Review Article ISSN (Print) : 2231-1947 RGUHS J Med Sciences, Vol 8(1), 13-17, January 2018 DOI: 10.26463/rjms/2018/v8/i1/121003 Coloring – Hair Dyeing

K. Hanumanthayya1, G. Balasubrahmanyam2, Menakaa Mohan3, Sunitha Mohan3 and N. Nikhil3 1Professor and Head, Department of Dermatology, Vydehi Institute of Medical Sciences & Research Centre, Bangalore – 560066, Karnataka, India; [email protected] 2Assistant Professor, Department of Dermatology, Vydehi Institute of Medical Sciences & Research Centre, Bangalore – 560066, Karnataka, India 3Junior Residents, Department of Dermatology, Vydehi Institute of Medical Sciences & Research Centre, Bangalore – 560066, Karnataka, India

Abstract History of the coloring of the gray can be traced back to Sumerians and Pharaohs 2000 BC. Women in the past used hair colors to hide their gray hairs. Today men are also applying hair color to hide their gray hairs and younger people color their hair as a fashion. The discovery of paraphenylenediamine and better understanding of chemistry of hair have resulted in safe and customer friendly products. Now men and women can apply the hair dyes in their own home in just one easy step 30-45 minutes.

Keywords: Hair, Hair , PPD,

Introduction History of Hair Coloring

The scalp has the most striking feature for every person. Human’s use of hair dye traces back to the beginning of For a long time, hair has been considered more than just a civilization. The extraordinary history of hair color can biological feature, and is more often center of beautification. be traced back to Sumerians who lived in 2000 BC. Nobel For women, hair is an ornament that has transformed their Sumerians used to color their gray hairs with golden dye, beauty at higher level. symbolizes the younger using silver or gold combs. Ancient Egyptians, Romans, age, youthfulness, energy and active life. As we grow older, and Greeks began to use hair color regularly which was hair turns gray and silver white. Graying becomes visible made from plant and animal extracts. Egyptian women in when 20% of black hair turns gray. Hence gray hair and 1500 BC, colored their hair using plant extracts. The white hair symbolizes the old age, sluggish and inactive Romans believed that hair dyeing and coloring was a symbol life. Today everyone wants to look younger, energetic, of woman’s eroticism, and highlighted her gracefulness and enthusiastic and visually appealing to other people. Hence elegancy. By 27 BC, hair dye became a much accepted trend, they hide gray hair by applying color to the hair and and both men and women in Rome used color hair as a way this process is called “Hair coloring – Hair dyeing”. Hair of enhancing their looks and appearance. Roman Empire coloring is more for cosmetic reason and to hide their gray insisted prostitutes to color their hair yellow or to wear hairs by people. Often, younger people color their hair as yellow colored wig to indicate their profession. Prostitutes a fashion. were coloring their hair with ashes of burnt plants, flowers Hair coloring was done earlier by hair dressers at and nuts to achieve a yellow hue. saloon. Today hair coloring is very simple, user friendly Hair dyes were made using henna (Lawsonia inermis), and can be done at their house in 30-40 minutes. indigo, Cassia obovata, senna, turmeric, amla, crushed nut

Author for Correspondence : K. Hanumanthayya Professor and Head, Department of Dermatology, Vydehi Institute of Medical Sciences & Research Centre, Bangalore – 560066, Karnataka, India; [email protected] K. Hanumanthayya et al : Hair Coloring – Hair Dyeing

shells, berries, and vinegar[4]. dye was prepared by The cuticle consists of 6-8 layers of flat, thick, colorless fermenting leeches in vinegar for two months. This mixture closely adherent cells laid out overlapping one another was applied on the hair and then exposed to the sun for as roof shingles. The individual cuticular cells are made hours to get red hue. Eighteen Books on the Secrets of Art up of proteins, lipids and polysaccharides. The cuticular and Nature published in 1661 explained various methods cells closely overlap on one another; only one-sixth of of coloring hair black, gold, green, red, yellow, and white. each surface is exposed. The open ends of the overlapping In 1860s, hydrogen peroxide was a common option for cuticular cells are directed away from the scalp, toward the hair bleaching. With time, this came to be known as growing tip. The cuticular cells are hydrophobic and provide dye, until the 1930s. Hydrogen peroxide was used along first line defense against water and other environmental with other ingredients such as and soap powder. harsh chemicals. An intact well organized cuticle protects This combination damaged the hair, and burnt the scalp. the hair and directs the water to run along the shaft from Soon this combination became less popular. scalp downwards. The function of cuticle is like that of Hair coloring and dying took a major leap when stratum corneum of the epidermis, barrier function[2]. paraphenylenediamine (PPD) was discovered by August The cortex lies immediately beneath the cuticle and Wilhelm in 1863. This was the magic substance that was forms the major component of human hair. Cortex consists used in creating the first synthetic dye. PPD along with of fusiform spindles cells of 100 microns long, arranged Hydrogen peroxide, which was a gentler option for hair longitudinally. Each spindle cell has keratin bundles bleaching, together led to a major invention. The invention within a cysteine rich matrix. Disulfide bonds between of this synthetic dye PPD resulted in further research and the cysteine residues within the cortex are strongest and development in hair colors. In 1932, a New York chemist structurally the most important bonds that hold the keratin Lawrence Gelb, created a hair dye that would actually protein together. Disulfide bonds are responsible for the penetrate the shaft of the hair without harming the shaft shape of the hair. The cortex contains keratin bundles in of hair. Today women could lighten, color, , and cell structure along with hair coloring material called condition their hair in just one easy step, in 30-45 minutes[1]. . All natural color of hair is due to melanin granules present in colorless keratin bundles. There are two types of Anatomy of Hair melanin called 1) Eumelanin and 2) Pheomelanin. In India eumelanin is the dominant pigment present in hairs and Healthy hair is pigmented, smooth, glossy, flexible and gives black color to the hairs. Pheomelanin is dominant also strong. The healthy hair withstands shearing forces. color in Europeans and gives red hair. As the person grows The hair which is visible to eyes on the scalp is called hair older, melanin production decreases and stops. The hair shaft. The part of the hair which is inside the skin is called shaft with no melanin loses its natural color and turns gray hair root. The shaft is the hard filamentous part that extends - to - white color of old age. above the skin surface. The glossiness of hair depends upon The medulla is an open area at the fiber’s center. It the smooth layering of the cuticle and the strength depends contains specialized cells rich in glycogen and citrulline. on the integrity of the cortex. The cortex is made up of 15% In between these cells air spaces are present and are called hard keratin (skin contains 2% keratin). The healthy hair fauces. Medulla is present in the thick hairs only, as the surface has a pH of 4.5 to 5.5. This acidic pH helps to keep person grows older, slowly medulla disappears. cells of the cuticle closely opposed to the cortex. The structure of healthy hair is perfectly designed and A cross section the hair shaft may be divided into three outermost layer is smooth and well protected. It dries zones. They are 1) Cuticle 2) Cortex 3) Medulla (Figure 1). quickly when wet and resists diffusion of water into the cortex. This maintains the structural integrity of the hair[3]. Hair dye or hair color is a chemical substance that is used to change the color of hair. Hair dye is used mostly to hide gray hair by elderly people. Young people apply hair dye to change their hair color as a fashion[4,5].

Chemistry of Hair Dye

Modification of the hair color can be achieved by two Figure 1. Healthy shaft with normal cuticle, cortex and medulla.

14 Vol 8(1), January 2018 | www.rjms.in RGUHS J Med Sciences K. Hanumanthayya et al : Hair Coloring – Hair Dyeing methods. They are removal of existing melanin pigment is non-toxic but messy. Similarly extracts of flowers, from hair called bleaching and addition of artificial pigment leaves, fruits and walnut are used to color the hairs. via application of a hair dye. Food grade dyes are also used. Henna powder is mixed In the 1860s, hydrogen peroxide was used for bleaching with indigo leaves and other ingredients. hairs. Hydrogen peroxide was oxidizing melanin pigment 2. Permanent Hair Color – The most popular dye prod- and lighten the intensity of black color; the hairs were ucts give permanent hair color. They are easily available, becoming light colored. Hence it was called blond dye. user friendly, range of colors and they color the hairs In 1907, Eugene Schuler, a French chemist, developed an for 2-3 months. They are also called synthetic organic innovative hair color formula and called it “Aureole”. This dyes and oxidative dyes. Permanent hair coloring dyes name was later changed to “L’Oreal”. L’Oreal became very consist of three components. They are a) Primary inter- famous with Parisian and soon it became mediates and couplers, coloring agent, b) Oxidants household product, and women started applying hair dye (Hydrogen peroxide) and c) An alkali usually ammonia. in their home. The modern permanent dyes consist of The hair colors can be classified into 4 types. “Paraphenylenediamine (PPD or similar Para 1) Temporary hair color, 2) Permanent hair color, 3) compounds like para-toluenedimine, and para-amin- Semi-Permanent, 4) Demi-Permanent ophenol)” as primary intermediates and “Resorcinol” 1. Temporary Hair Color – The pigment molecules are as couplers. Hydrogen peroxide oxidizes colorless large and cannot penetrate the outer cuticle layer. The Paraphenylenediamine dye to colorful chemical and color particles remain adsorbed (closely adherent) to also lightens melanin. Ammonia causes cuticle to swell the hair shaft and are easily removed with 1 or 2 sham- and rise from cortex and also creates few openings, pooing (Figure 2). Dye molecules only coat the hairs, it through these openings oxidized PPD dye enters cutic- is physical action. The dye molecules do not penetrate ular layer and reach cortical cells. Once oxidized PPD the hair shaft; hence there is no chemical action. There dye accumulates in cortical cells, and it gives color to is no damage to the hair. These are the least hazardous hair shaft. Once the PPD dye has entered the cortical of all dyes. Vegetable dyes like “Henna” is very popular cells, it cannot be dislodged from the hairs even 15- 20 dye and is used throughout the World. Henna coats the times washes with shampoo. Hence PPD dye is called shaft of hair and increases the thickness of hair shaft. Permanent hair dye. Repeated application of henna improves the hair shaft Alkaline ammonia action continues to act on hair, and do not damage the hair. Henna is obtained from swelling and rising of cuticle cells continues, hence it shrubs found in North Africa and the Middle East: is to be neutralized by acidic rinse or to be washed by Lawsonia alba, L. spinosa and L. intermis. shampoo, then only ammonia action stops. If ammo- nia action is not neutralized, hair damage continues and hair becomes brittle and dry. Everyday 0.1 mm hair grows, on 10th day, 1 mm hair grows, and this newly grown hair will not have this new pigment. Hence per- manent hair dye is to be applied once in 2 or 3 months. The newly growing hair from root will be devoid of color; hence touch-up of dye to roots is required to have satisfactory color. 3. Semi-Permanent Hair Dyes- Semi-permanent hair dyes coat the hair shaft rather than penetrate. They Figure 2: The temporary hair dye has colored only the do not change melanin. Heat is used to deepen the cuticle of hair shaft; molecular size is bigger, not color penetration rather than the use of chemicals like entered cortex, hair shaft is healthy. ammonia and hydrogen peroxide. The color lasts for 4-6 weeks (6-12 shampoo wash). They do not harm The henna dye is obtained from dried leaves. The the hair as Permanent hair dye harms the hair (Figure active principle is an acidic naphthoquinone (Lawsone). 3). These are water soluble, non-ionic, low molecular Traditionally, henna is applied as thick paste pack, mixture of pre-formed dyes. They are usually anthra- which is left in situ for 20-30 minutes, then washed. The quinone, aromatic amines or aminonitrobenzenes, and effect of henna dye last for up to 10 weeks. This process may other dyes to give the required shade. The product

Vol 8(1), January 2018 | www.rjms.in RGUHS J Med Sciences 15 K. Hanumanthayya et al : Hair Coloring – Hair Dyeing

is applied to shampoed and towel dried hair, left on for before one buys a product, and follow the instructions of 20 minutes and rinsed off. A conditioner can be used manufacturer. It is necessary to use products from trusted after shampooing the hair, and then dye can be applied. brands that do not use many harmful chemicals. It may cost some extra money. It is necessary always to color hair in well lit and well ventilated areas only.

Hair Dyes Available in Market

Today Indian market is full of hair coloring products. They Fig.4 Ammonia has opened cuticular cells and allowed hydrogen peroxide range from Rs 15 to 200 to 2000 Rs. They are user friendly Fig.3 Semi permanent hair dye has entered the cuticle Figureand permanent stain4: toAmmonia enter the hair cortex,H2O2 has has opened lightened the Figureand stained the hair3: cortex Semi ; molecular perma size of the - existing melanin pigment, permanent stain has combined with lightened and entire process will be over by 30 to 45 minutes. They stain is smaller, neglible damage to hair shaft. cuticularmelanin and produced cells color to theand hair. Cuticular allowed cells are damaged. hydro- nent dye has entered are safe also. gen peroxide and permanent stain the cuticle and stained Few of the popular brands in Indian market are the hair cortex; molec- to enter the hair cortex, H2O2 has ular size of the stain lightened the existing melanin is smaller, negligible pigment, permanent stain has L’OREAL Paris Clairol Natural Olia damage to hair shaft. combined with lightened melanin instincts Brilliant and produced color to the hair. Matrix BBLUNT Naturint Cuticular cells are damaged. Godrej rich cream Dabur Vatica Schwarzkopf Shahnaz Husain Nature’s Essence 4. Demi-Permanent Hair Dye- Demi-permanent hair Colorveda natural natural hair color dye falls between the semi-permanent and permanent hair color – Burgundy dye process. It uses a catalyst such as a 2% mild perox- Nupur mehendi Biotique Bio Henna Henna coca ide developer with a non-ammonia alkali to swell the fresh powder hair burn cuticle, allow dye molecules to penetrate into the cor- color tex and deposit color inside the hair shaft (Figure 4). Habib’s Henna Kolestrix Streax A neutral or slightly acid after-rinse or shampoo wash VLCC Ayurve- Khadi natural henna Banjar’s black is used to stop the alkaline swelling reaction, allow the dic henna henna cuticle to close, and trap the color molecules inside. The mild chemical reaction does not lighten the melanin Side Effects and hardly changes the hair structure[6-8]. Today the hair dyes available in India are good and if patch Precaution test is performed and then used, it is safe practice. Side effects are seen sometimes, if poor quality hair dye is used, Hair dye reactions are most commonly present as allergic not applied properly, over treating, and under treating. contact dermatitis or irritant contact dermatitis. Less Allergic reactions, irritation to dye are noted. Repeated use [9] common side effects are Photoallergic dermatitis, dye of permanent hair dye may damage hairs . induced depigmentation. Hair dyes change the texture The allergen in hair dye is PPD. The most common of the hair shaft, making it coarse and dull. Uncommon symptoms include itchy scalp, redness and swelling in the reactions include lymphomatoid reaction, erythema scalp, mild dandruff, swelling around the eyes and eyelids, multiforme, and anaphylaxis. and scaly skin around eyes, nose and face. Scalp skin may In such a situation it is always necessary to conduct become irritable and will not allow combing the hairs. If a patch test before one uses any coloring products. Small patient is suffering from allergic skin problems or asthma, amount has to be applied on right forearm, volar aspect flare up of these lesions may happen. If caution is not taken (front) or behind the ear lobule and watch for 48 hours while applying hair dye, hair dye may trickle into eye and for the signs of irritation or allergy. If no untoward effects conjunctivitis and keratoconjunctivitis may develop. develop, then only the coloring products can be used on The alkaline action of ammonia has to be neutralized the scalp. It is always necessary to read the ingredients list immediately, otherwise hair damage will continue and hair

16 Vol 8(1), January 2018 | www.rjms.in RGUHS J Med Sciences K. Hanumanthayya et al : Hair Coloring – Hair Dyeing will lose lustiness and silkiness, and may become rough 3. Horvath AL. Solubility of structurally complicated materials: and break. 3. Hair Sci World J. 2009; 9:255–71. Laboratory experiments have proven that PPD can 4. Feughelman M. Morphology and properties of hair. In, Hair and ; Johnson D H, Ed; Marcel Dekker: New York, damage human DNA cells and cause . But, small NY, USA; 1977. amount of PPD found in hair dyes is capable of causing 5. Madnani N and Khan K. Hair . Indian J Dermatol cancer is not yet established [10]. Venereol Leprol 2013; 79:654-67 Resorcinol is another chemical present in hair colors. It 6. Morel OJX and Christie RM. Current trends in the chemistry is an endocrine abnormality disrupting chemical that can of permanent hair dying. Chem Rev. 2011; 111:2537–61. 7. Bouillon C and Wilkinson JD. The Science of Hair Care; Tay- increase the risk of breast cancer by disrupting the natural lor & Francis: Boca Raton, FL USA; 2005. balance of hormones. 8. David AR and de Berker. Hair Cosmetics. In: Rook’s Text- book of Dermatology. Vol 3. 9th edn. John Wiley; 2016. p. 71–89. References 9. Handa S, Mahajan R and De D. Contact dermatitis to hair dye: An update. Indian J Dermatol Venereol Leprol. 2012; 1. Sherrow V. Encyclopedia of Hair: A Cultural History; Green- 78:583–90. wood Press: Westport, CT, USA, 2006. 10. Shafer N, Shafer RW, Potential of carcinogenic effects of hair 2. Wolfram LJ. Human hair: A unique physicochemical com- dyes. N Y State J Med. 1976; 76:394–6. posite. J Am Acad Dermatol. 2003: 48:106–40.

Vol 8(1), January 2018 | www.rjms.in RGUHS J Med Sciences 17