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Photochromic microcapsules by coacervation and in situ polymerization methods for product-marking applications

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Abstract

Photochromic materials can change their colour quickly and reversibly when exposed to light of certain wavelengths. These materials have recently been of great interest for intelligent and functional textile applications. In this study, two different photochromic dyes, including 1′,3′-dihydro-1′,3′,3′-trimethyl-6-nitro-spiro[2H-1-benzopyran-2,2′-(2H)-indole] and 1′,3′-dihydro-8-methoxy-1′,3′,3′-trimethyl-6-nitrospiro[2H-1-benzopyran-2,2′-(2H)-indole], were microencapsulated by coacervation and in situ polymerization methods. Ethyl cellulose and melamine–urea–formaldehyde were used as polymers. The Fourier transform infrared spectroscopy, particle size and size distribution analysis, scanning electron microscopy, and ultraviolet spectrophotometry evaluations were utilized to characterize the structure, morphology, size distribution, and absorbance maxima of the photochromic microcapsules. The results indicated that photochromic microcapsules were in spherical shape, smooth, and homogeneous characteristics. These microcapsules were applied successfully onto cotton fabric using printing technique. Then, the activities of photochromic microcapsules on the fabrics were analysed by colour analysis under different light sources, fatigue resistance, washing, and rubbing fastness tests. After printing, the colours of the fabrics changed very quickly under different light sources. At the same time, these fabrics showed a reversible photochromic response and good fatigue resistance. Mechanical and physical properties of the fabrics such as thickness, air permeability and tensile and tear strength were also investigated. It can be concluded that photochromic microcapsules are well appropriate for brand protection and prevention of imitation in textile materials.

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References

  1. Brown GH (1971) Photochromism, techniques of chemistry. Wiley Interscience, New York

    Google Scholar 

  2. Barachevsky VA (1999) In: Crano JC, Guglielmetti RJ (eds) Organic photochromic and thermochromic compounds. Plenum, NewYork

    Google Scholar 

  3. Bamfield P (2001) Chromic phenomena: the technological applications of colour chemistry. The Royal Society of Chemistry, Cambridge

    Google Scholar 

  4. Shibaev V, Bobrovsky A, Boiko N (2003) Photoactive liquid crystalline polymer systems with light-controllable structure and optical properties. Prog Polym Sci 28:729–836

    CAS  Google Scholar 

  5. Lin JS (2003) Interaction between dispersed photochromic compound and polymer matrix. Eur Polym J 39:1693–1700

    CAS  Google Scholar 

  6. Luo QF, Cheng H, Tian H (2011) Recent progress on photochromic diarylethene polymers. Polym Chem 2:2435–2443

    CAS  Google Scholar 

  7. Larkowska M, Wuebbenhorst M, Kucharski S (2011) Spirooxazine photoisomerization and relaxation in polymer matrices. Int J Polym Sci 2011:1–6

    Google Scholar 

  8. Ding H, Wang Z, Sheng LJ, Song GW (2011) Synthesis, self-assembly behavior and biological application of a new photochromic azo amphiphilic diblock copolymer. Polym Eng Sci 51:1662–1668

    CAS  Google Scholar 

  9. Klajn R (2014) Spiropyran-based dynamic materials. Chem Soc Rev 43:148–184

    PubMed  CAS  Google Scholar 

  10. Jiang F, Chen S, Cao Z, Wang G (2016) A photo, temperature, and pH responsive spiropyran-functionalized polymer: synthesis, self-assembly and controlled release. Polymer 83:85–91

    CAS  Google Scholar 

  11. Rad JK, Mahdavian AR (2016) Preparation of fast photoresponsive cellulose and kinetic study of photoisomerization. J Phys Chem C 120:9985–9991

    Google Scholar 

  12. Durr H, Bouas-Laurent H (2003) Photochromism: molecules and systems. Elsevier, Amsterdam

    Google Scholar 

  13. El-Shishtawy RM (2009) Functional dyes and some hi-tech applications. Int J Photoenergy 2009:434897

    Google Scholar 

  14. Periyasamy AP, Vikova M, Vik M (2017) A review of photochromism in textiles and its measurement. Text Prog 49:53–136

    Google Scholar 

  15. Peng L, Guo R, Jiang S, Lan J, He Y, Huang X (2015) Ultrasound-aided dyeing of cotton fabric with spirooxazines and photochromic properties. Fiber Polym 16:1312–1318

    CAS  Google Scholar 

  16. Billah SMR, Christie RM, Shamey R (2008) Direct coloration of textiles with photochromic dyes. Part 1: application of spiroindolinonaphthoxazines as disperse dyes to polyester, nylon and acrylic fabrics. Color Technol 124:223–228

    CAS  Google Scholar 

  17. Billah SMR, Christie RM, Morgan KM (2008) Direct coloration of textiles with photochromic dyes. Part 2: the effect of solvents on the colour change of photochromic textiles. Color Technol 124:229–233

    CAS  Google Scholar 

  18. Billah SMR, Christie RM, Shamey R (2012) Direct coloration of textiles with photochromic dyes. Part 3: dyeing of wool with photochromic acid dyes. Color Technol 128:488–492

    CAS  Google Scholar 

  19. Little AF, Christie RM (2010) Textile applications of photochromic dyes. Part 1: establishment of a methodology for evaluation of photochromic textiles using traditional colour measurement instrumentation. Color Technol 126:157–163

    CAS  Google Scholar 

  20. Little AF, Christie RM (2010) Textile applications of photochromic dyes. Part 2: factors affecting the photocoloration of textiles screen-printed with commercial photochromic dyes. Color Technol 126:164–170

    CAS  Google Scholar 

  21. Little AF, Christie RM (2011) Textile applications of photochromic dyes. Part 3: factors affecting the technical performance of textiles screen-printed with commercial photochromic dyes. Color Technol 127:275–281

    CAS  Google Scholar 

  22. Aldib M, Christie RM (2011) Textile applications of photochromic dyes. Part 4: application of commercial photochromic dyes as disperse dyes to polyester by exhaust dyeing. Color Technol 127:282–287

    CAS  Google Scholar 

  23. Aldib M, Christie RM (2012) Textile applications of photochromic dyes. Part 5: application of commercial photochromic dyes to polyester fabric by a solvent-based dyeing method. Color Technol 129:131–143

    Google Scholar 

  24. Little AF, Christie RM (2016) Textile applications of commercial photochromic dyes. Part 6: photochromic polypropylene fibres. Color Technol 132:304–309

    CAS  Google Scholar 

  25. Younes B, Ward SC, Christie RM, Vettese S (2019) Textile applications of commercial photochromic dyes: part 7. A statistical investigation of the influence of photochromic dyes on the mechanical properties of thermoplastic fibres. J Text Inst 110:780–790

    CAS  Google Scholar 

  26. Aldib M (2015) An investigation of an instrument-based method for assessing colour fastness to light of photochromic textiles. Color Technol 131:298–302

    CAS  Google Scholar 

  27. Vik M, Vikova M (2016) A method and device for fatigue testing of photochromic, fluorescent or phosphorescent dye/dyes, or of a mixture of at least two of them, and a device for carrying out this method. United States Patent: US 2016/0299054 A1

  28. Shah PH, Patel RG, Patel VS (1985) Azodisperse dyes with photochromic mercury(II)-dithizonate moiety for dyeing polyester, nylon and cellulose triacetate fibres. Indian J Text Res 10:179–182

    CAS  Google Scholar 

  29. Lee SJ, Son YA, Suh HJ, Lee DN, Kim SH (2006) Preliminary exhaustion studies of spirooxazine dyes on polyamide fibers and their photochromic properties. Dyes Pigments 69:18–21

    CAS  Google Scholar 

  30. Son YA, Park YM, Park SY, Shin CJ, Kim SH (2007) Exhaustion studies of spiroxazine dye having reactive anchor on polyamide fibers and its photochromic properties. Dyes Pigments 73:76–80

    CAS  Google Scholar 

  31. Galbraith J (2004) An assessment of the technical performance of photochromic dyes in textile printing. AATCC Rev 4:26–30

    CAS  Google Scholar 

  32. Kozicki M, Sasiadek E (2012) UV-assisted screen-printing of flat textiles. Color Technol 128:251–260

    CAS  Google Scholar 

  33. Feczkó T, Samu K, Wenzel K, Neral B, Voncina B (2013) Textiles screen-printed with photochromic ethyl cellulose-spirooxazine composite nanoparticles. Color Technol 129:18–23

    Google Scholar 

  34. Khattab TA, Rehan M, Hamouda T (2018) Smart textile framework: photochromic and fluorescent cellulosic fabric printed by strontium aluminate pigment. Carbohyd Polym 195:143–152

    CAS  Google Scholar 

  35. Ghosh S, Hall J, Joshi V (2018) Study of chameleon nylon and polyester fabrics using photochromic ink. J Text Inst 109:723–729

    CAS  Google Scholar 

  36. Aldib M (2015) Photochromic ink formulation for digital inkjet printing and colour measurement of printed polyester fabrics. Color Technol 131:172–182

    CAS  Google Scholar 

  37. Seipel S, Yu J, Periyasamy AP, Vikova M, Vik M, Nierstrasz VA (2017) Characterization and optimization of an inkjet printed smart textile UV-sensor cured with UV-LED light. IOP Conf Ser Mater Sci Eng 254:072023

    Google Scholar 

  38. Seipel S, Yu J, Vikova M, Vik M, Koldinska M, Havelka A, Nierstrasz VA (2019) Color performance, durability and handle of inkjet-printed and UV cured photochromic textiles for multi-colored applications. Fiber Polym 20:1424–1435

    CAS  Google Scholar 

  39. Pinto TV, Costa P, Sousa CM, Sousa CAD, Monterio A, Pereira C, Soares OSGP, Silva JSM, Pereira MFR, Coelho PJ, Freire C (2016) Photo switchable silica nanoparticles for the production of light responsive smart textiles: from fabrication to coating technology. In: “nanoPT2016 International Conference”. Braga, Portugal

  40. Pinto TV, Costa P, Sousa CM, Sousa CAD, Pereira C, Silva CJSM, Pereira MFR, Coelho PJ, Freire C (2016) Screen-printed photochromic textiles through new inks based on SiO2@naphthopyran nanoparticles. ACS Appl MaterInterface 8:28935–28945

    CAS  Google Scholar 

  41. Parhizkar M, Zhao Y, Wang X, Lin T (2014) Photostability and durability properties of photochromic organosilica coating on fabric. J Eng Fiber Fabric 9:65–73

    Google Scholar 

  42. Cheng T, Lin T, Fang J, Brady R (2007) Photochromic wool fabrics from a hybrid silica coating. Text Res J 77:923–928

    CAS  Google Scholar 

  43. Cheng T, Lin T, Brady R, Wang X (2008) Fast response photochromic textiles from hybrid silica surface coating. Fiber Polym 9:301–306

    CAS  Google Scholar 

  44. Ayazi Yazdi S, Karimi L, Mirjalili M, Karimnejad M (2017) Fabrication of photochromic, hydrophobic, antibacterial, and ultraviolet-blocking cotton fabric using silica nanoparticles functionalized with a photochromic dye. J Text Inst 108:856–863

    CAS  Google Scholar 

  45. Fan F, Zhang W, Wang C (2015) Covalent bonding and photochromic properties of double-shell polyurethane-chitosan microcapsules crosslinked onto cotton fabric. Cellulose 22:1427–1438

    CAS  Google Scholar 

  46. Brinker CJ, Scherer GW (1990) Sol-gel science: the physics and chemistry of sol-gel processing. Academic, San Diego

    Google Scholar 

  47. Hou L, Hoffmann B, Schmidt H, Menning M (1997) Effect of heat treatment and additives on the photochromic and mechanical properties of sol-gel derived photochromic coatings containing spirooxazine. J Sol-Gel Sci Technol 8:923–926

    CAS  Google Scholar 

  48. Mahlting B, Textor T, Akçakoca Kumbasar EP (2015) Photobactericidal and photochromic textile materials realized by embedding of advantageous dye using sol-gel technology. CBU J Sci 11:306–315

    Google Scholar 

  49. Jalan V, Butola BS (2018) Influence of binder type on color characteristics of cotton fabric colored with a photochromic colorant. J Nat Fiber 15:229–238

    CAS  Google Scholar 

  50. Nelson G (2002) Application of microencapsulation in textiles. Int J Pharm 242:55–62

    PubMed  CAS  Google Scholar 

  51. Su JH, Chen J, Zeng F, Chen QM, Wu SZ, Tong Z (2008) Synthesis and photochromic property of nanoparticles with spiropyran moieties via one-step miniemulsion polymerization. Polym Bull 61:425–434

    CAS  Google Scholar 

  52. Lee EM, Choi MS, Han YA, Cho HJ, Kim SH, Ji BC (2008) Preparation and photochromism of poly(methyl methacrylate) microspheres containing spirooxazine. Fiber Polym 9:134–139

    CAS  Google Scholar 

  53. Han M, Lee E, Kim E (2003) Preparation and optical properties of polystyrene nanocapsules containing photochromophores. Opt Mater 21:579–583

    CAS  Google Scholar 

  54. Feczkó T, Varga O, Kovács M, Vidóczy T, Voncina B (2011) Preparation and characterization of photochromic poly(methyl methacrylate) and ethyl cellulose nanocapsules containing a spirooxazine dye. J Photochem Photobio A222:293–298

    Google Scholar 

  55. Valh JV, Vajnhandl S, Skodic L, Lobnik A, Turel M, Voncina B (2017) Effects of ultrasound irradiation on the preparation of ethyl cellulose nanocapsules containing spirooxazine dye. Hindawi J Nanomater 2017:4864760

    Google Scholar 

  56. Çay A, Akçakoca Kumbasar EP, Morsunbul S (2017) Exergy analysis of encapsulation of photochromic dye by spray drying. In: IOP conference series: mater sci eng

    Google Scholar 

  57. Akçakoca Kumbasar EP, Voncina B, Çay A, Elemen S, Vivod V (2012) Application of encapsulated photochromic dye for UV protective textile materials (oral presentation). ‘Egemeditex-International Congress on Healthcare and Medical Textiles. Izmir, Turkey, pp 196–202

    Google Scholar 

  58. Akçakoca Kumbasar EP, Çay A, Elemen S, Voncina B, Vivod V (2013) An investigation on the fatigue resistance (loss of reversibility) of photochromic textiles. In: “13. Autex World Textile Conference”. Dresden, Germany

  59. Akçakoca Kumbasar EP, Çay A, Morsunbul S, Voncina B (2016) Color build-up and UV-protection performance of encapsulated photochromic dye-treated cotton fabrics. AATCC J Res 3:1–7

    Google Scholar 

  60. Kert M, Gorjanc M (2017) The study of colour fastness of commercial microencapsulated photoresponsive dye applied on cotton, cotton/polyester and polyester fabric using a pad-dry-cure process. Color Technol 133:491–497

    CAS  Google Scholar 

  61. Periyasamy AP, Vikova M, Vik M (2019) Photochromic polypropylene filaments: impacts of mechanical properties on kinetic behavior. FibreText East Eur 27:19–25

    CAS  Google Scholar 

  62. Abate MT, Seipel S, Vikova M, Vik M, Ferri A, Jinping G, Chen G, Nierstrasz VA (2019) Comparison of the photochromic behaviour of dyes in solution and on polyester fabric applied by supercritical carbon dioxide. IOP Conf Ser Mater Sci Eng 459:012026

    Google Scholar 

  63. Bao B, Bai S, Fan J, Su J, Wang W, Yu D (2019) A novel and durable photochromic cotton-based fabric prepared via thiol-ene click chemistry. Dyes Pigments 171:107778

    Google Scholar 

  64. Fischer E, Hirshberg Y (1952) Formation of coloured forms of spirans by low-temperature irradiation. J Chem Soc 1:4522–4524

    Google Scholar 

  65. Samoladas A, Bikiaris D, Zorba T, Paraskevopoulos KM, Jannakoudakis A (2008) Photochromic behavior of spiropyran in polystyrene and polycaprolactone thin films—effect of UV absorber and antioxidant compound. Dyes Pigments 76:386–393

    CAS  Google Scholar 

  66. Heiligman-Rim R, Hirshberg Y, Fischer E (1962) Photochromism in spiropyrans. Part V. On the mechanism of phototransformation. J Phys Chem 66:2470–2477

    CAS  Google Scholar 

  67. Chibisov AK, Helmut Gorner (1997) Photoprocesses in spiropyran-derived merocyanines. J Phys Chem A 101:4305–4312

    CAS  Google Scholar 

  68. Lenoble C, Becker RS (1986) Photophysics, photochemistry, kinetics and mechanism of the photochromism of 6′-Nitroindolinospiropyran. J Phys Chem 90:62–65

    CAS  Google Scholar 

  69. Cottone G, Noto R, Manna GL (2004) Theoretical study of spiropyran-merocyanine thermal isomerization. Chem Phys Lett 388:218–222

    CAS  Google Scholar 

  70. Khatri Z, Ali S, Khatri I, Mayakrishnan G, Kim SH, Kim IS (2015) UV-responsive polyvinyl alcohol nanofibers prepared by electrospinning. Appl Surf Sci 342:64–68

    CAS  Google Scholar 

  71. Parhizkar M, Zhao Y, Lin T (2015) In: Tao X (ed) Handbook of smart textiles. Springer, Singapore

    Google Scholar 

  72. Thies C (1996) In: Benita S (ed) Microencapsulation methods and industrial application. Marcel Dekker Incorporated Press, New York

    Google Scholar 

  73. Badulescu R, Vivod V, Jausovec D, Voncina B (2008) Grafting of ethylcellulose microcapsules onto cotton fibers. Carbohyd Polym 71:85–91

    CAS  Google Scholar 

  74. Zandi M, Pourjavadi A, Hashemi SA, Arabi H (1998) Preparation of ethyl cellulose microcapsules containing perphenazine and polymeric perphenazine based on acryloyl chloride for physical and chemical studies of drug release control. Polym Int 47:413–418

    CAS  Google Scholar 

  75. Philbrook A, Blake CJ, Dunlop N, Easton CJ, Keniry MA, Simpson JS (2005) Demonstration of co-polymerization in melamine-urea-formaldehyde reactions using 15N NMR correlation spectroscopy. Polymer 46:2153–2156

    CAS  Google Scholar 

  76. Zhou Y, Yan Y, Du Y, Chen J, Hou X, Meng J (2013) Preparation and application of melamine-formaldehyde photochromic microcapsules. Sensor Actuator B 188:502–512

    CAS  Google Scholar 

  77. Erkan G (2008) The microencapsulation of some antifungal agents and their applications to textiles. Ph.D. Thesis, The Graduate School of Natural and Applied Sciences, Dokuz Eylul University, Turkey

  78. Erkan G, Sarıışık AM (2015) Antifungal microcapsules of ethyl cellulose by solvent evaporation and their application to cotton fabric. FibreText East Eur 23:125–130

    CAS  Google Scholar 

  79. Liu X, Sheng X, Lee JK, Kessler MR (2009) Microcapsules for self-healing polymers. Macromol Mater Eng 294:389

    CAS  Google Scholar 

  80. Erkan G, Sarıışık AM, Pazarlıoğlu NK (2014) Antifungal cotton fabric via molecular encapsulation of terbinafine. Cell Chem Technol 48:753–760

    CAS  Google Scholar 

  81. Kubelka P (1948) New contributions to the optics of intensely light-scattering materials part I. J Opt Soc Am 38:448–457

    PubMed  CAS  Google Scholar 

  82. Sharma A (2004) Understanding color management. Thomson Delmar Learning, USA

    Google Scholar 

  83. Ingle JD, Crouch SR (1988) Spectrochemical analysis. Prentice Hall College Book Division, New Jersey

    Google Scholar 

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Acknowledgements

The work was supported by The Republic of Turkey, Ministry of Science, Industry and Technology in the frame of the Project number 0547.STZ.2013-2, The Scientific Research Department of Dokuz Eylul University (Project no: 2014.KB.FEN.010) and Soktas Weaving Industry Co. We are grateful to the financial support from The Republic of Turkey, Ministry of Science Industry and Technology, The Scientific Research Department of Dokuz Eylul University and Soktas Weaving Industry Co.

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Authors and Affiliations

  1. The Graduate School of Natural and Applied Sciences, Dokuz Eylul University, 35390, Izmir, Turkey

    Ozlem Topbas

  2. Department of Textile Engineering, Faculty of Engineering, Dokuz Eylul University, 35397, Izmir, Turkey

    Ayse Merih Sariisik & Gokhan Erkan

  3. Soktas Weaving Industry Company, 09201, Aydın, Turkey

    Orhun Ek

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  1. Ozlem Topbas
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Correspondence to Ayse Merih Sariisik.

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Topbas, O., Sariisik, A.M., Erkan, G. et al. Photochromic microcapsules by coacervation and in situ polymerization methods for product-marking applications. Iran Polym J 29, 117–132 (2020). https://doi.org/10.1007/s13726-019-00781-9

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