goes back thousands of years.  Lipstick can transform, re-invent, brighten and finish. Lipstick is one product that has more choice than anyone could ever require. Five basic categories of lipsticks are matte, high gloss, long lasting, satin and frosted.

Matte is a flat, stained look with no gloss. This is a long-lasting lipstick but can be drying. Matte lipsticks have more wax than other types of lipstick but fewer emollients. High gloss has a shimmery appearance and helps make lips appear fuller. High gloss lipsticks can be sticky and tend to wear off quickly. Long-lasting lipsticks contain silicone oil. Silicone oil helps to keep the color on the lips and allows the lipstick to stay on all day long. Only mineral oil takes it off. Most lipsticks have a satin finish. Satin is a combination of gloss and matte. Satin lipstick is creamy, which moisturizes the lips, but is not as greasy as other types of lipstick. Satin lipsticks are preferred by many women today. Frosted lipstick contain pearlizing agents. Pearlizing agents are generally bismuth compounds which add luster to the lipstick (ACS).

Lipstick contains a variety of emollients, emulsifiers, preservatives, colorants and binders. According to Ultra Chemical Inc., the emollient ingredients for lipsticks are Lipovol CO, caprylic triglyceride and isostearyl isostearate (UltraChem – lipstick). Lipovol or castor oil can be obtained from the castor plant (essential) and has a preferred weight percent of 51.6 in the Ultra Chemical formulation (UltraChem – lipstick). Castor oil creates a protective barrier on the skin (essential) and forms a film when it dries (ACS). Caprylic triglyceride, used at 10 weight percent in the Ultra Chemical formulation (UltraChem – lipstick), is an oily liquid that can be obtained from plants, vegetable oil, and dairy fats. It also can be synthesized from coconut oil or palm kernel oil (csmt). Isostearyl isostearate has a preferred weight percent of 10 in the Ultra Chemical formulation. It acts as an emollient (UltraChem - lipstick).

Lipstick contains a variety of waxes for emulsifiers, including ozokerite wax and paraffin wax (UltraChem – lipstick). Ozokerite is a ceresin wax and is a naturally occurring mineral wax (csmt), and is used at 1.0 percent by weight in Ultra Chemical formulation (UltraChem – lipstick). Paraffin wax is derived from petroleum (csmt) and is used at 2.0 weight percent in the Ultra Chemical formulation (UltraChem - lipstick). The function of the waxes is to give lipstick its shape and make application easier (ACS). Perfluorocarbons are used in lipstick to increase the interfacial surface area between the pigment and the wax bases. This larger interfacial boundary is ideal for entrapping water within the lipstick, causing it to feel moist. However, the trapped water creates two issues affecting the stability of the lipstick. The first involves packaging. The lipstick must be packaged in an airtight container to avoid the evaporation of the water in the lipstick. The second involves electromagnetic force stability of pigments, which is affected by the pH at the surface of the lips (stepex). Other ingredients in lipstick include emulsifiers. An emulsifier is a chemical compound that allows oil and water to form a stable mixture, which is called an emulsion. Due to both a hydrophobic and hydrophilic end of the molecule, an emulsifier is able to attract both water and oil (essential).

The compound used as a preservative agent in lipstick is propyl paraben. Propyl paraben has a proper name of propyl-4-hydroxybenzoate (essential) used at 0.1weight percent in the Ultra Chemical formulation (UltraChem - lipstick). It is prepared from p-bromophenol by adding hydrogen gas under high pressure to a liquid oil in order to obtain semisolid fats. Propyl paraben is the most common preservative because of it is a nontoxic compound that does not irritate the skin. Also, it is stable over a broad range of pH values and is water-soluble (essential). It has both fungicidal and antibacterial properties, which help to prevent the growth of yeast and mold in the lipstick (csmt).

Lipstick gets its color from a variety of added pigments. Among them are D&C Red #7 CA Lake, Ultrapure HMP-S, and Red Oxide (UltraChem – lipstick). Ultrapure HMP-S is a petrolatum product created to add color to lipstick. It is a petrolatum and wax blend that combines the ideal properties of each. The wax portion gives the mixture a high melting point and stiffness, while the petrolatum gives the mixture moisturizing properties (UltraChem - petrolatum). The color agents are based on red oxide or titanium dioxide with iron oxides, occasionally in combination with ultramarine blue. Titanium dioxide acts as a facial concealing or covering agent (UltraChem - lipstick). Coloring agents used in lipsticks must be safe because it is used so close to the mouth.

Candelilla wax is used as a binder compound. The genetic name of Candelilla Wax is Euphorbia antisyphilitica (essential), and it is used 3.0 weight percent in the Ultra Chemical formulation (UltraChem – lipstick). Candelilla wax is obtained from the candelilla plant (csmt). It is produced by soaking the plants in a solution of sulfuric acid and boiling water and then skimming the wax from the surface (ACS).

The following table shows the compositions of the components in matte lipstick (UltraChem – lipstick).

 COMPOSITION
     
COMPONENTS RANGE % BY WEIGHT PREFERED BY WEIGHT
 
(1) Candelilla Wax (Wax)  3.00 - 9.00   3.0
(2) Ozokerite (Wax) 1.00 - 4.00 1.0
(3) Paraffin Wax (Wax) 2.00 - 5.00 2.0
(4) Ultrapure HMP-S 8.00 - 10.00   10.0 
(5) Isostearyl Isostearate 2.00 - 10.00     10.0
 (Emollient)
(6)  Capric/Caprylic Triglyceride 2.00 - 10.00 10.0
 (Emollient)
(7) Castor Oil (Emollient)   QS 51.6
(8) Propyl Paraben (Preservatives) .10 .1
(9) Tocopheryl Acetate (Antioxidant) .10 - 1.00 .1
(10) Colorants :  
 D&C Red #7 CA Lake .00 - 4.00 .3
 Red Oxide .00  - 3.00 1.5
(11) Rhapsody Talc 4M 2.00 - 10.00 10.0
(Filler/Matrix) 
  Total 100.0

To make lipstick, the ingredients besides the waxes and oils are pulverized. Then, the waxes are added, along with the oils (ACS). The mixture of ingredients is heated to 75ºC to 85ºC and mixed until the batch is smooth and uniform (UltraChem - lipstick). The hot mixture is formed into its shape by cooling it in metal molds. Imperfections are removed by putting the cooled lipstick in a flame for approximately half a second, which also gives the lipstick its finish (ACS). Recently, ingredients have been added to lipstick formulations for various reasons. Sunscreen is added to prevent lips from becoming sunburned, while aloe vera and vitamins are added to keep lips soft and moist (ACS).

Eyeshadow and Rouge

The sole purpose of eyeshadow and rouge is to provide color. In order to satisfactorily achieve this goal, the cosmetic must contain pigments, adhere to skin, have adequate slip to spread onto skin, and have limited water and oil solubility for decent wear in varying conditions, in other words not run with perspiration. In addition, the cosmetic should be easily removable with cleansers. The cosmetic must also be safe for skin and eyes.

Both eyeshadow and rouge may be found in several forms. Rouge may be found as a liquid suspension or emulsion, a cream, a lipstick-like solid, or as a dry, compact powder. The liquid form contains pigments suspended in water, alcohol, glycerol, or other fluid emulsion. Eyeshadow can be found in dry, compact form, as well as a thick, creamy, almost solid form.

Today, of the above, the dry compact is the most common type to be found. Application is done with the use of a powder puff, brush, or sponge or fabric applicator. The solid form is similar in composition to lipstick, and, in fact, some women use lipstick as a substitute for rouge, though solid rouge will have a much more diluted color than lipstick. It is applied and then blended. The creams and emulsions are applied and blended with the fingers, which has probably led to the higher popularity of the dry, compact form. (Sagarin 229-255).

Mascara is available today in liquid form. In mascara, a low molecular weight polyethylene is used to form a gel with the solvent to suspend the color. The object is to leave a pigmented film on the lashes after evaporation of the solvent (Poucher III 305).

Pigments are strongly colored substances. Since the sole purpose of eyeshadow and rouge is to provide color, pigments are important ingredients, which will be present no matter the type of eyeshadow or rouge. They provide the color for the cosmetic. In order to be ideal for use in cosmetics, pigments should not change color with pH changes, water, or oil, and should have limited solubility in water and the oils found in perspiration. Otherwise, color may bleed or streak, or change during wear, which is generally not desired in eyeshadow, and especially not rouge. Pigments should not fade significantly when exposed to light, though organic pigments will fade to some extent. Since powder-milling may involve high temperatures, the pigments must be heat stable. The pigments should also be relatively easy to add into the product. This will affect the choice between whether to use a pigment in the form of a dry powder or a wet pulp or solution. It is of course necessary that the pigment be non-toxic. This is untrue of many of the most brilliantly colored pigments, such as lead and arsenic salts, which were often used in the past to much detriment. It is also important that all pigments used be of same particle size, otherwise rubbing of finished product will bring out the colors of largest size (Sagarin 229-235), (Poucher III 283).

Pigment particle size will affect the result of the final applied cosmetic. Pigment particles should be sufficiently reduced in size and thoroughly blended with the rest of the formula to prevent streaking. Large particle sizes in the pigments scatter light better and increase opacity. It is important to note here that the cosmetic color when applied will differ from that in the compact. Color in the compact is the result of light being reflected from the powder surface itself. On skin, the pigment will be in a thin film, allowing light to be transmitted through it rather than reflected from its surface. This defines the undertone of the cosmetic pigment. This is often tested by wetting the finished powder with a little mineral oil and spreading on a flat white surface. The color will also be affected by the color of the skin (Sagarin 230-232,234).

The following are some of the common pigments found in eyeshadow and rouge. Most of the white pigments also serve as opacifiers, giving the rouge or eyeshadow more opaqueness or coverage. Organic Pigments, which can be found at the bottom of the following list, tend to be brighter and more vibrant (Sagarin 233).

Pigment	Structure	Color(s)	Additional Information	References
Talc	MgO·4SiO2·H2O	White	Main Ingredient in Powder cosmetics.	Marmion 106
Zinc Oxide	ZnO	White/yellowish white	Opacifier, slight drying affect on skin.	Marmion 108-109, Sagarin 228
Titanium dioxide	TiO2	White	Much better opacifier than zinc oxide, but has a tendency to produce blue undertones and doesn’t blend well with other ingredients..	Marmion 107, Sagarin 228
Mica	K2Al4(Al2Si6O20)(OH4) or H2KAl3(SiO4)3	White, pearlescence	White powder obtained from the naturally occurring mineral, muscovite mica. Provides pearly luster. Also an opacifier.	European Commission Andersen Marmion 111
Carbon black	C(s)	Black	May be used from any source, animal or vegetable.	Sagarin 233
Iron Oxides	Fe3O4	Black	Iron oxides must be synthetically prepared	PCI, Andersen
Iron Oxides, ochres, umbers	Fe2O3	Red, brown	ochres: iron ore known as hematite, containing 60 to 80% Fe2O3. Umber is a brown ochre. Synthetic brown iron oxide obtained by controlled oxidation of precipitated ferric hydroxide, resulting in a mixture of red Fe2O3 and black Fe3O4.	PCI, Sagarin 233
Iron Oxides, Yellow ochres	Fe2O3·H2O (FeOOH)	Yellow-orange	Yellow ochre: Clay colored with up to 25% hydrated ferric oxide, Fe2O3·H2O.	Sagarin 233 PCI
Siennas		Yellow, Brown	Sienna (yellow): Mixture of hydrated oxide plus some manganic oxide. Burned sienna is a brown pigment.	Sagarin 233
Ultramarines	~Na7Al6Si6O24S3	Blues, violets, greens, pinks, reds	The ultramarines were originally made from the powdered naturally occurring semiprecious gem, lazurite (Lapis lazuli). They are now synthesized from kaolin, silica, sulfur, soda ash, sodium sulfate, and rosin or charcoal pitch. Used in eyeshadow and mascara.	Sagarin 233, Marmion 108, Andersen
Chromium oxides, hydroxide	Cr2O3, Cr2O3·3H2O	Yellowish (sage) green, bluish green	Anhydrous Cr2O3 (sage green) has good opacity and stability. (Cr2O3); Hydrated or Guignet’s green (bluish), Cr2O3·3H2O, is somewhat transparent.	Sagarin 233 Marmion 100-101
Aluminum powder	Al (s)	Silver		Sagarin 233
Ferric Ferro-Cyanide, ferric ammonium ferrocyanide	Fe4[Fe(CN)6]3XH2O,	Prussian blue		Marmion 110, Jones, “True Blue”
Manganese Violet	~Mn^3+NH4P2O7	violet	Obtained by reacting phosphoric acid, ammonium dihydrogen orthophosphate, and manganese dioxide at temperatures above 450°F.	Marmion 111
Bismuth Oxychloride	BiOCl	Pearly lustre	Synthetically prepared pearlescent pigment.	Andersen, Marmion 109
Carmine (Carminic acid)	C22H20O13	Orange-red, Rich purplish-red, pink	Carmine is ~50% carminic acid, which is extracted from cochineal beetle., little solubitity in most solvents, can be solubilized by strong acids and bases.	Andersen, Marmion 99-100
Guanine	C5H5N5O	Iridescence	Crystalline material from fish scales. Used to provide iridescence. Typically supplied as a paste or suspension in water, castor oil, or nitrocellulose. Silvery or pearly white, though other pigments may also be in the fish scales, which may change the product color.	Andersen, Marmion 101
Lithol Rubin B	C18H12N2O6S(Na2/Ca)	Medium dark red with blue undertone	D&C Red No. 6 (at left), 7	Marmion 77, Sagarin 235
Lake red C	C17H12N2O4S(NaCl/Ba1/2Cl)	Scarlet	D&C Red No. 8 (at left), 9	Sagarin 235, Marmion 78-79
Tetrabromofluorescein	C20H8O5Br4	Med. Red w/ blue undertone	D&C Red No. 21	Sagarin 235, Marmion 80
Rhodamine B	C28H31N2O3Cl	Bright cerise (red) w/ yellow cast	D&C Red No. 19	Sagarin 235, Marmion 79-80
Flaming Red		Bright orange	D&C Red No. 36	Sagarin 235, Marmion 84-85
Persian Orange		Transparent orange	D&C Orange No. 4	Sagarin 235, Marmion 74
Permatone orange		Bright opaque orange	D&C Orange No. 17	Sagarin 235, Marmion 76
Acid Fuchsine		Red	D&C Red No. 33	Sagarin 235, Marmion 83-84
Allura™ Red AC		Red	FD&C Red No. 40	Sagarin 235, Marmion 67
Tartrazine		Yellow	FD&C Yellow No. 5	Marmion 67-68
Brilliant Blue FCF		Blue	FD&C Blue No. 1	Marmion 53,64

Talc is the main ingredient in dry compact makeup, composing approximately 60 to 90 weight percent of the product. It is a magnesium silicate with the approximate formula 3MgO·4SiO₂·H₂O. It is a naturally found material, not synthesized. “The good grades possess a lamellar structure which shows cleavage in the same manner as mica. This property accounts for the shine and slip of the material” (Sagarin 223-224). It is also a very soft material. Mined talc varies in grade, so properties range from shiny to dull, white to dark grey in color, and in softness. Talc adheres to skin evenly and absorbs oil and moisture. These properties, as well as the softness, and “slip” of cosmetics grade talc make it ideal for use as the main ingredient in compact rouge and eyeshadow.

Talc particles are sifted and milled, so that almost all of the particles are no larger than 74 microns. Even finer “micronized” talc is available. The size of the talc particles is important. If the talc particle size is too big, it will not adhere well to the skin. If the size is too small, the talc structure and corresponding properties are lost. (Marmion 105-106), (Sagarin 223-225), (Poucher I 350).

In liquid or gel blushes, the main ingredient is usually water. In cream eyeshadows or blushes, it tends to be binder-emollients such as caprylic/capric tryglyceride or octyl palmitate. In solid rouges, the main ingredient is often castor oil, as in lipsticks.

Binders are substances which are added to solid cosmetic mixtures to provide cohesion. Emulsifying agents promote the mixing of otherwise immiscible liquids. Surfactants lower surface tension, thereby promoting more even mixing. Most blush and eyeshadow is sold in dry compact form, in solid lipstick-like form, or in an almost solid cream form. Thus, binders and emulsifiers are very important in holding the cosmetic mixture together. They hold pressed powder cosmetics together, improve emulsion stability and shelf-life, and allow the cosmetic to form a continuous film on skin when applied. The choice of binders is important in the manufacture of dry compact cosmetics, since inadequate binders will cause the product to crumble in the compact as well as on application. Poor or no emulsifiers will lead to an unmixed mess of ingredients in emulsion eyeshadows. Emollients are also included in this section since many of the emollients used in cosmetics also serve as binders for pressed powder cosmetics. Emollients soften and smooth the skin. They are important in keeping cosmetics from drying out skin. The most commonly used binders are described below (“European Commission”), (Sagarin 257).

Zinc and Magnesium Stearate act as binders in dry form. In addition, they coat the powder particles, making the powder more waterproof. They also make the powder more apt to adhere to the skin. Because of the ease of mixing in dry ingredients and the properties described above, zinc or magnesium stearate can be found in almost every powder makeup formulation (Sagarin 227, 256, 257-258), (European Commission).

Squalane, C₃₀H₆₂, is a binder and emollient. It is a liquid miscible with vegetable and mineral oils (European Commission),(Poucher I 344).

Caprylic/capric triglyceride is the mixed triester of glycerin and caprylic and capric acids, having 8 and 10 carbons in the chain, respectively. They are derived from coconut oil, and serve as an emollient and solvent in cream-type eyeshadows and blushes (“Product Dictionary”), (European Commission), (Sagarin 390).

Octyl Palmitate is also an ester emollient and binder. It is a liquid, and serves as a solvent in the formulation of cream-type eyeshadows, as well as a binder in powder cosmetics.

Mineral oil, a liquid blend of hydrocarbons obtained from petroleum, and petroletum have largely been used as bases in cream eyeshadow in the past, though they have largely been replaced by the vegetable oils above, since they are much more skin friendly (“Product Dictionary”).

Waxes are a complex combination of hydrocarbons obtained from petroleum fractions. They consist mostly of straight chain hydrocarbons with a length great than 20 carbons. Waxes serve as binders, emulsion stabilizers, emollients, and viscosity controlling agents. Beeswax, in particular, is used in stabilizing water-in-oil emulsions in making cosmetic creams (European Commission), (Poucher I 50). Ozokerite or ceresin (its purified form) is a mineral wax. It is a complex combination of hydrocarbons consisting predominantly of saturated straight chain hydrocarbons with 20-50 carbons each. It is used as a binder and emulsion stabilizer. It is also used to raise the melting point of solid cosmetics, and is a substitute for beeswax or hard paraffin in this respect. (European Commission), (Poucher I 96-97).

Isopropyl Myristate is a synthetic fatty acid ester, and a liquid binder (Sagain 288).

Castor and safflower oils are both emollients used in cosmetics. Castor oil is the main constituent in solid rouge and consists primarily of the glycerides of the fatty acid ricinoleic. Safflower oil consists primarily of the glycerides of the fatty acid linoleic. (“Product Dictionary”).

Glycerin, also known as Glycerol or propan-1,2,3-triol, acts as a solvent to dissolve other components and as a humectant, meaning that it serves to hold and retain moisture in the cosmetic product. It is prepared by the hydrolysis of fats and oils. It has the formula CH₂OHCHOHCH₂OH (European Commission), (“Product Dictionary”), (Poucher I 181).

Cetyl alcohol, C₁₆H₃₃OH, is a waxy powder. It is stable in the presence of acids, alkalis, light and air. It is soluble in alcohol, ether, glycol, and diglycol ethers and miscible with mineral and vegetable oils and fats. It serves as an emulsifying agent for both oil-in-water and water-in-oil emulsions. It also serves as an emollient (Poucher I 97-98).

Lanolin is the fat extracted from the wool of sheep. It is an emollient readily absorbed by the skin. It consists of a complex mixture of esters of high molecular weight fatty alcohols and acids. Liquid lanolins are soluble in mineral oil (Poucher I 214).

Oleyl alcohol, C₁₈H₃₅OH, serves as an emollient, emulsion stabilizer, super fatting agent, and a “pigment dispersing material”. It is used to improve the texture of creams and in stick cosmetics. It is soluble in ether and alcohol and insoluble in water (Poucher I 283).

Diethylene glycol monostearate (C₁₇H₃₅COOCH₂CH₂OCH₂OH) is an emulsifying agent for the preparation of oil-in-water emulsions (Poucher I 142). As a chain hydrocarbon with a polar end, it makes a good surfactant.

Preservatives are added to cosmetics to inhibit the growth of micro-organisms within. From a safety standpoint, preservatives are most important in eye make-up, and especially in mascara, where it is possible to cut the eye with the applicator wand and infect it. Bacteria will especially be a problem in water-based cosmetics, where bacteria will grow readily. (Draelos),(Stehlin), (European Commission). Preservatives frequently used in cosmetics are listed below.

The parabens are esters of p-hydroxybenzoic acid (C₆H₄OHCOOH) . They are the most commonly used preservatives in cosmetics today. They include methylparaben (methyl parahydroxybenzoate), which is water-soluble, ethylparaben (Ethyl 4- hydroxybenzoate), propylparaben (Propyl 4- hydroxybenzoate), which is less water soluble than methylparaben, and butylparaben, which is oil-soluble (Poucher I 197-198), (“Product Dictionary”), (European Commission).

Glyceryl Monolaurate (monoglyceride) (empirical formula C₁₅H₃₀O₄) is both a preservative and a good emulsifier, distributing between both lipophilic and hydrophilic phases of formulations, which helps to make it a cost effective preservative (Utlra Chem). EDTA (Ethylene Diamine Tetra Acetic Acid) is a synthetic compound used mainly in lotions as a preservative (“Product Dictionary”). Imidazolidinyl Urea (N, N''- methylenebis[N'- [3- (hydroxymethyl)- 2, 5- dioxoimidazolidin- 4- yl]urea]) is another preservative (“Product Dictionary”), (European Commission).

The role of absorbents is to take up excess water and oil, such as from perspiration, and to lower the shine created by the talc in powder cosmetics, if so desired. Perfume carriers tend to be absorbent materials.

Magnesium carbonate is an absorbent due to the high porosity of magnesium carbonate. However, excessive absorption of perspiration may cause gumminess and streaking if there is too much magnesium carbonate in the formula. Magnesium carbonate may also cause drying. It removes the shine of talc. It is also a perfume carrier and slight opacifier. Too much magnesium carbonate will make a compact brittle because of the absorbency. It is decomposed by acids. (Sagarin 226-227,256). Kaolin (2SiO₂Al₂O₃·2H₂O) is an absorbent and removes the shine of talc. It also has soothing properties. Unfortunately, it causes many perfumes to deteriorate. Chalk is used as a perfume carrier. Only a small amount may be used as it tends to make compacts brittle (Sagarin 225-227,256).

Sample eyeshadow, rouge and mascara formulations are given in the tables below, along with a description of the manufacturing process.

Dry Rouge:

(Almay)

Talc (Filler) 48% Kaolin (Absorbent) 16% Titanium Dioxide (Opacifier) 12% Color Pigments 12% Zinc stearate (Binder) 4% Chalk (Perfume carrier) 4% Magnesium carbonate (Perfume carrier) 4% Perfume q.s. (Sagarin 261)

In older processes which required less equipment, the pigments, including the titanium dioxide, and dry powder ingredients, were first pre-mixed in spiral ribbon or pony mixers. Binder solution or water was added to convert the mixture into a dough-like paste. The paste was then dried in ovens on shallow trays. The hard, dry cakes were then reground in hammer or ball mills. These operations were then repeated. A fairly large amount of binder was used, and operators could tell if the binder was uniformly distributed.

In the more modern “American” process, more powerful grinders are used, which precludes the need for wetting and baking cycles. Hammer mills with air classifiers, cyclone mills, attrition mills, and edge runner mills are used. A fairly small amount of binder and emulsifier is sprayed into the powder while it is being mixed. The emulsifiers act as wetting agents and are needed to make sure that the binder is evenly distributed. This is especially so if the binder contains water since the powder is usually water repellant.

The mixed rouge is then distributed into pans and then pressed. A small amount of air should be left between the press and the edge of the pan to allow for the escape of air from the interstices between the powder particles. The press should bring the powder particles into physical contact with each other and then “weld” the binder film around each particle to that of the adjacent particles (Sagarin 258-261).

Liquid-Gel Rouge:

(L’Oreal)

Water (softened or distilled) 67% Glycerin (solvent) 19% Diethylene glycol monostearate (emulsifier) 4.3% Cetyl alcohol ethoxylate 2.9% Titanium dioxide 2-3% Pigment 2.0% Iso-Propyl myristate (binder) 1.9% Cetyl alcohol (emulsifier/emollient) 0.48% Perfume 0.2% Methyl paraben (preservative) 0.15% Bromo acid (colourant) 0.02% (Poucher III 284)

The emulsion base is prepared by heating together the cetyl alcohol ethoxylate, iso-propyl myristate, cetyl alcohol, and diethylene glycol monostearate to a temperature of 70-75°C. In a separate vessel the methyl paraben is dissolved in the glycerine by heat. The water is added to the glycerin and heated to 75°C. The water-glycerin mixture is then added to the emulsion base with slow continuous stirring, and allowed to cool with continued stirring. The perfume is added when the temperature reached about 35°C. Then, the pigment, including titanium dioxide, is added and the mixture mixed well (Poucher III 284).

Solid Rouge:

(Wet N Wild)

Castor Oil 77.4% Candelilla wax 9.9% Carnauba wax 2.7% Color 10.0% Perfume q.s. (Sagarin 254)

More details about these ingredients and the manufacture can be found under “Lipstick.”

Dry Eyeshadow:

These formulations are very similar to those of compact rouge.

(Almay, Inc.)

Talc (Filler) 64.7%(wt) Ultramarine Blue (Pigment) 20.0% Octyl Palmitate (Liquid Binder) 7.0% Squalane (Liquid Binder) 3.5% Iron Oxides (Pigment) 2.6% Zinc Stearate (Solid Binder) 2.0% Glyceryl Monolaurate (monoglyceride) (Preservative) 0.5% EDTA (Preservative) 0.1% (UltraChem - eyeshadow)

The pigments, preservatives, and zinc stearate are combined with an equal portion of talc. The mixture pulverized and blended with the remaining talc. The oil-phase binders (octyl palmitate, squalane) are sprayed and mixed into the powder. The mixture is then compressed into suitable containers (UltraChem - eyeshadow).

Creamy Solid Eyeshadow:

(Black Opal/BioCosmetic Research Labs)

Petroleum jelly* (binder/base) 25.6% Paraffin wax (binder/emollient) 22.6% Isopropyl palmitate (binder/emollient) 16.4% Lustre Pigments 10.3% Pigments 8.2% Beeswax (binder/emollient) 5.1% Oleyl alcohol (emulsion stab.) 5.1% Lanolin (emollient) 4.1% Cetyl alcohol (emulsifier/emollient) 3.1% Perfume 0.5% Butylparaben (preservative) 0.02% Propylparaben (preservative) 0.01% (Poucher III 294)

The isopropyl palmitate, petroleum jelly, oleyl alcohol, and lanolin are heated together, and the preservatives are added. The pigment is mixed into the melted mixture and milled. The waxes are melted, and then added to the mixture, along with the luster pigment. The mixture is allowed to cool. Perfume is added after cooling. The mixture is then poured into moulds and allowed to set (Poucher III 294).

Today, the petroleum jelly is almost always replaced by caprylic/capric triglyceride.

Mascara:

(Almay)

Isoparaffin (Solvent) 69.7% Pigments 12.0% Beeswax 5.4% Ozokerite wax 5.4% Polyethylene 4.2% Carnauba wax 2.0% Microcrystalline wax 1.2% (Poucher III 305)

The polyethylene is mixed with about half the solvent using a propeller type mixer with moderate agitation. The mixture is heated to about 100°C with stirring. The remainder of the solvent is added and the mixture is cooled rapidly. Rapid cooling is essential for the preparation of a stable gel. The pigments and melted waxes are added, and the mixture is mixed thoroughly. Water and petroleum distillates are the common solvents used in mascara.

Face Powder

Face powder is a type of pressed powder that is used to enhance the appearance of the skin of a person. It makes the skin of a person having dark skin appear brighter and makes the skin of a person having pale skin appear darker. It also has the ability to give a smooth finish, cover blemishes, absorb perspiration, and absorb excess oil on the skin. Modern face powders do not merely consist of cosmetic active ingredients or vitamins but are blends of other additives such as polymers, surfactants, solvent, colorant and Rhapsody, a type of talc. These additives are added to promote slip, adhesiveness, lubricity, and long wear.

Adhesion is the physical attraction of unlike molecules for each other. By promoting a strong contact, adhesion works to enhance the retentive force of the interfacial surface tension. The hydrophobic and hydrophilic behavior have tendency to orient their long hydrocarbon chain into the non-aqueous environment at an aqueous environment. This kind of oriented adsorption consequently reduces the interfacial tension.

Rhapsody is the main composition used in the cosmetic products with 70-90 weights in percent in total (Rhapsody Formulation). This mineral has tendency to spread the active ingredients of the cosmetic easily and give a smooth feeling on the skin. It has excellent lubricity and skin adhesion. There are two type of Rhapsody. Each has a difference in reflectance due to the presence of different average particle sizes, based on the specification provided by the Ultra Chemical Inc. in the physical properties. The Rhapsody 2M having average particle size of 14-16 is suitable for the person having pale skin, causing the skin to appear darker, while Rhapsody 4M having average particle size of 3.0-4.5 has the opposite effect for dark skin. The typical properties for Rhapsody include a melting point of 110^oC and a specify gravity close to 0.919.

Figure 1: Rhapsody reflectance and translucent compared to standard talc.

*Picture from Ultra Chemical Inc.

Rhapsody is a new approach designed to replace standard talc and give low translucency; this will reduce the color enhancement overall.

In addition to promoting slip and adherences, zinc stearate is added. This metallic stearate type of surfactant comprises only 2.0 to 6.0 percent of total weight. It is a kind of solid binder that dissolves in mineral oil 70 cst. Zinc stearate is a white fine crystalline powder that helps cosmetics adhere to the skin. It has chemical formula of

Zn (C₁₈H₃₅O₂)₂ with a molecular mass of 632.3 (INCI). The following structure indicates the zinc stearate has a long hydrocarbon chain. This adheres the cosmetic to the skin for a longer period of time.

Figure 2 : Chemical structure of Zinc Stearate.

*Picture from VIVA Company.

The ideal physical properties are that it is white powder, containing less than 6% moisture and having alkaline properties with a pH ranging from 10 to 11. The melting point is in the range of 118 to 122 ^oC, and the bulk density for this material is 260 to 360 grams per liter where it is only soluble in mineral oils. The properties of zinc stearate are use to lubricate raw beads to prevent them from fusing together or forming lumps. This is due to the increase of the die-filling density by promoting the powder flow ability.

Octyl palmitate is added to the formulation of long wearing pressed powder for a person having pale skin. This is an octyl ester type of surfactant that behaves as liquid binder. It has the same function to provide cohesion for the cosmetic ingredients on the skin by imparting a dry, light silky feel (Cosmetic Ester, Stepan). The forming of this alky ester is by reacting 2-ethylhexyl alcohols with palmitic acid. Palmitic acid is used as emulsifier to promote the formation of intimate mixtures of immiscible liquids. The chemical structure for the formation of octyl palmitate is shown below:

Figure 3: Typical Octyl Ester structure from reacting 2-ethylhexyl alcohol with palmitic

Acid.

*picture from Stepan Company

This type of octyl ester is used to smoothen and soften the skin and is known as an emollient and a conditioning agent. It has good qualities because it does not feel oily, thus it is suitable to serve as a protectant and to help in replacing the natural ester missing from older skin.

There are other relevant ingredients that work in perfecting the cosmetic product. Coloring material such as yellow, brown or black iron oxides (Fe₂O₃) contained at approximately 0.1 to 10 percent by weight. Iron oxides are the main pigment besides other inorganic pigments such as chrome oxide and chrome hydrate. This powder will help in augmenting the underlying skin and foundation tones, using the different strength of transparency for a person either having dark or pale skin. In contrast to a small amount of iron oxide in face powder for pale skin, there is increase of 95% when dealing with dark skin. The high colorant used here is serving the purpose to enhance the skin shininess.

Long Wearing Pressed Powder
(for a person having pale skin and dark skin)

COMPOSITION

  
    Preferred by weight
   Range 
 Components   % by weight   Pale skin /   Dark skin
 
 (1) Talc, Rhapsody 70.0 - 90.0  90.5 (2M)  74.5 (4M)
 (Filler/Matrix)
 (2) Iron Oxides (Colorants)  0.1 - 10.0  0.5  15.0
 
 (3) Polyethylene, Micronized  2.0 - 6.0  3.0  0.0
 (4) Octyl Palmitate  2.0 - 8.0  6.0  0.0
 (Liquid Binder)
 
 (5) Zinc Stearate   2.0 - 6.0  0.0    3.5
 (Solid Binder) 
 (6) Mineral Oil 70 cst.   2.0 - 9.0  0.0  7.0
 (Liquid Binder)

Total 100.0 100.0

Table #1: The main composition of the formulation of face powder for both the person having pale and dark skin. *Source from Ultra Chemical Inc.(Long Wearing formulations-pale and dark)

The qualities of the products have achieved the objective of transparent pressed powder with high lubricity and good adhesion. In addition, it exhibits prolonged wearing characteristics without overpowering the appearances on the skin, for example noticeable chalkiness.

Based on the Ultra Chemical Inc. processing procedures, the first step is to pulverize or to crush the iron oxides on equal quantities of Rhapsody talc in powder form. This mixture is then compressed into pan utilizing pressures in the range of 200 to 2000 psi.

Liquid Cream

Liquid cream makeup is designed to cover blemishes in the skin and even skin tone and texture. In order to satisfy these design objectives, the cream must have an even color, last all day without rubbing off, but also be removable with cleansers that are not harsh to the skin. This is achieved through a mixture of humectants, emulsifiers, emollients, gums, colorants, fragrance, preservatives, filler, and matrix components.

The main humectants used in the formulation of liquid creams are butylene glycol and other polyols. Humectants must be able to hold moisture at a variety of relative humidities (DeNavarre 165). This helps the cream to keep from drying out when it is opened or balling up when it is applied to the skin (Harry Cosmetics 734). The humectant should readily absorb moisture from the atmosphere to keep the cream from drying. However, the amount of water that the humectant absorbs must also not change too much with changing humidity (DeNavarre 168). This keeps the cream from having drastically different properties as the weather changes (Harry Cosmetics 740). The humectant also functions to moisturize the skin, plasticize the liquid cream, and control the texture (DeNavarre 165). In the Ultra Chemical formulation of liquid cream makeup, butylene glycol is the humectant used, at a weight percent of 0.0 to 8.0.

Emulsifiers are types of surfactants added to cream makeup to reduce surface and interfacial tension between the water and oil phases (Balsam 575). They allow the oil-like components of the cream to be stable in the water base as small droplets. Emulsifiers are large molecules such as lecithin, polysorbate 20, stearic acid, SE glycerol mono stearate, and cetyl alcohol (UltraChem – liquid cream), which contain both a long-chain hydrocarbon and a polar end. This polar end may be the COOH group of an acid, the OH group of an alcohol, or the double-bonded oxygen of an ester (Harry Principles 259). The long hydrophobic tails trap oil droplets in them, while the hydrophilic heads allow the molecule to be soluble in the water base (Harry Cosmetics 650). An ideal emulsifier will reduce the surface tension between the water and oil phases enough to create a stable emulsion. This is achieved through a balance of the size of the long-chain hydrocarbon and the degree of hydrophilicity of the head group. A variety of emulsifiers are used in the Ultra Chemical formulation of liquid cream makeup. The total weight percent of all the emulsifiers ranges from 1.7 to 11 weight percent (UltraChem – liquid cream).

Emollients are used to smooth and soften the skin. The emollients used in the Ultra Chemical formulation of liquid cream are capric triglyceride at 1.0 to 8.0 weight percent, isopropyl myristate at 1.0 to 8.0 weight percent, and squalane at 0.0 to 5.0 weight percent (UltraChem – liquid cream). Capric triglyceride and isopropyl myristate are esters, formed by the reaction of an acid with an alcohol. Squalane, in comparison, is a long-chain hydrocarbon with the molecular formula C₃₀H₆₂ and a molecular weight of 422.80. It is soluble in fixed and mineral oils, while only slightly soluble in alcohol and acetone, due to the presence of a hydrophobic chain and no hydrophilic groups (Harry Principles 455).

Gums are added to the liquid cream to act as a protective colloid, suspending agent, and film former. They are long-chain carbohydrate polymers containing sugar units (DeNavarre 109). The gums used in the Ultra Chemical formulation of liquid cream are hydroxethyl cellulose at a weight percent of 0.10 to 0.40 and xanthan gum at a weight percent of 0.40. Hydroxethyl cellulose is a series of cellulose derivatives with a wide range of viscosities and solubilities. Ideal properties for gums include little change in viscosity with pH (Harry Principles 122).

Other chemicals that are added to the liquid cream makeup are iron oxides, titanium dioxide, Rhapsody 4M, fragrances, and preservatives. The iron oxides and titanium dioxide are added for color, while Rhapsody 4M is added as a filler and matrix. Fragrances make the cream smell pleasant as opposed to like chemicals. Preservatives keep the cream usable for long periods of time.

The complete formulation can be found in the table below.

According to the formulation by Ultra Chemical Corporation, liquid cream makeup is created in a series of steps. First, the water base is added to a kettle and the other water-soluble ingredients are added in order. The gums and pulverized pigments are allowed to completely disperse in the water phase at 75 °C before the oil phase is added. The ingredients in the oil phase are combined at 70 °C and then added to the water phase. The entire mixture is then cooled to 35°C before the fragrances and preservatives are added. Finally, the mixture is cooled to 28°C and put into containers to be sold.

Marketing

In today’s cosmetic market, the sellers are targeting people of all ages and both genders to market their products efficiently. Advertisement is a likely approach to inform the consumer regarding new products and to persuade them to buy them because of the distinct features from others comparable cosmetic in the current market. New breakthroughs are under development, the purposes being to attract and give the opportunity for the customer to go through the product directories, compare prices and ingredients to find a type available online that suits them, and have the product shipped to their front door. The Internet is another powerful tool to send product information online without printing pamphlets. Customers visit shopping malls often during the holiday season. This is a chance to promote the company product where free samples can be given away. Experienced and trained sales personnel are required to entice the customer to buy the cosmetic products that they are promoting. Customer complaints and suggestions are a valuable asset to help cosmetic companies make improvements. In general, customer assessment through questionnaires provides information on changing requirements in both packaging and cosmetic performance.

Cost

According to ACNielsen, the market for cosmetics reached $3.4 billion in the fiscal year ending in June of 1999. Yearly retail sales are approximately $300 million, although this number depends on the amount of disposable income. It is expected by Euromonitor International, a global information provider (euromonitor), that sales will top $23 billion by 2003 (ecrm).

Labeling

The Food and Drug Administration regulates the labeling of cosmetics. Labels must contain a list of ingredients in descending order. Professional grade cosmetics, those designed to be used only by trained beauticians, must be labeled “For Professional Use Only.” Also, specific warnings must appear on cosmetics. For example, any flammable products must be labeled as such (cfsan-labl).

Conclusion

Beauty can be pleasing, lovely and pretty to the eye. In general, characteristics of polymers and surfactants in modifying the cosmetic adhesive properties, slip and smooth feeling, longer wearing, and more importantly reducing the allergic reaction between the cosmetic ingredients and the skin. Face powder, dry eyeshadow, and rouge ingredients consisting of zinc stearate and octyl palmitate have made a great contribution in reducing the interfacial tension and increasing the adhesiveness and the slip at the same time. The emulsifiers in liquid cream makeup, including lecithin, polysorbate 20, stearic acid, SE glycerol mono stearate, and cetyl alcohol allow emulsions of water-based ingredients and oil-based ingredients to exist. Glycerin, isopropyl myristate, and cetyl alcohol allow the same for gel-type eyeshadows, while caprylic and capric triglycerides allow such emulsions in cream-type eyeshadows and rouges.

References

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