ProcessDevelopmentforPrintingonCotton FabricwithTerminaliaChebulaDye

By:B.H.PatelandDr.D.P.Chattopadhyay
Department of Textile Chemistry, Faculty of Technology & Engineering, The M.S.University of Baroda Vadodara, India.

Abstract The study was done on the process development for printing on cotton fabric with terminalia chebula. Extracted natural dye was used for printing with different mordants (copper sulphate, ferrous sulphate, and stannous chloride). In all 4 different shades were developed. Effect of various mordant on shades in terms of colour strength (K/S values) was evaluated. Fastness properties (light, washing, and crocking) were also studied on these samples. There is a need to carry out further research in this field and explore the possible way for its use in other natural fiber viz., jute, silk etc. Natural fabric printed with natural dyes in soft and subdued shades creates a fashion statement. Thus it can be exploited commercially to create opportunities for rural employment. Keywords: Cotton, Natural dye, Mordant, Printing, Terminalia chebula.

1.Introduction Natural dye selected for the present investigation was Terminalia chebula, generally in India known as harde, which are described as follows: Terminalia chebula occurs scattered in teak forest, mixed deciduous forest, extending into forests of comparatively dry types (1-3). Biophysical limits Altitude: up to 1500 (-2000) m, Soil type: The species is found on a variety of soils, clayey as well as shady. Botanic Description Terminalia chebula is a medium to large deciduous tree attaining a height of up to 30 m, with widely spreading branches and a broad roundish crown. The leaves are elliptic oblong, with an acute tip, cordate at the base, margins entire, glabrous above with a yellowish pubescence below. The flowers are monoecious, dull white to yellow, with a strong unpleasant odour, borne in terminal spikes or short panicles. The fruits are glabrous, ellipsoid to avoid drupes, 1

yellow to orange brown in colour, containg a single angle stone. Terminalia chebula is found throughout deciduous forests of the Indian subcontinent, on dry slopes up to 900 meters in elevation. Parts used : fruit Dravyguna : Fresh fruit Rasa : kasaya, tikta, amla, katu, madhura Vipaka : madhura Virya : usna Karma : dipanapacana, bedhanam (curna), grahi (kvatha, tincture), krmighna, Mutravirecana, jvaraghna, svasahara, kasahara, kusthaghna, sothahara, Medhya, vedanasthapana, sandhaniya, cakusya, hrdaya, rasayanam, tridosaghna

Prabha:named for the god Siva (Hari), who brings fearlessness (abhaya) in the face of death and disease, and because it purifies the mind of attachment. (5, 6). Species in Ayurveda: Bhava Prakasha, the author of famous Ayurvedic Materia Medica described the seven species of Terminalia chebula. This classification is based on the location, qualities and actions of the plant (4,7,8). Generally speaking the Vijaya variety is preferred, which is traditionally grown in the Vindhya mountain range of central India, and has a roundish as opposed to a more angular shape (4). For practical purposes, the fruit of Terminalia chebula is of three types actually these are the different stages of maturity of fruits (9,10) . (a) Small myrobalan - the unripe fruit (b) Yellow myrobalan - After the development of seed, the adult stage of the fruit (c) Large Myrobalan - The fully matured fruit Chemical constituents: Terminalia chebula is rich in tannin. The chief constituents of tannin are chebulic acid, chebulagic acid, corilagin and gallic acid (11-14). Tannin of Terminalia chebula is of pyrogallol (hydrolyzable) type. A group of researchers found 14 components of hydrolyzable tannins (gallic acid, chebulic acid, punicalagin, chebulanin, corilagin, neochebulinic acid, ellagic acid, chebulegic acid, chebulinic acid, 1,2,3,4,6- penta-O-galloyl-H-D-glucose, 1,6,di-O-galloyl-D-glucose, casuarinin, 3,4,6-tri-O-galloyl-D- glucose, terchebulin) from

Terminalia chebula fruits (15). One source lists Terminalia chebula as having 32% tannin content (16). The tannin content of Terminalia chebula varies with geographical variation (17). Besides, fructose, amino acids, succinic acid, betasitosterol, resin and purgative principle of anthroquinone and sennoside nature is also present (14, 18). Flavonol glycosides, triterpenoids, coumarin conjugated with gallic acids called chebulin as well as other phenolic compounds were also isolated (19-22). The chemical structures of some compounds are given in Fig.1. With alum, powdered rind of the fruit yields a traditional dye-range of fast yellow. With iron sulphate, it is used in the production of various shades of black (23-26). Production of various can be done with effective and controlled use of mordant. Keeping the above points in mind, it was thought worthwhile to further extend the use of Terminalia chebula dye for printing of textile fabric.

2.MaterialsandMethods 2.1PreparationofFabrics Mill scoured cotton fabric was selected for the study. For pre-treatment of fabric, a detergent solution containing 0.5 ml of mild detergent, per 100 ml of warm water was prepared. Fabric was dipped into this solution and stirred gently for 30 minutes in it, temperature was maintained at 70C; Fabric was kneaded, squeezed and removed from the solution. Rinsing was done under tap water till the fabric was free from detergent completely. fabric was hung in shade to dry and ironed when still half wet.

2.2Selectionofwoodenblock Wooden block with sharp designed was selected for the study.

2.3Selectionofmediumfordyeextraction The dye solution was prepared separately by using 20 gm (Terminalia chebul) powder per 100 ml of water in alkaline medium. The dye material was entered into the alkaline solutions and heated at 80C for an hour. Solutions were then filtered and pre-coaked samples of known weight were added to each beaker and dyeing was carried out for an hour at 95C. After that samples were taken out, rinsed in water, dried in shade and ironed while still half wet. The medium which gave the best shade was selected for further study.

2.4Selectionofdyeconcentrate The fresh dye source was taken for the extraction of dye. Twenty gram of powder boiled in 100 ml of water in an alkaline medium for an hour, cooled at room temperature and filtered through a sieve to get a clear dye solution. The dye solution was made into concentrate (100 ml reduced to 5ml) by evaporation using hot plate for approximately half an hour. Three dyes concentrates i.e. 3.0 ml, 5.0 ml and 7.0 ml were taker from the prepared dye concentrate. The dye concentrate which obtained highest percentage rank through visual evaluation was selected for further experiments.

2.5Selectionofthickener Two thickeners namely gum tragacanth and gum acacia were used to print the cotton fabric with selected dye concentrates. The pastes for both the gums were made by mixing 10 gm of gum powder with 100 ml of water and left overnight. Total 110 gm paste was made

separately for both the gums. 100 gram of above gum paste and dye concentrations was used to prepare the printing paste. Printing was done on cotton fabric using the prepared printing paste. Printed samples were dried and steamed at 102C for 15minutes than washed under running tap water. The washing fastness of each printed sample was tested for the selection of the best thickener.

2.6ConcentrationofMordant 2.61MetallicMordants: Metallic mordants namely copper sulphate, ferrous sulphate, and stannous chloride were used for the study. The concentrations of mordants were: Ferrous sulphate Stannous chloride Copper sulphate 1.0, 1.0, 1.0, 2.0 and 3.0 per cent 2.0 and 3.0 per cent 1.5 and 2.0 per cent

O.w.f. - on weight of thickener Three samples for each mordant for dye on cotton fabric were prepared. Mordanting Method Two methods of mordanting namely, simultaneous mordanting and printing and post mordanting were tried to select best mordanting method.

2.7Aftertreatment Printed samples were steamed at 102C for 15 minutes in the steamer for fixation of dye, immediately after steaming. Printed and steamed sample was rinsed in water, soaped with nonionic detergent, dried in shade and ironed while half wet.

2.8Evaluationofprintedsample 2.8.1.MeasurementofColourValues The samples were assessed for L, a*, b* colour coordinates and K/S values (illuminant D65/100 observer) on spectra scan 5100 (RT) spectrophotometer (premier colorscan instrument). 2.8.2.FastnessTests Wash fastness of the samples printed under the optimized conditions, was tested according to ISO 105-CO3 method. The samples were washed in standard soap solution at 60 C for 30 min, keeping liquor to material ratio as 1:50. Dry and wet rubbing fastness of the samples

was tested according to ISO 105-X12 method. Light fastness was tested according to ISO 105-BO2 method. The printed samples were exposed to xenon arc lamp for 24 h at standard testing conditions [27].

3.ResultsandDiscussion The present investigation was carried out to explore the usefulness of widely available material, termenbelia chebula. In case of natural dye to obtain a wide range of colours on fabric various metallic salts can be used. Thus, experiments were conducted to standardize the recipe for application of metallic salt for printing of cotton by using termenbelia chebula (C.I. Natural brown 6) dye. The effect of metallic salt on colour development and their methods of application were studied.

3.1.Effectofmetallicsaltsoncolourstrength. When cotton fabric was printed with formulation 1, it has been observed that the different metallic salt gives different colour prints on light brown colour background (i.g. copper sulphate, ferrous sulphate & stannous chloride gives brown, gray & pale brown colour print). When the cotton sample was printed with formulation 2, it has been observed that the formulation gives dark brown colour print on white background when copper sulphate was used in printing paste with termenbelia chebula dye. Ferrous sulphate when used with the dye, shade of black colour print was produced on cotton fabric. In case of stannous chloride, cream colour print was observed. Fig.2 represents the various colours and shades of print which can be produced on cotton fabric with termenbelia chebula with two different formulations. It has been observed from the printed samples that out of two methods used for the printing, second formulation gives the best results in terms of depth of prints. Table 1 represents the K/S values and colour coordinates of different samples. The K/S values are found to be maximum for sample printed with the paste contains ferrous sulphate followed by copper

sulphate and stannous chloride printed samples (formulation-1). Furthermore, it can also be seen that the highest K/S values are obtained with formulation-1 and least for formulation-2. Table 2 also shows the colour characteristics of printed samples with formulation-1 and formulation-2 using different metallic salts. The printed samples show significant tonal variation on mordanting as is evident from the values of colour coordinates. Here, L* represents lightness/ darkness; a*, the red / green values; and b*, the yellow / blue value.

Very slight variation is observed in the

a* and b* values of samples printed with

formulation-1and 2. However, the samples printed with ferrous sulphate are duller in tone. 3.2.Colourfastnessofthesamples Table 3 shows that the fastness properties of the sample printed with formulation-1, with copper sulphate, ferrous sulphate and stannous chloride are better than those of the samples printed with formulation-2. On comparing the fastness ratings of samples printed by three metallic salts stannous chloride always exhibits better fastness properties than the other two salts. From Table 2, it can also be seen that all samples printed either with formulation-1 or 2, exhibits adequate all round good to very good fastness properties.

4.Conclusion It can be concluded from the present investigation that the natural dye source termenbelia chebula used to dye the fabric can also be employed to print the fabric by using different printing paste formulation. In this way by utilizing some of the natural material, which is cheap and easily available, termenbelia chebula as an important dyeing and printing material for cotton fabric. The ecological and toxicological problems caused by synthetic dyes can be resolved to some extent.

References 1. C. K. Kokate, A. P. Purohit and S. B. Gokhale, Pharmacognosy, 12th Edition; Nirali Prakashane, Pune; (1990) 151. 2. B. C. Mohanty, National Seminar on Natural Dyes, Jaipur, NHDC (1989). 3. M.L. Gulrajani, Colourage, XLVI (July, 1999), 29. 4. K.R. Srikanthmurthy. Bhavaprakasha of Bhavamishra. Vol. 1, (Krishnanda Academy, Varanasi, 2001). pp. 159-160.

5. R.H.M.J. Lemmens, I. Soerianegara , W.C. Wong (Eds). Plant Resources of SouthEast Asia. No. 5(2): Timber Tree, Minor Commercial Timber (Bosea Foundation, Bogor, Indonesia, 1995), pp. 475-478. 6. R.H.M.J. Lemmens, N. Wilijarni-Soetjpto (Eds). Plant Resources of South- East Asia.No. 3: Dye and tannin producing Plants. (Propsia Foundation, Bogor, Indonesia, 1992), pp. 122-125. 7. Terminalia chebula : Ayurvedic Herbal Rejunvenating Herb. Available In http://www.holistic-herbalist.com/terminalia-chebula-1-html. 8. B. Das, M. Junius. A Handbook of Ayurveda (Concept Publishing, New Delhi,1983), pp. 84-87. 9. D. Frawley, V. Lad. The Yoga of Herbs : An Ayurvedic Guide to Herbal Medicines (Lotus Press, Santa Fe, 1986), pp. 174. 10. P.K. Varnick, V.P.K. Nambiar, C. Ramakuthy (Eds). Indian Medicinal Plants : A Compendum of 500 species. Vol. 5, (Orient Longman, Hyderabad,1996), pp. 263. 11. Dr. P. Sharma . Avyagunvigyana, 9th Ed, Chaukhambha Bharat Academy, Samat,2004, 239-760. 12. J. Bruneton. Pharmacognosy, Phytochemistry, Medicinal Plants. Paris, France, (Laviosier Publishing, 1995), pp.333. 13. R.M. Ber. Phytosterol in some plants materials. Indian Sopa J. 35 : 275-77 (1970). 14. Chevallier. Encyclopedia of Medicinal Plants, New York, N.Y., (D.K. Publishing, 1996), pp. 273.

15. L.J. Juang, S.J. Sheu, T.C. Lin. Determination of hydrolyzable tannins in the fruit of Terminalia chebula by high-performancc liquid chromatography and capillary electrophoresis. J. Sep. Sci. 27 (9) : 718-24 (2004). 16. W. Evans. Trease and Evans Pharmacology. 14th Ed., (W.B. Saunders Co. Pvt.Ltd., 1996), pp. 493. 17. K. Jayaramkumar. Effect of geographical variation on content of tannic acid, gallic acid, chebulinic acid, and ethyl gallate in Terminalia chebula fruits. Natural Products. 2(3-4) : 170-5 (2006). 18. E. Creencia, T. Eguchi, T. Nishimura, K. Kakinuma. Isolation and structure elucidation of the biologically active components of Terminalia chebula Retzius (Combretaceae). KIMIKA 12: 1-10, (1996). 19. L.D. Kapoor. CRC Handbook of Ayurvedic Medicinal Plants (CRC Press, Boca Ralon, 1990), pp. 332. 20. P. Asish, B. Sashi. Triterpenoids and their glycosides from Terminalia chebula. Phytochemistry. 32(4): 999: 1002 (1993). 21. E.N. Williumson (Ed). Major Herbs of Ayurveda (Churchill Livingstone, (London, 2002), pp. 299. 22. S.N. Yoganarasimhan. Medicinal Plants of India, Vol. 2 (Tamil Nadu, Self Publication, Bangalore, 2000), pp. 541. 23. B.H.Patel and B.J.Agarwal, Man-Made Textiles in India, XLIII (Nov.2000), 11. 24. B.H.Patel and B.J.Agarwal, Asian Textiles Journal, 11 (April, 2002) 4. 25. B. H. Patel, B. J. Agrawal and H. M. Patel, Colourage (Jan, 2003), 21. 26. B.H.Patel, Texmach India,Jan-Feb. 2006, Vol. No.5, P.09-12.

27. Anon, Methods of test for colour fastness of textiles and leather, The Society of Dyers and Colourists (1990).

FiguresandTables
OH HO

COOH
OH COOH

OH

COOH COOH

HO OH

OH
OH

OH

Chebulic acid

Gallic acid

Pyrogallol

CO

O OH

HO OH

CO

OH

Ellagic acid

Fig.1. Hydrolysable tannins present in termenbelia chebula.

CuSO4

FeSO4

SnCl2

Samples printed with Formulation 1.

CuSO4

FeSO4

SnCl2

Samples printed with Formulation 2.

Samples printed with CuSO4 and FeSO4 Fig.2. Various print produced on cotton fabric.

10

Table 1 Printing paste formulation. Formulation Metallic salt Dye (gpl) Mordent (gpl) Thickener Gum arabica (ml) Formulation - 1 Formulation - 2 Formulation -1 Formulation -2 Formulation -1 Formulation - 2 Copper sulphate Copper sulphate Ferrous sulphate Ferrous sulphate Stannous chloride Stannous chloride --20 --20 --20 2.0 2.0 2.0 2.0 2.0 2.0 68 60 68 60 68 60 30 18 30 18 30 18 Hot water (ml)

Table 2 Effect of metallic salts on colour characteristics of printed cotton fabric.

Formulation

Metallic salt

K/S values

L*

a*

b*

Formulation - 1

CuSO4 FeSO4 SnCl2

19.12 24.31 5.12 7.97 22.27 3.52

69.45 59.78 65.87 62.56 61.59 63.23

1.58 0.74 0.87 2.59 5.65 1.17

24.24 15.11 19.18 20.09 21.16 18.02

Formulation - 2

CuSO4 FeSO4 SnCl2

11

Table 3 Effect of metallic salt on fastness properties of printed cotton fabric.

Formulations

Metallic salt Light

Fastness to

Washing Shade change

Staining to

Rubbing Dry Wet

Formulation - 1

CuSO4 FeSO4 SnCl2

5 4-5 6-7 4 4-5 5

5 4-5 4-5 4-5 4-5 4-5

4-5 4 4-5 4-5 4 4-5

4-5 4-5 4-5 4-5 4-5 4-5

4 4 4-5 4 4 4

Formulation - 2

CuSO4 FeSO4 SnCl2

12