Some challenges in modern hair colour formulations

Formulation of hair coloring product involves two stages, first a development of product base followed by formulation of desired shade. During that process a special consideration needs to be given to a whole range of product characteristics such as dye stability in the product medium, colour wearability on hair, light fading and finally rheology of the product. This paper reviews improvement in permanent coloring products as it relates to dye and base composition. Examples are shown where a reduction or elimination of certain dyes, m-phenylenediamine or sodium picramate, improves long term stability and product performance on hair. In cases when only reduction of the dyes was carried out, improvement in stability was achieved through their use as secondary colour contributors and not as primary ones. There are also other composition aspects that impact colour performance of the final product. For example, pH of the coloring mixture has a pronounced effect on the final colour developed in hair. It is shown that a shift in tonality caused by pH change can be predicted for finished product using a simple system composed of the main coupler-intermediate pair employed in the product. The colour response to pH change of this simple system was found to mirror that of the product. This predictability can be used as a formulation tool to develop more efficient dye systems. Effects of some functional materials on colour result such as propylene glycol, ascorbic acid or silicone are also shown.     

UV protection of artificially coloured hair using a leave-on formulation

The present article describes the use of a polymeric organosiloxane sunscreen (SLX), to protect the artificial colour of human hair upon simulated solar radiation. The cosmetic vehicle used to treat the coloured hair is a leave-on formula. It has been found that the semi-permanent and permanent colours can both be degraded when exposed to simulated sunlight. The efficacy of SLX to protect the artificial colours was compared to ethylhexyl methoxycinnamate (EHMC), the most often used UV filter in marketed sun sprays. SLX (1-5%) was more effective than EHMC (1-5%) to protect the artificially coloured hair, especially by protecting the lightness of the hair.     

Application of TLC and HPTLC in the analysis of semipermanent hair dyes

Semipermanent or direct colouring includes any product capable of affecting to some extent a change in the natural hair colour that will last through at least five shampoo washings. Semipermanent dyes are simple and easy to use, as opposed to oxidation dyes, and are normally formulated for application on nonbleached hair. Following increases in supply of such formulations, we have started an analysis for quality control purposes of 21 commonly marketed dyestuffs (nitroaminobenzenes, anthraquinone and Arianor dyes) and 20 colouring products manufactured by four leading companies. By using TLC (silica gel and reversed phase) and HPTLC (silica gel) procedures we have determined relative retention values to 1,3-diamino-4-nitrobenzene of standards and dyes found in the commercial products. All the values reported (standards and samples) are the average of five analytical results (+/-SD).     

The measurement of hair colour

The colour of the hair of 65 subjects was measured using a Minolta Chromameter model CR200. Readings were taken by holding the unit against the back of the subject's head, and recorded using the L*a*b* system of colour co-ordinates.
All subjects had hair in which yellow and red (rather than blue or green) dominated. The lightness (L*) of all hair fell in the range 17–67, the redness (a*) in the range 0–6 and the yellowness (b*) 0–20. These limits can be seen as effectively outlining the range of colours which can be said to be natural.
The chromameter gave rapid and reproducible results on hair in situ and was easy to use. The method should be of use to those who wish to quantify the effects brought about by bleaching or dyeing formulations.     

How different is human hair? A critical appraisal of the reported differences in global hair fibre characteristics and properties towards defining a more relevant framework for hair type classification

This review critically appraises the reported differences in human hair fibre within three related domains of research: hair classification approaches, fibre characteristics and properties. The most common hair classification approach is based on geo-racial origin, defining three main groups: African, Asian and Caucasian hair. This classification does not account sufficiently for the worldwide hair diversity and intergroups variability in curl, shape, size and colour. A global classification into eight curl types has been proposed but may be too complex for reproducibility. Beyond that, hair cross-sectional shape and area have been found to have an inverse relation to curl: straighter fibres are circular with larger cross-sectional area, whilst the curlier fibres are elliptical with smaller cross-sectional area. These geometrical differences have been associated with bilateral vs homogenous distribution of cortical cell in curly vs straight hair respectively. However, there is no sufficient data demonstrating significant differences in hair amino composition, but proteomic studies are reporting associations of some proteins with curly hair. Eumelanin’s relative abundance has been reported in all hair colours except for red hair which has a high pheomelanin content. Higher tensile and fatigue strength of straight hair are reported, however, curly hair fragility is attributed to knotting, and crack and flow formations rather than the structural variations. African hair has been found to have the highest level of lipids, whilst the water sorption of Caucasian hair is the highest, and that of Asian hair the lowest. Not all comparative studies clearly report their hair sampling approaches. Therefore, to strengthen the robustness of comparative studies and to facilitate cross-study data comparisons, it is recommended that the following hair defining characteristics are reported in studies: hair cross sectional diameter/area, curl type, hair assembly colour, as well as where possible donor data (age/gender) and sample pooling approach.     

Effect of pyruvic acid and ascorbic acid on stability of 3‐deoxyanthocyanidins

BACKGROUND: 3‐Deoxyanthocyanins are a rare class of plant pigments primarily found in sorghum and known to possess distinct chemical and bioactive properties. They have potential as natural food colourants. This work investigates how 3‐deoxyanthocyanin pigments react with pyruvic acid and their stability in the presence of ascorbic acid. RESULTS: Substitution at C‐5 was the major determinant of the mechanism of 3‐deoxyanthocyanidin complexation with pyruvic acid: hydroxyl substitution favoured cyclic condensation, whereas methoxyl substitution favoured oxidative ring contraction. Pure 3‐deoxyanthocyanidins generally showed poor stability in the presence of 500 mg L^?1 ascorbic acid at pH 2.0 and 3.2 but were stable at pH 5.0; pyruvic acid improved their stability at pH 2.0 and 3.2 and enhanced their colour intensity at pH 5.0. Crude sorghum pigment extract was very stable in the presence of ascorbic acid: 31% colour loss at pH 2.0; 1.9‐ and 1.3‐fold increases in colour intensity at pH 3.2 and 5.0 respectively. In contrast, red cabbage pigment lost 30–85% of its colour in the presence of ascorbic acid under the conditions used in the study. CONCLUSION: Crude sorghum pigments are very stable in the presence of ascorbic acid and may be useful as natural food colourants. Copyright © 2008 Society of Chemical Industry     

Evaluation of an in vitro percutaneous permeation model with two oxidative hair dyes

The percutaneous permeation of two oxidative hair dyes was measured by means of pig skin in a flow-through diffusion cell system entirely constructed from Teflon. Pig skin membranes were prepared by reducing full thickness skin with a dermatome to a more in vivo -like barrier layer and their integrity was checked by measuring the steady-state permeation of tritiated water. Initially, the inter- and intraindividual variability of percutaneous permeation was determined with an aqueous solution of 1-(2'-hydroxyethyl)-amino-3,4-methylenedioxybenzene-hydrochloride, an oxidative hair dye component. In the same way the proper flow rate of elution fluid through the receptor cell was found to be most favourable at 10 ml h^-1, the thickness of permeation membranes was fixed at 1 mm, and it was shown that storage of the skin at −20°C for up to 35 days did not change the permeability. The percutaneous permeation of the same hair dye component and of 4-amino-2-hydroxymethylphenol-hydrochloride was determined after application to pig skin membranes under practical conditions of hair dyeing. The in vitro skin permeation was in the same order of magnitude as results from comparable in vivo skin absorption studies in rats.
Perméation percutanée in vitro de colorants d'oxydation pour cheveux     

Age‐induced hair greying – the multiple effects of oxidative stress

An obvious sign of ageing is hair greying, or the loss of pigment production and deposition within the hair shafts. Numerous mechanisms, acting at different levels and follicular locations, contribute to hair greying, ranging from melanocyte stem cells defects to follicular melanocyte death. One key issue that is in common to these processes is oxidative damage. At the hair follicle stem cells niche, oxidative stress, accelerated by B‐cell lymphoma 2 gene (BCL‐2) depletion, leads to selective apoptosis and diminution of melanocyte stem cells, reducing the repopulation of newly formed anagen follicles. Melanotic bulbar melanocytes express high levels of BCL‐2 to enable survival from melanogenesis‐ and ultraviolet A (UVA)‐induced reactive oxygen species (ROS) attacks. With ageing, the bulbar melanocyte expression of anti‐oxidant proteins such as BCL‐2, and possibly TRP‐2, is reduced, and the dedicated enzymatic anti‐oxidant defence system throughout the follicle weakens, resulting in enhanced oxidative stress. A marked reduction in catalase expression and activity results in millimolar accumulation of hydrogen peroxide, contributing to bulbar melanocyte malfunction and death. Interestingly, amelanotic melanocytes at the outer root sheath (ORS) are somewhat less affected by these processes and survive for longer time even within the white, ageing hair follicles. Better understanding of the overtime susceptibility of melanocytes to oxidative stress at the different follicular locations might yield clues to possible therapies for the prevention and reversal of hair greying.     

Fading of artificial hair colour and its prevention by photofilters

Fading of artificial hair colour has been investigated by simulating actual usage conditions through exposure to artificial radiation in a weatherometer, with 0.35 mW (m(2)nm)(-1) at 340 nm, for 16-48 h, and by periodical washing. Hair colour was produced by using commercial two-part, permanent hair dyes with light auburn, medium auburn and dark auburn shades. Formulations based on red couplers, such as 4-amino-2-hydroxytoluene and 1-naphthol, as well as primary intermediates, such as 1-hydroxyethyl-4,5-diamino pyrazole sulphate, were employed. Results indicate that the extent of fading, as measured by the total colour change parameter, dE, is greatest for coloured hair subjected to both irradiation and shampooing, and significantly smaller for hair undergoing only irradiation or washing. Colour loss has been also found to be dependent upon the hair type employed, with coloured natural white and bleached hair undergoing much greater change than coloured brown hair. It has been also shown that hair colour based on pyrazole intermediates displayed the deepest fading as a result of shampooing (dE 4-6 after 10 shampooings) and irradiation per shampooing (dE 14-16 after 32 h of light exposure and four shampooings). The contribution of UV light (UVB + UVA) to the artificial hair-colour loss was found experimentally to be dependent upon the irradiation dose and varied from 63% at 16 h of irradiation time to 27% at 48 h of light exposure. The theoretical extent of photoprotection by a formulation was assessed by calculating the percentage of UV light it attenuates in the wavelength range from 290 to 400 nm. The results indicate that UVB photofilters, such as octyl methoxy cinnamate, absorb <25% of the total UV irradiation at concentrations as high as 30 mg (g hair)(-1). UVA absorbers were found to be more effective, with benzophenone-3 and benzophenone-4 absorbing about 40% of UV at the same concentration. Corresponding experimental data were in reasonable agreement with the theoretical predictions. The data are also presented for colour protection with treatments containing two photo-absorbers: benzophenone-3-ZnO; benzophenone-4-ZnO; octyl methoxy cinnamate-ZnO; and dimethylpabaimidopropyl laurdimonium tosylate-benzophenone-3.     

Colloidal approach to prepare colour blends from colourants with different solubility profiles

Food colouring plays a vital and a determining role in the processing and the manufacturing of food products because the appearance of products is critical for attracting consumers and influencing their food choices. However, factors such as legislative restrictions, limited number of approved colourants and the processing, formulation and stability issues of the natural colourants severely limits the application of food colouring in actual product formats. Hence, finding alternatives to the currently utilised formulation practises, represents an important area of research. Here, we report a simple colloidal approach to prepare colour blends by co-incorporating colourants with contrasting aqueous solubility profiles in composite colloidal particles. Curcumin and indigocarmine were selected as water insoluble and water soluble food-grade colourants respectively and incorporated in the colloidal particles prepared from food protein-zein. Composite particles obtained by loading of curcumin and indigocarmine (at different ratios) had mean particle size ranging from 76 to 300 nm. The spherical shape of the colloidal particles was confirmed using transmission electron microscopy and the colloidal dispersions were further characterised using UV–Vis and fluorescence spectroscopy. The incorporation of colourants in colloidal particles led to the generation of different shade of colour in yellow–green–blue range. The encapsulation also led to the stabilization of individual pigments against photodegradation. Such composite colloidal particles could potentially serve as an approach for developing tuneable colouring system for food and nutraceutical applications.     

Liquid crystal colloidal structures for increased silicone deposition efficiency on colour‐treated hair

An approach is described to increase the deposition efficiency of silicone conditioning actives from a shampoo on colour‐treated hair via liquid crystal (LC) colloidal structures, created with a high charge density cationic polymer, poly(diallyldimethyl ammonium chloride) and negatively charged surfactants. LCs are materials existing structurally between the solid crystalline and liquid phases, and several techniques, including polarized light microscopy, small angle X‐Ray analysis, and differential scanning calorimetry, were used to confirm the presence of the LC structures in the shampoo formula. Silicone deposition from the LC‐containing shampoo and a control shampoo was measured on a range of hair substrates, and data from inductively coupled plasma optical emission spectroscopy analysis and ToF‐SIMS imaging illustrate the enhancement in silicone deposition for the LC shampoo on all hair types tested, with the most pronounced enhancement occurring on hair that had undergone oxidative treatments, such as colouring. A model is proposed in which the LC structure deposits from the shampoo onto the hair to: (i) provide ‘slip planes’ along the hair surface for wet conditioning purposes and (ii) form a hydrophobic layer which changes the surface energy of the fibres. This increase in hydrophobicity of the hair surface thereby increases the deposition efficiency of silicone conditioning ingredients. Zeta potential measurements, dynamic absorbency testing analysis and ToF‐SIMS imaging were used to better understand the mechanisms of action. This approach to increasing silicone deposition is an improvement relative to conventional conditioning shampoos, especially for colour‐treated hair.     

The isolation and properties of a concentrated red‐purple betacyanin food colourant from Opuntia stricta fruits

A red‐purple food colourant from Opuntia stricta fruits was obtained and studied. Four steps were involved in its isolation: washing, extraction, centrifugation and concentration. Ethanol:water 60:40 (v/v) was selected as the optimum extraction solvent to reduce the viscosity caused by the presence of mucilage and pectins. The resulting 40‐fold concentrated extract had a high colour strength (3.9, OD 535 nm, 1% v/v sol), a high betanin concentration (4.7 g L⁻¹) and low viscosity (59.0 cP). It also showed high stability (t_1/2 = 236.6 d, 4 °C) mainly due to its low pH (3.4) and low water content (571 g kg⁻¹). These characteristics were in the same range as shown by three commercially available liquid concentrated colourants studied (red beet, red carrot and red grape skin). The colour parameters of this concentrated extract of Opuntia stricta were compared with those of commercial red colourants (red beet, red carrot, red grape skin, cochineal, elderberry, hibiscus and red cabbage). CIELAB values of Opuntia stricta (1.5 mL L⁻¹) were L* = 69.8, a* = 59.7 and b* = −23.5. Opuntia stricta presented a vivid red‐purple colour which was distinguishable from the colours shown by the other natural red food colourants. Copyright © 2005 Society of Chemical Industry     

Significance of hair‐dye base‐induced sensory irritation

Oxidation hair ‐ dyes, which are the principal hair ‐ dyes, sometimes induce painful sensory irritation of the scalp caused by the combination of highly reactive substances, such as hydrogen peroxide and alkali agents. Although many cases of severe facial and scalp dermatitis have been reported following the use of hair ‐ dyes, sensory irritation caused by contact of the hair ‐ dye with the skin has not been reported clearly. In this study, we used a self‐assessment questionnaire to measure the sensory irritation in various regions of the body caused by two model hair‐dye bases that contained different amounts of alkali agents without dyes. Moreover, the occipital region was found as an alternative region of the scalp to test for sensory irritation of the hair‐dye bases. We used this region to evaluate the relationship of sensitivity with skin properties, such as trans‐epidermal water loss (TEWL), stratum corneum water content, sebum amount, surface temperature, current perception threshold (CPT), catalase activities in tape‐stripped skin and sensory irritation score with the model hair‐dye bases. The hair‐dye sensitive group showed higher TEWL, a lower sebum amount, a lower surface temperature and higher catalase activity than the insensitive group, and was similar to that of damaged skin. These results suggest that sensory irritation caused by hair ‐ dye could occur easily on the damaged dry scalp, as that caused by skin cosmetics reported previously.     

The biology of hair diversity

Hair diversity, its style, colour, shape and growth pattern is one of our most defining characteristics. The natural versus temporary style is influenced by what happens to our hair during our lifetime, such as genetic hair loss, sudden hair shedding, greying and pathological hair loss in the various forms of alopecia because of genetics, illness or medication. Despite the size and global value of the hair care market, our knowledge of what controls the innate and within‐lifetime characteristics of hair diversity remains poorly understood. In the last decade, drivers of knowledge have moved into the arena of genetics where hair traits are obvious and measurable and genetic polymorphisms are being found that raise valuable questions about the biology of hair growth. The recent discovery that the gene for trichohyalin contributes to hair shape comes as no surprise to the hair biologists who have believed for 100 years that hair shape is linked to the structure and function of the inner root sheath. Further conundrums awaiting elucidation include the polymorphisms in the androgen receptor (AR) described in male pattern alopecia whose location on the X chromosome places this genetic contributor into the female line. The genetics of female hair loss is less clear with polymorphisms in the AR not associated with female pattern hair loss. Lifestyle choices are also implicated in hair diversity. Greying, which also has a strong genetic component, is often suggested to have a lifestyle (stress) influence and hair follicle melanocytes show declining antioxidant protection with age and lowered resistance to stress. It is likely that hair research will undergo a renaissance on the back of the rising information from genetic studies as well as the latest contributions from the field of epigenetics.     

二氧化氯对活性染料的脱色

 为寻求一种理想的活性染料氧化脱色技术,用二氧化氯(ClO2)对存在于染料废水及有色纺织品中的3种不同结构的活性染料进行脱色处理,分别用紫外可见光谱仪和测色配色仪对染料废水和织物中的染料进行脱色性能测试。结果表明:在常温常压下,ClO2对以这2种形式存在的染料均有较好的处理效果;染料废水中的3种染料经脱色处理1 h后脱色率均达到95%以上;有色纺织品中的3种染料经剥色处理1 h后K/S值明显下降,为有色纺织品的剥色提供了一种新思路。     

染发剂中对苯二胺等32种染料检测结果分析

目的了解染发剂中染料使用情况和染发剂类化妆品安全风险点,为监管提供技术支撑。方法根据《化妆品安全技术规范》(2015年版),采用高效液相色谱法和超高效液相色谱-串联质谱法对湖南地区14个市、州地区抽样的50批染发剂类化妆品进行检测,分析其中染料种类、含量及使用情况。结果 50批染发剂共检出对苯二胺、对氨基苯酚等14种染料成分,其中对苯二胺、间氨基苯酚、间苯二酚3种染料的使用频率最高,均超过了60%。有2批染料的苯基甲基吡唑啉酮超出规定限量,其余均未超标。19批染发剂产品批件标识成分与实际检出结果不一致,不合格率为38%。结论染发剂使用情况及批件标识有待规范,应加强对染发剂类产品的监管。     

A highly sensitive method to determine the washing resistance of artificial hair colours

Citation: IFSCC Magazine, 11 (2008) (2) 139–142 Abstract: Due to the improved performance of modern hair colorants, the high natural variability in hair qualities and the individual influences of manual product applications, colour care effects of cosmetic treatments are very difficult to detect. A new, highly sensitive test method to study the colour fading behaviour of human hair was established for a large variety of cosmetic treatments. This method is based on an automatic multistage application of standard wool tissues combined with automatic colour evaluation by means of CIE L × a × b × measurements (DIN 5033). The delta E values are the main interest because they include all information regarding the L (black vs. white), a (red‐green) and b (blue‐yellow) axes defined in the Hunter Lab colour space. For validation of this new method, different permanent and non‐permanent hair colour shades were applied to undamaged light brown Caucasian hair strands. The hair strands were washed manually stepwise 30 times and the colour loss compared with the results obtained on wool tissues using an automatic application system. For most of the investigated hair colours, a coefficient of determination of r2 > 0.99 was achieved. Modern permanent hair colours show a high resistance to cosmetic treatments. Over 90% of the initial colour result was retained after 30 product applications. Shampoo and conditioner formulations induce different degrees of colour loss in hair. In basic formulas significant influences of single surfactants could be detected. The new method using wool tissues correlates very well with that using manually washed Caucasian hair strands. This automatic method is very time‐effective and offers an excellent reproducibility with a high sensitivity for assessing product influences on artificial hair colours. Keywords: Color fading, color protection, color retention, hair color resistance, hair wash simulation Paper presented at the IFSCC Conference 2007, Amsterdam, The Netherlands     

Metals in female scalp hair globally and its impact on perceived hair health

Globally, billions of individuals wash their hair in water, which acts as an exogenous metal source. Many studies which measure the metal levels found on human hair specifically aim to remove exogenous materials prior to analysis. Although this is needed when using hair analysis to probe the impact of the local environment on endogenous metal levels, it is not relevant for understanding exactly what is on hair as a result of contact with its daily environment. Understanding these levels are important, as the presence of redox active metals, such as copper and iron, can impact fibre health, either as a result of UV irradiation, or during the hair colouring process. A global hair sampling study of over 300 individuals from nine countries has been performed, and the combined endogenous and exogenous metals analysed. The levels measured vary widely, even within the narrow geography of each hair sampling location. The levels of calcium, magnesium, copper and iron were not correlated, and within each location, there are expected to be individuals with high metal levels. Levels increased from hair root to tip for calcium, magnesium and copper, attributed to hair contact with the environment showing the impact of exogenous metals in the overall levels on hair. Levels of redox metals were comparable between individuals who coloured or did not colour their hair, although water hardness ions were statistically significantly higher for hair colouring individuals. Individuals who perceived their hair health as poor had higher metal levels on their hair. Controlling metals on hair, either by preventing their binding during environmental contact, or through controlling their ability to cause hair damage, should lead to improved consumer perceived hair health.     

Assessment of tinctorial power of food colourants

Two model food systes were developed to assess the tinctorial power of colourants. Using synthetic colourants typically found in foods, and at appropriate concentrations, a range of colours was produced in each of the systems. The colours were measured as Hunter L, a, b values and plotted to define the region within the colour solid wherein acceptable food colours lie. Two natural colourants were tested in the model systems and the concentrations at which they exhibited acceptable colours determined. The systems are useful for assessing the tinctorial power of natural compounds in a quantitative and meaningful manner.     

Behenamidopropyl Dimethylamine: unique behaviour in solution and in hair care formulations

The rise of ecological awareness among consumers and industry has impacted the cationic surfactants market. The most used cationic surfactants present some drawbacks in this sense. Therefore, new molecules are being studied and developed which fulfil eco‐toxicological requirements without losing performance. One of these surfactants is Behenamidopropyl Dimethylamine (BAPDMA). This biodegradable amidoamine, which converts into a cationic surfactant at acidic pH, shows outstanding water solubility, despite its very long alkyl chain. Its behaviour in solution has been exhaustively studied. The conditioning performance of this product is superior to that of commonly used cationic surfactants, providing a superior sensorial profile and improved combing force reductions on hair. Moreover, other applications for this product in the non‐ionic form have been studied, such as conditioning agent in 2 in 1 shampoos, where it also shows colour protection effects, and as gelling agent in hair colouration creams. This multifunctional and high performance profile, together with an improved biodegradation and aquatic toxicity compared with currently used cationic surfactants, make this product a very interesting eco‐friendly alternative for the hair care market.