Gloss of hair surfaces: Problems of visual evaluation and possibilities for goniophotometric measurements of treated strands

W. Czepluch; G. Hohm; K. Tolkiehn

j. Soc. Cosmet. Chem., 44, 319-328 (November/December) Group selectivity of ethoxylation of hydroxy acids ANTHONY J. O'LENICK, JR., and JEFF K. PARKINSON, $iltech Inc., 4437 Park Drive, Norcross, GA 30093, Received June 15, 1993, Synopsis A study of the ethoxylation of two hydroxy acids was undertaken to determine if there was any group selectivity of ethoxylation. The hydroxy acids chosen for study were 12-hydroxystearic and lactic acid. Standard ethoxylation reactions were carried out using one mole of ethylene oxide to one mole of each hydroxy acid. Unlike typical fatty acids or alcohols, 12-hydroxystearic acid and lactic acid both ethoxylate without a catalyst. This could be explained by the presence of both a hydroxyl and carboxyl in the reaction solution or the presence of both groups in the same molecule. We suggest that this may be due to some type of complex forming between the oxide and the carboxyl and hydroxyl groups, since blends of stearic acid and stearyl alcohol fail to ethoxylate without a catalyst. Despite the fact that carboxyl groups of the hydroxy acids studied ethoxylate almost exclusively under base catalyst, and predominately with no catalyst, the reaction rate does not show an induction period, which would be expected for carboxyl group ethoxylation. The ethoxylation rates approximate those of primary alcohols under base catalyst. Ethoxylation of both hydroxyl groups and carboxyl groups has been practiced for many years in the preparation of many surface-active agents. Fatty acid ethoxylates and fatty alcohol ethoxylates are members of a wide range of ethoxylates that are excellent surfactants. Surfactants are surface-active agents that function as detergents, wetting agents, and emulsifiers. They are used as solubilizers, coupling agents, fiber lubricants, antistats, leveling agents, and dyeing assists (1). In addition, these materials are used in numerous personal care applications and are key raw materials in the preparation of other surfactants like fatty alcohol ether sulfates. Ethylene oxide reacts in an extremely exothermic manner with compounds having a labile hydrogen. Fatty acids and fatty alcohols are two of many such compounds containing a labile hydrogen. Alkaline and acidic catalysts make the reaction possible and accelerate it. FATTY ALCOHOL ETHOXYLATION Fatty alcohols react with ethylene oxide at the hydroxyl group to give an ether linkage and a new hydroxyl group. While conceptually the reaction is simple, the reality is that the reaction product is a complex mixture of oligomeric products that are a series of compounds that contain different amounts of ethylene oxide (2). A relatively wide distribution of species that have varying amounts of oxide reaction products present on the base hydrophobe is produced by the reaction. 319

Previous Page Next Page

Purchased for the exclusive use of nofirst nolast (unknown)
From: SCC Media Library & Resource Center (library.scconline.org)

Volume 44 No 6 resources

Download PDF Gloss of hair surfaces: Problems of visual evaluation and possibilities for goniophotometric measurements of treated strands (20)

Extracted Text (may have errors)

HAIR GLOSS 317 CONCLUSIONS ß The estimation of gloss on hair surfaces by goniophotometric measurements requires a restriction to few parameters that correspond with the visible hair properties. An increase in the reflected amount of light in the reflection maximum and a decrease in the half-value angle of the indicatrix result in an improvement of gloss. ß An often underestimated problem, the preparation of testing strands, has been solved. The development of an acceptable technique to fix hair strands in a repro- ducible manner allows comparisons of the same samples before and after treatments by goniophotometric measurements. ß Although the human eye is indeed able to perceive small differences in gloss, it has problems in realizing the order of magnitude. The objective goniophotometric method was of great significance in detecting these small differences in gloss in absolute values. ß In some samples one can see which way the cuticle surface is influenced by hair rinses and hair gels. Commercial products like care sprays and glazes are only suitable to improve gloss on damaged hair strands. An increase of gloss on undamaged brown hair results from products that are able to smooth the surface of the cuticle and where the light reflection occurs at the treatment area. ß Consisting of various detailed information, gloss is actually a perception of light reflection recognized by the naked eye. Through goniophotometric measurements we can receive a lot of this detailed information, such as surface behavior, cuticle reflec- tion, hair damage, mode of action by different product treatments, smoothing of the cuticle layer, light absorption, and also the coloring of the hair. In spite of the great number of very interesting results, further refinements of the measuring device will be helpful. The study of hair surfaces by goniophotometric measurements represents an efficient method to solve these problems. REFERENCES (1) V. W. G. Harrison, Definition and Measurement of Gloss (Hefer & Sons Ltd., Cambridge, 1945). (2) R. F. Stamm, M. L. Garcia, and J. J. Fuchs, The optical properties of human hair, Parts I and II, J. Soc. Cosmet. Chem., 28, 571-599, 601-699 (1977). (3) H. K. Bustard and R. W. Smith, Investigation into the scattering of light by human hair, Appl. Optics, 30, 3485-3491, (1991). (4) M. Tetsuo, O. Masaaki, and H. Tadashi, Cosmet. Toiletr., 107, 53-59 (1992). (5) International Commission on Illumination, International Lighting Vocabulary, CIE Publ. No. 17.4 (Bureau Central de la Commission Electrotechnique Internationale, Geneva, 1987), p. 125. (6) International Standard ISO 2813: Paints and varnishes--Measurement of specular gloss of non-metallic paint films at 20 ø, 60 ø and 85 ø. 2nd ed. (1978). (7) W. Wundt, Ober das Binocularsehen und subjektive Farben, Poggendorj5 Annalen der Physik, 114, 163-168 (1861). (8) W. Czepluch, Glanz beim binokularen Sehen, Fortschr.-Ber. VDI-Z Reihe 17, Nr. 24 (VDI-Verlag, Dusseldorf, 1984). (9) International Commission on Illumination, CIE research note: Evaluation of the attribute of appear- ance called gloss, CIEJournal, 5, 41-56 (1986). (10) International Commission on Illumination: Colorimetry (E-1.3.1), CIE Publ. No. 15, 1971 Supplement No. 2 (TC-1.3), 1978 (Bureau de la Commission Electrotechnique Internationale, Geneva). (11) T. N. Cornsweet, Visual Perception (Academic Press, New York and London, 1970), p. 345. (12) Francis X. D. O'Donnel, PsychometricScaling of Gloss, Thesis, Rensselaer Polytechnic Institute, 1984.

Help

316 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS L o c e PHUP13N PH1P13N PH4P13N PHSP13N 1.80 120 0 6o o oo -50 +2'5.0 +55 0 +85 0 permanent waved and bleached hair additional treatment Gloss and Styling Gel, measured after 3 minutes measured after 2 5 hours measured after 21 hours R e c e p t o r c n g I e Figure 18. Indicatrix change caused by treatment with "gloss and styling gel" on a permanent-waved and bleached hair. L n (3 n c PHUPO4N PH1PO4N PH4PO4N PHSPO4N 900' 600. ,500. +25 0 +5'5,0 +85 0 undamaged dark brown hair additional treatment Gloss and Styling Gel, measured after 5 minutes measured after 2 $ hours measured after 21 hours 17 e c e p t o r c n g I e Figure 19. The same treatment as in Figure 18 on undamaged dark brown hair. by spraying with gloss hair lacquer. The reflection of the incident light occurs mainly on the gel surface, which smoothes the cuticles. Also, on undamaged dark brown hair, we achieve a remarkable gloss improvement compared to previous observations. After several hours, the improvement fades and disappears after one day. But the smoothing effect of the gel persists, and the indicatrix maximum is still at a receptor angle of ½2 • 0 ø 3 .

HAIR GLOSS 317 CONCLUSIONS ß The estimation of gloss on hair surfaces by goniophotometric measurements requires a restriction to few parameters that correspond with the visible hair properties. An increase in the reflected amount of light in the reflection maximum and a decrease in the half-value angle of the indicatrix result in an improvement of gloss. ß An often underestimated problem, the preparation of testing strands, has been solved. The development of an acceptable technique to fix hair strands in a repro- ducible manner allows comparisons of the same samples before and after treatments by goniophotometric measurements. ß Although the human eye is indeed able to perceive small differences in gloss, it has problems in realizing the order of magnitude. The objective goniophotometric method was of great significance in detecting these small differences in gloss in absolute values. ß In some samples one can see which way the cuticle surface is influenced by hair rinses and hair gels. Commercial products like care sprays and glazes are only suitable to improve gloss on damaged hair strands. An increase of gloss on undamaged brown hair results from products that are able to smooth the surface of the cuticle and where the light reflection occurs at the treatment area. ß Consisting of various detailed information, gloss is actually a perception of light reflection recognized by the naked eye. Through goniophotometric measurements we can receive a lot of this detailed information, such as surface behavior, cuticle reflec- tion, hair damage, mode of action by different product treatments, smoothing of the cuticle layer, light absorption, and also the coloring of the hair. In spite of the great number of very interesting results, further refinements of the measuring device will be helpful. The study of hair surfaces by goniophotometric measurements represents an efficient method to solve these problems. REFERENCES (1) V. W. G. Harrison, Definition and Measurement of Gloss (Hefer & Sons Ltd., Cambridge, 1945). (2) R. F. Stamm, M. L. Garcia, and J. J. Fuchs, The optical properties of human hair, Parts I and II, J. Soc. Cosmet. Chem., 28, 571-599, 601-699 (1977). (3) H. K. Bustard and R. W. Smith, Investigation into the scattering of light by human hair, Appl. Optics, 30, 3485-3491, (1991). (4) M. Tetsuo, O. Masaaki, and H. Tadashi, Cosmet. Toiletr., 107, 53-59 (1992). (5) International Commission on Illumination, International Lighting Vocabulary, CIE Publ. No. 17.4 (Bureau Central de la Commission Electrotechnique Internationale, Geneva, 1987), p. 125. (6) International Standard ISO 2813: Paints and varnishes--Measurement of specular gloss of non-metallic paint films at 20 ø, 60 ø and 85 ø. 2nd ed. (1978). (7) W. Wundt, Ober das Binocularsehen und subjektive Farben, Poggendorj5 Annalen der Physik, 114, 163-168 (1861). (8) W. Czepluch, Glanz beim binokularen Sehen, Fortschr.-Ber. VDI-Z Reihe 17, Nr. 24 (VDI-Verlag, Dusseldorf, 1984). (9) International Commission on Illumination, CIE research note: Evaluation of the attribute of appear- ance called gloss, CIEJournal, 5, 41-56 (1986). (10) International Commission on Illumination: Colorimetry (E-1.3.1), CIE Publ. No. 15, 1971 Supplement No. 2 (TC-1.3), 1978 (Bureau de la Commission Electrotechnique Internationale, Geneva). (11) T. N. Cornsweet, Visual Perception (Academic Press, New York and London, 1970), p. 345. (12) Francis X. D. O'Donnel, PsychometricScaling of Gloss, Thesis, Rensselaer Polytechnic Institute, 1984.

Previous Page Next Page

Purchased for the exclusive use of nofirst nolast (unknown)
From: SCC Media Library & Resource Center (library.scconline.org)

Volume 44 No 6 resources

Download PDF Gloss of hair surfaces: Problems of visual evaluation and possibilities for goniophotometric measurements of treated strands (20)

Extracted Text (may have errors)

HAIR GLOSS 315 , ' ' I'" ,,!, ...... :'..:,,,,,,,,,,, I • J . untreated strands .•- • sprayed 0.2s sprayed 0.2s + 0.2s sprayed 0.2s + 0.2s + 0.4s Sample 3 Sample 2 Sample 2 Sample 1 Sample 1 Figure 17. Comparison of half-value angles in arbitrary units as a function of different spraying times and three different samples of gloss hair lacquers (sample 1 and sample 2 each applied on two different strands--sample 2 is identical with the sample in Figure 16). judged as the best. Comparison of the solid indicatrices of the untreated strands in Figures 15 and 16 again shows the difference between equally prepared strands and the necessity of measuring the same sample before and after treatment. Contrary to Figure 15, the solid line in Figure 16 shows a distinct maximum for a receptor angle of ½2 30 ø, which can be interpreted as surface reflection on the cuticle (ray C in Figure 5), and a second weak maximum at ½2 • 300- AccoMing to reference 2 and ray D in Figure 5, it may originate from a reflection at the opposite lying cuticle. The minor reflection is probably caused by the absorption loss in the fiber. Spraying the hair smoothes the fiber surface again. Most light seems now to be reflected from the lacquer surface (ray A in Figure 5), as in Figure 15. GLOSS AND STYLING GELS TREATMENTS The two last examples show the effect of so-called "gloss and styling gels." In Figure 18 the product was first used on a light base--a hair strand treated with both perm and hair bleaching--and in Figure 19 it's applied on undamaged hair. Although the initial indicatrices (solid curves) of both hair types differ in their shapes, a considerable and comparable improvement of the gloss parameters, indicatrix maximum, and half-value angle can be recognized immediately after application of the product. Moreover, it can be well recognized how the angle of the reflection maximum, originally displaced by 7 ø , moves to the specular direction at 30 ø . Here we get the same effect as

316 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS L o c e PHUP13N PH1P13N PH4P13N PHSP13N 1.80 120 0 6o o oo -50 +2'5.0 +55 0 +85 0 permanent waved and bleached hair additional treatment Gloss and Styling Gel, measured after 3 minutes measured after 2 5 hours measured after 21 hours R e c e p t o r c n g I e Figure 18. Indicatrix change caused by treatment with "gloss and styling gel" on a permanent-waved and bleached hair. L n (3 n c PHUPO4N PH1PO4N PH4PO4N PHSPO4N 900' 600. ,500. +25 0 +5'5,0 +85 0 undamaged dark brown hair additional treatment Gloss and Styling Gel, measured after 5 minutes measured after 2 $ hours measured after 21 hours 17 e c e p t o r c n g I e Figure 19. The same treatment as in Figure 18 on undamaged dark brown hair. by spraying with gloss hair lacquer. The reflection of the incident light occurs mainly on the gel surface, which smoothes the cuticles. Also, on undamaged dark brown hair, we achieve a remarkable gloss improvement compared to previous observations. After several hours, the improvement fades and disappears after one day. But the smoothing effect of the gel persists, and the indicatrix maximum is still at a receptor angle of ½2 • 0 ø 3 .

320 JOURNAL OF THE SOCIETY OF COSMETIC CHEMISTS Our analyses of the products that are produced when one mole of ethylene oxide is reacted with one mole of stearyl and coco alcohol are shown in Tables I and II, respec- tively. The analyses were done via gas-liquid chromatography. Table I shows that when one mole of ethylene oxide is reacted with one mole of fatty alcohol, adducts having no added ethylene oxide are the predominate material in the mixture, making up 60.3% of the mixture. The other adducts, ranging from 1 to 8 moles of ethylene oxide, make up the remainder. If the amount of ethylene oxide found on each adduct is multiplied by the percentage of that adduct, the EO contribution is calculated. The difference between the observed 0.978 moles and the 1.0 added is primarily polyoxyalkylene glycol formation. Table II shows that when one mole of ethylene oxide is reacted with one mole of coco fatty alcohol, adducts having no added ethylene oxide are the predominate material in the mixture, making up 54.8% of the mixture. The other adducts, ranging from 1 to 8 moles of ethylene oxide, make up the remainder. If the amount of ethylene oxide found on each adduct is multiplied by the percentage of that adduct, the EO contri- bution is calculated. The difference between the observed 0.993 moles and the 1.0 added primarily represents polyoxyalkylene glycol formation. Much work has been done in recent years to "peak" ethoxylates (3-6). Catalysts are chosen to produce peaked ethoxylates that have a more narrow distribution of ethoxy- lated oligomers. Some excellent pioneering work in ethoxylation of fatty acids and fatty alcohols was published in 1956 by Wrigley et al. (7). This work indicated two salient properties of ethoxylation of alcoholic hydroxyl groups. First, the products of the reaction sequence are complex mixtures, and second, the reaction begins immediately that is, there is no induction period prior to the start of the reaction. Induction time, as will be shown subsequently, is a salient property of fatty acid ethoxylation. Figure 1 shows the number of moles of ethylene oxide that react with stearic acid and stearyl alcohol, using 0.5% KOH at 160 C. Clearly, there is a significant difference in the kinetics of ethoxylation comparing fatty acid ethoxylation and fatty alcohol ethox- ylation. The differences are most dramatic in the initial stages of the reaction. Table I Ethoxylation of Stearyl Alcohol With One Mole Ethylene Oxide Moles of EO Area % EO Contribution Designation [Value A] [Value B] [Value (A) (B)] 18-0 0 60.3 O. 000 18-1 1 13.6 0.136 18-2 2 8.8 O. 176 18-3 3 7.9 0.237 18-4 4 5.9 0.236 18-5 5 2.2 0.110 18-6 6 0.9 0.054 18-7 7 0.3 0.021 18-8 8 0.1 0.008 Total 100.0% Total calculated moles added 0.978

ETHOXYLATION OF HYDROXY ACIDS 321 Table II Ethoxylation of Coco Alcohol With One Mole of Ethylene Oxide Moles of EO Area % EO Contribution Designation [Value A] [Value B] [Value (A) (B)] NO EO 0 54.8 0.000 EO 1 1 19.6 0.196 EO 2 2 10.2 0.204 EO 3 3 6.8 0.204 EO 4 4 5.5 0.220 EO 5 5 2.1 0.105 EO 6 6 0.7 0.042 EO 7 7 0.2 0.014 EO 8 8 0.1 0.008 Total 100.0% Total calculated moles added 0.993 Unlike the kinetics observed with the ethoxylation of fatty alcohols, the base-catalyzed reaction of ethylene oxide with fatty acids is divided into two stages. The first is a stage in which negligible product forms. Slowly, the reaction of the acid and ethylene oxide begins after an induction period to give mostly ethylene glycol monoester. In the second stage, after the addition of about one mole, the reaction rate increases (8). Clearly, the existence of an induction period in the ethoxylation process indicates that the reaction is one of a fatty acid and ethylene oxide, rather than a fatty alcohol and ethylene oxide. As seen in Figure 2, the ethoxylation of fatty alcohols will not occur to an appreciable extent without a catalyst. The catalyst can be either acidic or, more typically, alkaline. Alkaline catalysts generally produce fewer by-products. One of the by-products that is made in the ethoxylation of fatty alcohols is polyethylene 0 0.5 1 1.5 2 2.5 3 3.5 -• Stearic Acid + Stearyl Alcohol Reaction Condition 1. Temperature 150 C 2. Initial Pressure 45 psig 3. Catalyst 0.1 % KOH Time At Reaction Condition (in H .... Figure 1. Moles of ethylene oxide added versus time.

Previous Page Next Page

Purchased for the exclusive use of nofirst nolast (unknown)
From: SCC Media Library & Resource Center (library.scconline.org)

Volume 44 No 6 resources

Download PDF Group selectivity of ethoxylation of hydroxy acids (10)

Volume 44 No 6 resources

All section downloads (PDF)

Extracted Text (may have errors)

Help

loading

Volume 44 No 6 resources

Extracted Text (may have errors)

Volume 44 No 6 resources