Direct Dyes

Slide 1 of 40

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Direct Dyes

Slide 2 of 40

Direct dyes - dyes with a high affinity for cellulose fibres Substantive dyes are dyes used in a process in which dye molecules are attracted by physical forces at the molecular level to the textile substrates. The amount of this attraction is known as substantivity The "direct dye" classification in the Color Index system refers to various planar, highly conjugated molecular structures that also contain one or more anionic sulphonate group. It is because of these sulphonate groups that the molecules are soluble in water.

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Direct Dyes

Slide 3 of 40

Congo Red (Colour Index, No. 370), was the first Index, member of the direct cotton group of dyes. Patented by Paul Bttiger's (Friedrich Bayer Company in Elberfeld, Germany ) B.P. 4,416 of 1884

Congo red is the sodium salt of benzidinediazo-bisbenzidinediazo-bis1-naphthylamine-4-sulfonic acid (formula naphthylamineC32H22N6Na2O6S2, : molecular weight: 696.66 g/mol ) brownishbrownish-red powder,
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Direct Dyes Cellulose - Cellobiose

Slide 4 of 40

10.8

Benzedrine Hydrogen Bonding of Cellulose dyed with Congo Red

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Direct Dyes

Slide 5 of 40

Second Direct Dye

Benzopurpurine 4B

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Direct Dyes

Slide 6 of 40

Benzedrine Replacement 4,4 - diaminobenzanilide

C.I. Direct Black 166

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Direct Dyes

Slide 7 of 40

2,2'-dimethyl-5,5'2,2'-dimethyl-5,5'- dipropoxybenzidine is non-mutagenic non-

Synthesis and Evaluation of Non-genotoxic Direct NonDyes, Jin-Seok Bae* and Harold S. Freeman, fibres Jinand Polymers 2002, Vol.3, No.4, 140-146 140M. L. GULRAJANI

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Direct Dyes

Slide 8 of 40

C.I. Direct Yellow 59

Phenyalbenzothiazole Group Yellow substantive dyes

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Direct Dyes

Slide 9 of 40

C.I. Direct Green 28

Blue

Yellow

NonNon-substantive anthrquinone based blue dye is attached to substantive monoazo yellow dye via triazine molecule to get green dye
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Direct Dyes

Slide 10 of 40

C.I. Direct Yellow 12

Chrysophenine G Stilbene and azo chromophore: Dyeable on cotton, wool and silk
M. L. GULRAJANI

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Direct Dyes

Slide 11 of 40 Turquoise Blue shades

Phthalocyanine Direct Dyes Water soluble sodium salts of sulphonated copper phthalocyanine
M. L. GULRAJANI

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Direct Dyes Chemical Class Monoazo Disazo Polyazo CuCuComplex Stilbene Thiazole Dioxazine PhthaloPhthalocyanine
M. L. GULRAJANI

Slide 12 of 40 RED 14 71 10 3 2 VIO 4 83 3 9 1 BLU 52 31 12 3 2 GRE 8 21 64 4 2 BR 3 22 67 1 23 68 8 BL % 5 49 33 5 5 1 1 1

YEL ORG 4 58 8 17 13 7 53 16 23 1 -

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Direct Dyes

Slide 13 of 40

Reactant Fixable Dyes

Indosol SF dyes of Clariant have been one of the major development Original range had 12 copper complex dyes: C.I. Direct Violet 66 Indosol CR is the special dye fixing agent: N-methylol dicyandiamide C.I. Direct Violet 66

M. L. GULRAJANI

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Direct Dyes

Slide 14 of 40

Sorption Stage Diffusion and Migration Stage

Cooling Stage

Dyeing Cycle of a Direct Dye

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Direct Dyes

Slide 15 of 40

Classification of Direct Dyes

Class A - dyes that can be dyed with out salt and have good migration and levelling properties Class B dyes have a low rate of exhaustion and the rate of exhaustion may be adequately controlled by carefully regulated addition of common salt. Class C dyes that are highly sensitive to salt, and temperature. These are temperature controlable dyes
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Direct Dyes

Slide 16 of 40 Effect of Temperature Temperature increases the rate of diffusion of dyes in the fibre Temperature lowers the equilibrium dye uptake of the fibre
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Time, min Dye-bath exhaustion % 500C 500C

Dye - X

500C

900C 900C

Dye - Y

Log (Time of Dyeing) Sec

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Direct Dyes

Slide 17 of 40

Dye-bath exhaustion %

3% Glaubers Salt 1%

Effect of Salt
Salt Sensitive dye Durazol Fast Blue 4GS

0%

Time, min

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Direct Dyes

Slide 18 of 40

Effect of Salt

Sodium Ions
4

Electrostatic Repulsion

Dye ions

- - -

+ + + + + + + + + + +
100

Fabric

Affinity

Dyebath
M. L. GULRAJANI

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Direct Dyes

Slide 19 of 40

Effect of Electrolytes Adsorption of direct dyes on cellulosic fibres is influenced by the nature of the cation in dyebaths containing the alkali chlorides in equimolar concentrations, the extent of dye adsorption increasing markedly in the order Li' < Na' < K' < Rb' < Cs'.
Sivaraja lyer, Srinivasan and Baddi, Text. Research J., 38 (1968) 693

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Direct Dyes

Slide 20 of 40

BioBio-salt trisodium citrate in the dyeing of cotton

Direct Dye dyed with trisodium citrate

Direct Dye dyed with sod. chloride

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Direct Dyes

Slide 21 of 40

BioBio-salt trisodium citrate in the dyeing of cotton

Sodium Chloride Dye Reactive Direct S. Vat TDS 34800 3800 6900 Dye uptake 66.7 58.2 62.7 Trisodium citrate TDS 12300 2000 4000 Dye uptake 89.1 76.8 83.8

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Direct Dyes

Slide 22 of 40

Pretreatment No salt Dyeing

Treatment of cotton with cationic agents introduces positively charged group. These cationic groups form electrovalent bonds with the anionic dyes such as Direct and Reactive Dyes. There by eliminate the need of salt during dyeing
M. L. GULRAJANI

Polyepichlorohydrin dimethyl amine (PECH-amine) is (PECHprepared bu initial polymerization of of epichlorohydrin, followed by amination with diamine

Polyepichlorohydrin dimethyl amine (PECH-amine) (PECHINDIAN INSTITUTE OF TECHNOLOGY

Continued

Direct Dyes

Slide 23 of 40

Pretreatment No salt Dyeing

Chitosan derivative having a fibre-reactive fibregroup, namely OcrylamidomethylcrylamidomethylN-[(2-hydroxy-3[(2-hydroxytrimethyl ammonium) propyl] chitosan chloride (NMA(NMAHTCC
M. L. GULRAJANI

This compound when applied to cotton under alkaline conditions and is able to form a covalent bond with the fibre giving it good durability as an antimicrobial textile finish
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Direct Dyes

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Fixation of Direct Dyes

Mostly cation-active compounds are used as the cationfixation chemicals. These compounds form a complex of high molecular weight and low aqueous solubility with the dye resulting in high wet fastness of dyed fabrics C+ + D- = CD Amines, quaternary ammonium, phosphonium and tertiary sulphonium compounds can be used as dye fixing agents. By far the most important type of cationic fixing agents used in textile processing is quaternary ammonium salt

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Direct Dyes

Slide 25 of 40

Fixation of Direct Dyes

Cyanamide

Fibrofix Cyanamide condensation product

Formaldehyde condensation product of dicyandiamide

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Direct Dyes

Slide 26 of 40

Pretreatment No salt Dyeing

Azetidinium chloride

1,1-diethyl1,1-diethyl-3-hydroxy azetidinium chloride Sandene 8425 (Clariant)

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Direct Dyes

Slide 27 of 40

Pretreatment No salt Dyeing

Phenyl Monochlorotriazine Based compound

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Direct Dyes

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Mechanism of Dyeing Aggregation

All dyes have a tendency to associate in aqueous solution. An understanding of the association of dyes in water is of importance in both thermodynamic and kinetic studies of dyeing systems since almost all textile dyes are applied from aqueous systems systems. One can study the aggregation behaviour of dyes in solution by spectrophotometric analysis since dye aggregates normally have a lower extinction coefficient and their maximum absorbance is at shorter wavelengths compared to the monomolecular species with some exceptions
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Direct Dyes

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Mechanism of Dyeing Aggregation

Dye + Surfactant Absorbance Dye* Dye + Salt Promotes Aggregation Promotes Aggregation

*CI Direct Yellow 162

Wavelength, nm Continued

M. L. GULRAJANI

INDIAN INSTITUTE OF TECHNOLOGY

Direct Dyes

Slide 30 of 40

Mechanism of Dyeing Aggregation

Initially it was suggested that hydrogen bonds are responsible for the association of direct dyes. However layer studies suggest that the the aggregating forces are of the van der Waals type , including dipole-dipole (and induced dipole) forces dipoleand particularly dispersion forces, which are active over large numbers of planar-stacked molecules. planar


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Direct Dyes

Slide 31 of 40

Mechanism of Dyeing Aggregation

Aggregated direct dye with ionized salt is aqueous solution Continued

M. L. GULRAJANI

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Direct Dyes

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Mechanism of Dyeing Structure of Cotton

Cotton is a hydrophilic natural cellulose fibre whose porous structure facilitates the penetration of various solutes, including organic dyes. As a cellulose-based cellulosepolymer, it consists of D-glucose units joined by b-1,4Db-1,4glycosidic linkages, and it is well known that the cellulose chains associate with one another via intermolecular hydrogen bonds. The resultant system of polymer chains coalesces to form microfibrils that are organized into macrofibrils and subsequently into fibres. Continued

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Direct Dyes

Slide 33 of 40

Macro Structure of Cotton

Crystalline S fibrils S
2 1

20-30

20-35

Primary Wall Wax Fats Pectin

S3
Lumen

Reversal

Cuticle

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Direct Dyes

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Micro Structure of Cotton

Fibril Fibril

Pore Pore

Pore Pore

Fibril
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Fibril Continued
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Direct Dyes

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Mechanism of Dyeing Diffusion of Dyes Static Pore Model of Dye Diffusion

Continued

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Direct Dyes

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Mechanism of Dyeing Sorption on Internal Surface

Direct dyes are absorbed on the internal surface of cellulosic substrates, the amount of surface accessible to a dye anion depending on the form and size of the anion. The internal surface of the fibre also possesses an electric charge. The extent to which this initial charge is reinforced depends on the different absorption of the dye anions by different surfaces. Besides competition for dye sites, a mutual electrostatic repulsion occurs.
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Mechanism of Dyeing Sorption on Internal Surface

It is known that the accessible area on cellulosic substrates is a function of the molecule size. Recent research has shown that the accessible volume of a cellulosic fibre for a molecule with an effective diameter of 2.5 nm was about four times higher than that for a molecule with an effective diameter of 5 nm

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Direct Dyes

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Mechanism of Dyeing Void Size and Area

Viscose Rayon

Modal Fibres

Lyocell Fibres

Lyocell fibres consist of longer molecules, they have a greater degree of crystallinity, its crystallites are oriented in the fibre axis direction, and its void structure is similar to that of viscose fibres. Differences in the molecular and fine structure of these fibres cause different sorption properties.
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Direct Dyes
Internal Surface of Voids Void volume

Slide 39 of 40 Void Diameter Void Volume Vp, cm/g Viscose:3.1 Lyocell: 3.0 Modal : 2.4 Void Volume
Viscose:0.68 Lyocell: 0.62 Modal : 0.49

Specific Iner Surface, Sp [m2/g

500 475 450 425 400 375 350 325 300 275 250 2.2 2.4 2.6
MOD

0.75 0.70

VIS LYO

0.65 0.60 0.55 0.50 0.45 0.40

2.8

3.0

3.2

3.4

Void Diameter, nm

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Direct Dyes
References

Slide 40 of 40

The Diamond Jubilee of the Discovery of Direct Cotton Dyes, 1884 1944. By C. M. WHITTAKER, JSDC, 1945, 201. Direct Cotton Dyes, Common Salt, and Commonsense, By C. M. WHITTAKER, JSDC, 1942, 253. Effect of the bio-salt trisodium citrate in the dyeing of cotton, H Gurumallesh Prabu and M Sundrarajan, Color. Technol., 118 (2002) 131 Synthesis and Evaluation of Non-genotoxic Direct Dyes, Jin-Seok Bae* and Harold S. Freeman, fibres and Polymers 2002, Vol.3, No.4, 140-146. An investigation into direct dye aggregation, Martin Ferus-Comelo* and Andrew J Greaves, Color. Technol., 118 (2002) 15. Description of dyeing equilibria in the application of direct dyes, H Gerber, JSDC VOLUME11 2 MAY/JUNE 1996 153. The Application of Direct Dyes to Viscose Rayon Yarn and Staple, J. BOULTON, J.S.D.C. 67 (1951) 522. Structural Characteristics of New and Conventional Regenerated Cellulosic Fibers,Tatjana Kreze and Sonja Malej, Textile Research Journal 2003; 73; 675. Role of quaternary ammonium salts in improving the fastness properties of anionic dyes on cellulose fibres Saima Sharif,a,b Saeed Ahmadb,* and Mian Muhammad Izhar-ul-Haqa, Color. Technol., 123, 817

M. L. GULRAJANI

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End of Lecture 2 & 3

M. L. GULRAJANI
INDIAN INSTITUTE OF TECHNOLOGY