Polymers in Hair Products

  • Clarence R. RobbinsEmail author


Polymers have become increasingly important components of cosmetics over the past few decades. The original uses of polymers in hair care were as fixative agents and viscosity controlling additives; however, new polymers today are also used for hair conditioning and for the development of new style control products. Polymer substantivity to hair fibers increases with molecular size, with an increasing number of polar group attachments and especially with an increasing number of cationic groups for attachment to the negatively charged surface of hair fibers. From an anionic shampoo medium the cationic charge on polymers is neutralized and the adsorbing species is essentially a neutral or negatively charged species. The most successful silicone conditioning polymers for hair care have been used in both shampoo and conditioner compositions. Dimethicones in shampoos condition undamaged or lightly damaged hair better than they condition highly damaged, bleached hair or even tip ends because neutral hydrophobic conditioning agents adsorb more readily to an undamaged hydrophobic surface than to a damaged highly polar hair surface. New block co-polymers and a fairly large number of new cationic polymers have been introduced into hair care recently, while fractal polymers (highly irregular shapes) and nanoparticles have been developed and are receiving attention for potential use in hair care.


Volatile Organic Compound Anionic Surfactant Cationic Polymer Hair Fiber Hair Surface 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


  1. 1.
    Lockhead RY (2010) IP trends in hair care polymers. HAPPIGoogle Scholar
  2. 2.
    Gerstein T (1976) Shampoo conditioner formulations. US Patent 3,990,991Google Scholar
  3. 3.
    Lang EW (1968) Wave set retention shampoo containing polyethyleneimine polymers. US Patent 3,400,198Google Scholar
  4. 4.
    Parran J Jr (1970) Detergent compositions containing particulate deposition enhancing agents. US Patent 3,489,686Google Scholar
  5. 5.
    Parran J Jr (1971) Detergent compositions containing particle deposition enhancing agents. US Patent 3,580,853Google Scholar
  6. 6.
    Hough PS, Huey J, Tolgyesi WS (1976) Hair body. J Soc Cosmet Chem 27:571–578Google Scholar
  7. 7.
    Guskey SM et al. (2000) Styling shampoo compositions which deliver improved curl retention and hair feel. US Patent 6,040,282Google Scholar
  8. 8.
    Rufe RG (1975) Cellulose polymers in cosmetics and toiletries. Cosmet Perfumery 90:93–94Google Scholar
  9. 9.
    Kennerley MG (1976) Shampoo containing a water-soluble linear carboxylic polymer. US Patent 3,969,500Google Scholar
  10. 10.
    Kamath Y, Dansizer CJ, Weigmann HD (1977) Wettability of keratin fiber surface. J Soc Cosmet Chem 28:273–284Google Scholar
  11. 11.
    Miller B, Young R (1975) Methodology for studying the wettability of filaments. Tex Res J 45:359–365CrossRefGoogle Scholar
  12. 12.
    Fawkes FM (1965) In: Gushee DE (ed) Chemistry and physics of interfaces. American Chemical Society, Washington, DC, pp 1–12Google Scholar
  13. 13.
    Wu S (1971) Calculation of interfacial tension in polymer systems. J Polym Sci (Part C) 34:19–30CrossRefGoogle Scholar
  14. 14.
    Steinhardt J, Fugitt CH, Harris M (1942) Further investigations of the affinities of anions of strong acids for wool. J Res Natl Bur Stand 28:201–216Google Scholar
  15. 15.
    Steinhardt J, Zaiser E (1949) Combination of wool protein with cations and hydroxyl ions. J Res Natl Bur Stand 35:789–802Google Scholar
  16. 16.
    Pauling L (1948) The nature of the chemical bond. Cornell University Press, Ithaca, p 3Google Scholar
  17. 17.
    Maron SH, Prutton CF (1958) Principles of physical chemistry. Macmillan, New York, p 742Google Scholar
  18. 18.
    Gilreath ES (1958) Fundamental concepts of inorganic chemistry. McGraw-Hill, New York, p 219Google Scholar
  19. 19.
    Morrison RT, Boyd RN (1960) Organic chemistry. Allyn and Bacon, Boston, p 19Google Scholar
  20. 20.
    Mark H (1943) In: Burk RE, Grummitt O (eds) The “chemistry of large molecules”, frontiers in science I. Interscience, New York, p 66Google Scholar
  21. 21.
    Mark H (1942) Intermolecular forces and mechanical behavior of high polymers. Ind Eng Chem 34:1343–1348CrossRefGoogle Scholar
  22. 22.
    Pauling L (1948) The nature of the chemical bond. Cornell University Press, Ithaca, p 160Google Scholar
  23. 23.
    Faucher JA, Goddard E (1976) Influence of surfactants on the sorption of a cationic polymer by keratinous substrates. J Colloid Interface Sci 55:313–319CrossRefGoogle Scholar
  24. 24.
    Wilkerson V (1935) The chemistry of human epidermis. J Biol Chem 112:329–335Google Scholar
  25. 25.
    Faucher JA, Goddard ED, Hannah RB (1977) Sorption and desorption of a cationic polymer by human hair: effects of salt solutions. Tex Res J 47:616–620Google Scholar
  26. 26.
    Paul DR, McSpadden SK (1976) Diffusional release of a solute from a polymer matrix. J Membr Sci 1:33CrossRefGoogle Scholar
  27. 27.
    Cooperman ES, Johnsen VL (1973) Penetration of protein hydrolyzates into human hair strands. Cosmet Perfumery 88:19–22Google Scholar
  28. 28.
    Chow C (1971) Interaction between polyethylene-imine and human hair. Tex Res J 41:444–450CrossRefGoogle Scholar
  29. 29.
    Crawford RJ, Robbins CR (1980) A replacement for Rubine dye for detecting cationics on keratin. J Soc Cosmet Chem 31:273–278Google Scholar
  30. 30.
    Scott GV, Robbins C, Barnhurst JD (1969) Sorption of quaternary ammonium surfactants by human hair. J Soc Cosmet Chem 20:135–152Google Scholar
  31. 31.
    Goddard E, Hannah RB (1976) Cationic polymer/anionic surfactant interactions. J Colloid Interface Sci 55:73–79CrossRefGoogle Scholar
  32. 32.
    Hannah RB, Goddard ED, Faucher JA (1978) Communications to the editor: desorption of a cationic polymer from human hair. Tex Res J 48:57–58CrossRefGoogle Scholar
  33. 33.
    Goddard ED et al (1975) Adsorption of polymer JR on keratinous surfaces-Part III. J Soc Cosmet Chem 26:539–550Google Scholar
  34. 34.
    Estrin F (ed) (1982) CTFA cosmetic ingredient dictionary, 3rd edn. Cosmetic, Toiletry and Fragrance Association, Washington, DCGoogle Scholar
  35. 35.
    Robbins CR, Scott GV (1970) Effect of pH on the Arrhenius activation energy for the diffusion into keratin fibers. Tex Res J 40:951–952CrossRefGoogle Scholar
  36. 36.
    Schwuger MJ (1973) Mechanism of interaction between ionic surfactants and polyglycol ethers in water. J Colloid Interface Sci 43:491–498CrossRefGoogle Scholar
  37. 37.
    Putnam FW, Neurath HJ (1944) The precipitation of proteins by synthetic detergents. J Am Chem Soc 66:692–697CrossRefGoogle Scholar
  38. 38.
    Putnam FW (1948) The interactions of proteins and synthetic detergents. Adv Protein Chem 4:79–122PubMedCrossRefGoogle Scholar
  39. 39.
    Isemura T, Imanishi J (1958) The dissolution of water-insoluble polymers in the surfactant solution. The polyelectrolyte-like behavior of the dissolved polymers. J Polym Sci 33:337–352CrossRefGoogle Scholar
  40. 40.
    Capalbi A, LaMesa C (2001) Polymer surfactant interactions. J Therm Anal Calorim 66:233–241CrossRefGoogle Scholar
  41. 41.
    Manuszak-Guerrini M, Lochhead RY et al (1997) Complexation of aminoalkyolcarbamoyl cellulosics as oppositely charged mixed micelles. J Soc Cosmet Chem 48:23–40Google Scholar
  42. 42.
    Woodard J (1972) Aziridine chemistry-application for cosmetics. J Soc Cosmet Chem 23:593–603Google Scholar
  43. 43.
    Sykes AR, Hammes PA (1980) The use of merquat polymers in cosmetics. Drug Cosmet Ind 126:35, 62, 64, 66, 68, 136, 159Google Scholar
  44. 44.
    Fevola MJ (2011) Ingredient Profile. Polyquaternium-6, Cosmetics & Toiletries 126:2–5Google Scholar
  45. 45.
    Idson B, Lee W (1983) Update on hair conditioner ingredients. Cosmet Toiletries 98:41–46Google Scholar
  46. 46.
    McMullen R, Jachowicz J (1998) Thermal degradation of hair. III: Effect of selected polymers and surfactants. J Cosmet Sci 49:245–258Google Scholar
  47. 47.
    Herd J, Marriot R (1959) The sorption of amino acids from shampoos onto hair. J Soc Cosmet Chem 10:272–277Google Scholar
  48. 48.
    Newman W (1972) The sorption of tryptophan onto human hair. Tex Res J 42:207–214CrossRefGoogle Scholar
  49. 49.
    Karjala SA et al (1967) The effect of pH on the sorption of collagen-derived peptides by hair. J Soc Cosmet Chem 18:599–608Google Scholar
  50. 50.
    Karjala SA et al (1966) Studies on the substantivity of collagen derived polypeptides to human hair. J Soc Cosmet Chem 17:513–524Google Scholar
  51. 51.
    Cooperman E, Johnson V (1973) Penetration of protein hydrolyzates into human hair strands. Cosmet Perfumery 88(7):19–22Google Scholar
  52. 52.
    Stern ES, Johnson V (1976) 9th IFSCC U.S.A. 753Google Scholar
  53. 53.
    Goertz H (1989) Preparation of 3-methyl-1-vinylimidazolium chlorides. US Patent 4,844,066Google Scholar
  54. 54.
    Lockhead RY, Jones S, Happi (2004)
  55. 55.
    Lockhead RY (2009) Trends in Polymers for Skin Care, Part I, HAPPIGoogle Scholar
  56. 56.
    Somasundaran P et al (2004) Surfactants, polymers and their nanoparticles for personal care applications. J Cosmet Sci 55:S1–S17PubMedGoogle Scholar
  57. 57.
  58. 58.
    Guth J et al (1993) Addressing the low VOC hair spray issue: new options. Cosmet Toiletries 108:97–103Google Scholar
  59. 59.
    Rocafort C (1995) Polymers in hair care. Spray Technol Market 108:28–34Google Scholar
  60. 60.
    Martino G, Vitale M, Vanemon P (2003) Polyurethane-14-AMP-acrylates copolymer; a hair fixative technology wish memory. Cosmet Toiletries 118:49–56Google Scholar
  61. 61.
    Dallal J, Rocafort C (1997) Hair styling/fixative products. In: Johnson EH (ed) Hair & hair care. Marcel Dekker, New York, pp 105–165Google Scholar
  62. 62.
    Berger FJ (1957) In: Sagarin E (ed) Cosmetics science and technology. Interscience, New York, p 531Google Scholar
  63. 63.
  64. 64. To GAFQUAT 440, brochure, page 10, ISP document
  65. 65.>Active Ingredients Selector (BASF website)
  66. 66.
  67. 67.
  68. 68. Balance 47 polymer-Akzonobel Personal Care
  69. 69.
    Bohac S (1972) Amino alcohols for neutralization of carboxylic acids. J Soc Cosmet Chem 23:125–131Google Scholar
  70. 70.
    Erlemann GA (1971) Objektive und subjective methoden zur beurterlung von hairsprays. J Soc Cosmet Chem 22:287–302Google Scholar
  71. 71.
    Reed AB Jr, Bronfein I (1964) Curl retention with hair sprays. Drug Cosmet Ind 94:178Google Scholar
  72. 72.
    Micchelli A, Koehler FT (1968) Polymer properties influencing curl retention at high humidity. J Soc Cosmet Chem 19:863–880Google Scholar
  73. 73.
    Ganslaw S, Koehler FT (1978) Evaluation of hair fixatives-a new technique utilizing torsional measurements. J Soc Cosmet Chem 29:65–78Google Scholar
  74. 74.
    Frosch F, Vogel F (1988) 6th international hair science symposium of the German wool research institute, LuneburgGoogle Scholar
  75. 75.
    Wickett R, Sramek J (1990) 7th international hair science symposium of the German wool research institute, Bad NeuenahrGoogle Scholar
  76. 76.
    Wickett R, Sramek J, Trobaugh C (1992) Measurement of the adhesive strength of hair-hairspray junctions. J Soc Cosmet Chem 43:169–178Google Scholar
  77. 77.
    Jachowicz J, Yao K (1996) Dynamic hairspray analysis. I: Instrumentation and preliminary results. J Soc Cosmet Chem 47:73–84Google Scholar
  78. 78.
    Lang G, Sendelback G (1992) 8th international hair-science symposium of the German wool research institute, KielGoogle Scholar
  79. 79.
    Ayer R, Thompson J (1972) Scanning electron microscopy and other new approaches to hair spray evaluation. J Soc Cosmet Chem 23:617–636Google Scholar
  80. 80.
    Eckardt W (1970) Physikalische messungen an filmbildnern fur haarsprays. J Soc Cosmet Chem 21:281–287Google Scholar
  81. 81.
    Berthiaume MD, Baum AD (1997) Organofunctionalized silicone resins for personal care applications. J Soc Cosmet Chem 48:1–21Google Scholar
  82. 82.
    Imperante J, O’Lenick AJ Jr (1992) Fatty carboxylic silicone amine salts. US Patent 5,115,049Google Scholar
  83. 83.
    Lenick AJ Jr (1991) Phosphated silicone polymers, US Patent 5,070,171Google Scholar
  84. 84.
    Lenick AJ Jr, Parkinson JK (1992) Silicone phosphobetaines. US Patent 5,091,493Google Scholar
  85. 85.
    Lenick AJ Jr (1992) Silicone protein polymers. US Patent 5,100,956Google Scholar
  86. 86.
    Nanavati S, Hami A (1994) A preliminary investigation of the interaction of a quat with silicone and its conditioning benefits on hair. J Soc Cosmet Chem 45:135–148Google Scholar
  87. 87.
    Yahagi K (1992) Silicones as conditioning agents in shampoos. J Soc Cosmet Chem 43:275–284Google Scholar
  88. 88.
    Kropfbans M, Musiol S, Nienstedt S (2004) Silicone quats-color retention benefits and influence of structure modifications and blending. J Cosmet Sci 55:S133–S141Google Scholar
  89. 89.
    Sandhu S, Ramachandran R, Robbins CR (1995) A simple and sensitive method using protein loss measurements to evaluate damage to human hair during combing. J Soc Cosmet Chem 46:39–52Google Scholar
  90. 90.
    Gamez-Garcia M (1998) The cracking of human hair cuticles by cyclic thermal stresses. J Cosmet Sci 49:141–153Google Scholar
  91. 91.
    Gamez-Garcia M (1998) Cuticle decementation and cuticle buckling produced by Poisson contraction on the cuticular envelope of human hair. J Cosmet Sci 49:213–222Google Scholar
  92. 92.
    Berthiaume MD, Jachowicz J (1991) Heterocoagulation of silicon emulsions on keratin fibers. J Colloid Interface Sci 141:299–315CrossRefGoogle Scholar
  93. 93.
    Robbins CR, Anzuino G (1971) Ionic reactions of keratin fibers containing synthetic polymer. J Soc Cosmet Chem 22:579–588Google Scholar
  94. 94.
    Robbins C (1972) Form-setting keratin substrates by a chemical treatment involving a vinyl monomer. US Patent 3,634,022Google Scholar
  95. 95.
    Brody F, Burns M (1968) Studies concerning the reactions of oxidation dye intermediates. J Soc Cosmet Chem 19:361–379Google Scholar
  96. 96.
    Corbett J (1969) p-Benzoquinonediimine-a vital intermediate in oxidative hair dyeing. J Soc Cosmet Chem 20:253–263Google Scholar
  97. 97.
    Corbett J (1973) The role of meta difunctional benzene derivatives in oxidative hair dyeing. I: Reaction with p-diamines. J Soc Cosmet Chem 24:103–134Google Scholar
  98. 98.
    Madaras GW, Speakman JB (1954) Formation of polymers in wool. J Soc Dyers Colour 70:112–116CrossRefGoogle Scholar
  99. 99.
    Negishi M et al (1967) Graft copolymerization of vinyl monomers in wool fibers. J Appl Polym Sci 11:115–126CrossRefGoogle Scholar
  100. 100.
    Ingram P et al (1968) Radiation grafting of vinyl monomers to wool. III: Location of the grafted polymer. J Polym Sci 6:1895–1912Google Scholar
  101. 101.
    Campbell J et al (1968) Preirradiation grafting in the presence of swelling agents. Pol Lett 6:409–413CrossRefGoogle Scholar
  102. 102.
    Fong W et al. (1965) Proceedings of the 3rd International wool textile research conference III:417Google Scholar
  103. 103.
    Robbins CR et al (1974) Polymerization into human hair. J Soc Cosmet Chem 25:407–421Google Scholar
  104. 104.
    Wolfram LJ (1969) Modification of hair by internal deposition of polymers. J Soc Cosmet Chem 20:539–553Google Scholar
  105. 105.
    Hermann KW (1963) Hair keratin reaction, penetration and swelling in mercaptan solutions. Trans Faraday Soc 59:1663–1671CrossRefGoogle Scholar
  106. 106.
    Jenkins AD, Wolfram LJ (1963) The chemistry of the reaction between tetrakis-hydroxymethylphosphonium chloride and keratin. J Soc Dyers Colour 79:55CrossRefGoogle Scholar
  107. 107.
    Crank J (1967) Mathematics of diffusion. Oxford University Press, Oxford, UK, p 71Google Scholar
  108. 108.
    Windholz M (ed) (1976) The Merck index: an encyclopedia of chemical and drugs, 9th edn. Merck & Co, Rahway, p 127Google Scholar
  109. 109.
    Windholz M (ed) (1976) The Merck index: an encyclopedia of chemical and drugs, 9th edn. Merck & Co, Rahway, p 500Google Scholar
  110. 110.
    Selikoff IJ, Hammond EC (eds) (1975) Toxicity of vinyl chloride-polyvinylchloride. Ann NY Acad Sci 246:1–337Google Scholar

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Authors and Affiliations

  1. 1.Clarence Robbins Technical ConsultingClermontUSA

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