Chapter-1

INTRODUCTION
Nature expresses itself in a wide spectrum of colors all around us. The alchemy of colors started from an early time. Indians have been forerunners in the art of natural dyeing. The advent of synthetic dyes caused rapid decline in the use of natural dyes, which were completely replaced by the former within a century. Earlier understanding of dyeing techniques and their applications was empirical and was not backed by scientific reasoning. Natural dyeing had developed essentially as a folk art. However, in recent times the dyeing technique is interpreted on sound scientific principles, and the interaction between the dye and the dyed material is well understood. Recently, the utilization of natural dyes in textile applications has been increasing due to the strict environmental standard imposed by many countries in a response to the hazard associated with synthetic dye stuffs. In this study, dyeing of Wool fabric with green tea as natural colorant has been investigated. Green tea plants are classified as Camellia sinensis. The different classes of compound found in green tea include amino acids, caffeine, carbohydrates, carotenoids, chlorophyll, lipids, minerals, nucleotides, organic acids, polyphenols, saponins, unsaponifiable and volatile compounds. In this project the dyeing process was carried out with dye extracted from three different qualities of Tea Leaves using three different

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solvents. The dyeing was initially carried out on various substrates and the depth was found best in case of Wool & Silk. This thesis reports the dyeing of Wool fabric with dye extracted from Tea Leaves and comparative study of Washing Fastness, Light fastness, K/S & Reflectance values.

References
1. Chemistry of Natural Dyes; Padma S Vankar. 2. Handbook of Natural Coloran t s Edited by Thomas Bechtold and Rita Mussak 2009 John Wiley & Sons, Ltd. ISBN: 978-0-470-51199-2. 3. F. Braudel, The Mediterranean in the Ancient World, Penguin Books, 2002. 4. E. Ferreira, A. Hulme, H. McNab and A. Quye, The natural constituents of historical textile dyes, Chem. Soc. Rev., 33, 329336 (2004).

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Chapter-2

REVIEW OF LITERATURE
2.1 General
Tea is produced from the leaves and stems of Camellia sinensis. It is an evergreen shrub or tree and can grow to heights of 30 feet, but is usually pruned to 2-5 feet for cultivation. The leaves are dark green, alternate and oval, with serrated edges, and the blossoms are white, fragrant, and appear in clusters or singly. It is the most popular non-alcoholic beverage in the world.

2.2 Tea Classification

Green Tea leaves are made from the more mature leaves of Camellia sinensis than the buds used for white tea production. The harvested leaves may be slightly withered prior to steaming or pan frying. This allows for a slight oxidation of the catechins. Oolong Tea leaves are initially wilted by the sun or air to remove some of the moisture. A time to allow oxidation is chosen and then stopped at a known time by pan frying. The leaves are then cooled and dried to remove all moisture. Black Tea leaves are made by oxidizing the leaves much longer than oolong tea leaves. The leaves are withered by air and then crushed and rolled to maximize full oxidation.

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2.3 Dyeing with Tea Leaves

Tea leaves are collected to use immediately as green tea or are used for dyeing purposes. These leaves dye fabric in brown, yellow-green and even black shades, after mordanting with iron sulfate. Since the tea yield In Vietnam is high, being planted in many regions, and it is an export product, it is possible to dye fabric with those leaves not used for either small production or industrial purposes. In addition, the leaves can be used for medical applications and for deodorizing. Colorings ingredients in the leaves include polyphenols and flavonols. To prepare the dye the leaves are placed in boiling water and the extract is used directly for dyeing silk, Wool or cotton fabric. The dyeing show good light fastness and wash fastness.

2.4 Green Tea Chemistry

Flavonoids, flavonols and phenolic acids make up approximately 30% of dried Camellia Sinensis by weight. Most of the polyphenols present are flavonols commonly known as catechins, with epicatechin and its derivatives being the most predominant forms. The gallic acid ester epigallocatechin gallate (EGCG) is present in the highest concentration, making up over 61% of the epicatechin derivatives included in the green tea leaves. Other green tea polyphenols include flavonoids, and their glycosides, depsides such as chlorogenic acid and coumarylquinic acid, and a phenolic acid unique to tea, theogallin. Caffeine makes up an additional 3%, and there are trace amounts of the methylxanthines theophylline and theobromine, and an amino acid unique to tea, theanin.

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2.3.1 Chemical Composition

2.3.2 Biochemical compounds responsible for Color

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2.3.3 Biochemical compounds responsible for Taste

2.4 The components Caffeine

Caffeine is a purine derivative, which is 1,3,7-tri- methyl xanthine. Caffeine content in black tea is around 3 4% of dry weight. It has stimulating property and removes mental fatigue.

Tea Fibre
The leaf cell wall, containing cellulostic materials surrounded by hemicellulose and a lignin seal, prevents the penetration of hydrolyzing enzymes. The reduced succulence in the matured shoot is believed to be due to structural bonding between phenolic components of lignin, polysaccharides and cutin of cell wall.

Carbohydrates
The free sugars found in tea shoot are glucose, fructose, sucrose, raffinose and stachyose. Maltose in Assam variety and rhamnose in china variety appeared special. Pectic substances contain galactose, arabinose, galacturonic acid, rhamnose and ribose.

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Free sugars are responsible for the synthesis of catechins in tea shoot, formation of heterocyclic flavor compounds during processing of black tea and contributing towards water-soluble solids in tea liquor. Cellulose, hemi-cellulose, pectins and lignins are responsible for the formation of crude fibre content in black tea.

Amino acids
Aspartic, glutamic, serine, glutamine, tyrosine, valine, phenylalanine, leucine, isoleucine and theanine (5-N-ethylglutamine) were found to be the principal amino acids present in tea leaf. Theanine alone contributed around 60% of total amino acid content. Asparagine was formed during withering. The amino acids play an important role in the development of tea aroma during the processing of black tea. Volatile Carbonyl Compounds formed from the amino acids during processing: Glycine formaldehyde Alanine acetaldehyde Valine isobutyraldehyde Leucine isovaleraldehyde Isoleucine 2-methylbutanol Methionine methional Phenyl alanine phenylacetaldehyde

Lipids and fatty acids

The neutral, glyco and phospholipid contents and their fatty acid composition varied in Assam, China and Cambod varieties and also
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during different stages of black tea manufacture. Total lipid contents (%) and total fatty acids ( g/g) at different stages i.e. green leaf, withered leaf, rolled leaf, fermented leaf and black teas are about 6.5, 5.7, 4.5, 4.3 and 2.8 and 9.8, 8.4, 6.6, 4.8 and 3.7 respectively. The major fatty acids available in tea are linolenic, linoleic, oleic and palmitic.

Carotenoids
The four major carotenoids, -carotene, lutein, violaxanthine and neoxanthine were estimated spectroscopically in four different Tocklai released clones, namely, TV-1 (China hybrid), TV-2 (Assam Betjan variety), TV-9 (Assam-Cambod variety) and TV-17 (China hybrid).

Anthocyanidins
Delphenidin and cyanidin were the major anthocyanidins present in tea leaf.

Organic acids
Citric, tartaric, malic, oxalic, fumaric and succinic acids were detected in Assam leaf. Role of organic acids towards the biochemical influence on the quality of black tea is not yet reported.

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Wool
Wool is the generally accepted generic description of the hair of various breeds of domesticated sheep, although it is also commonly used as the generic name of all animal hair, particularly including the so called fine animal hair. Wool contains a-keratins (protein molecules in a-helix conformation, in a complex mixture with proteins of irregular structure) as shown:-

From a macromolecular point of view, wool is a composite fiber, i.e. a Fibril-reinforced matrix material with both the fibrils and the matrix
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consisting of polypeptides (thus of chemically similar nature), interconnected physically and chemically. From a morphological point of view, the wool fiber is a nanocomposite (the reinforcing fibrils have a diameter of about 10 nm) of high complexity with a clear hierarchy indicating an enormous degree of self-organization.

General chemical composition: Wool is a protein fiber and as such

consists of the elements carbon, hydrogen, oxygen, nitrogen and sulphur. Except for the large sulphur content, the elemental composition is typical of proteins. The sulphur mainly derives from the amino acid cystine, which has two sulphur atoms forming a disulphide bond, this being the most important cross linking element of wool. Beside cystine, 20 other amino acid residues are found in wool .They are distinguished by their side chain, which imparts a special character, being either hydrophilic or hydrophobic, acidic or basic.

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Amino Acid Composition:

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Composition and structure of morphological components of Wool

The classical morphology of wool is represented by Fig.1, showing the gross hierarchy of morphological elements. The fiber is surrounded by cuticle cells which overlap in one direction and which consist at least of four layers, the epicuticle, the Alayer and the Blayer of the exocuticle, and the endocuticle. The cuticle surrounds a compacted mass of cortical cells of spindle form aligned with the fiber axis and with their fringed ends interdigitating with each other. Both cuticle and cortical cells are separated by the so-called cell
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membrane complex comprising internal lipids and proteins. This cell membrane complex is the component between the cells that guarantees strong intercellular bonding via proteins generally called desmosomes.

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References
1. Deo, H. T., and Desai, B. K. 1999. Dyeing of Cotton and Jute with Tea as a Natural Dye. Journal of the Society of Dyers and Colourists 115 (7-8):224227. 2. Kim, S. H. 2006. Dyeing Characteristics and UV Protection Property of Green Tea Dyed Cotton Fabrics - Focusing on the Effect of Chitosan Mordanting Condition. Fibers and Polymers 7 (3):255-261. 3. ChromadexTM Tea Testing FAQs. 4. Major flavonoids in dry tea J. Petersona,*, J. Dwyera, S. Bhagwatb, D. Haytowitzb, J. Holdenb, A.L. Eldridgec, G. Beecherd,1, J. Aladesanmia, 5. Medicinal Importance of natural dyes A Review B.Chenagiah*, K.Mallikarjun ,A Rao, K.Mahesh Kumar, M.Alagusundaram, 6. Wool: Science and technology Edited by W S Simpson and G H Crawshaw. 7. Lindley H, in Chemistry of Natural Fibres, ed. Asquith R S, Plenum Press, London, 1977, p 147.

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