What is polyamide

A polyamide is a polymer containing monomers of amides joined by peptide bonds. They can occur both naturally, examples being proteins, such as wool and silk, and can be made artificially through step-growth polymerization, examples being nylons, aramids, and sodium poly (aspartate).Here we get two word amide & peptide bond.

3-D Structure

Types of Polyamide
Mainly there are two types of poly-amide. Natural polyamide, examples being proteins, such as wool & silk. Synthetic polyamide such as nylon, aramid etc. Here well keep our discussion limited within synthetic polyamide if said more specifically then its on nylon

Physical & Chemical properties related to dyeing

Tenacity-4-9gm/den (in dry cond); remain 90% of dry, in wet condition. Its tensile strength is higher than that of wool, silk, rayon, or cotton. Elongation-26-32% (regular filament) Elastic recovery-about 100% upto 8% extension (no impact in textile use) Initial modulas-40-60g/den Average toughness-1.08

Physical & Chemical properties related to dyeing

Specific gravity:1.14 Moistur regain:4-4.5% Melting point: 250C(Approximately) No mildew or bacterial effects High resistance to: insects, fungi and animals molds, mildew, rot.

Physical & Chemical properties related to dyeing

Extremely chemically stable Acids: Dilute acid have little effect Hot mineral acid decomposes nylon Alkalis: excellent resistant to alkali. It can be boiled in strong caustic soda without damage Organic solvent: Fibre not attacked by solvent during dry- cleaning, conc. formic acid,phenol,cresol are suitable solvent.[29]

Preparation of nylon before dyeing

Nylon filaments are relatively free from impurities. Washing with a detergent and soda ash (Na2CO3) at 70 C usually removes spin finishes and lubricants present on the filaments and any polyvinyl alcohol or other synthetic size on woven fabric.

Heat setting:

Nylon is a thermoplastic polymer. When treated in hot water, the temperature is well above the glass transition temperature (Tg) of nylon. Fabrics may give considerable changes in dimensions as filament tensions introduced during manufacture relax. Heat setting avoids fabric deformation and shrinkage provided that the temperature is higher than that to which the material will be subsequently exposed. [25]

Selection of different dye types for nylon:

This scheme indicates that these polyamide polymers will have substantivity for hydrophobic dyes (interactions with tetramethylene and hexamethylene hydrophobic regions) Anionic dyes (for example, sulphonated acid dyes interacting with protonated amino end groups) Cationic dyes (interactions with ionised carboxy end groups).

Thus, below pH 3.5, nylon behaves as if it possesses a net positive charge and exhibits a strong attraction for bulky anions such as simple mono-, di- and trisulphonated acid dyes. Above pH 3.5, nylon shows a diminishing attraction for these anions, confirming that the overall positive charge is reducing to zero. Above pH 7.0, nylon is increasingly negatively charged and has a strong attraction for cations.

Some Major Nylon Fiber Uses:

Apparel: Blouses, dresses, foundation garments, hosiery, lingerie, underwear, raincoats, ski apparel, windbreakers, swimwear, and cycle wear. Home Furnishings: Bedspreads, carpets, curtains, upholstery Industrial and Other Uses: Tire cord, hoses, conveyer and seat belts, parachutes, racket strings, ropes and nets, sleeping bags, tarpaulins, tents, thread, monofilament fishing line, dental floss.

Properties

Acid dye is a water soluble dye. Its an anionic dye. These are usually sodium salts of sulphonic acids & less frequently of carboxylic acid. These are applied on substrate in acidic medium in the dyebath range from sulphuric acid (dyebath pH<2.0) to ammonium acetate (dyebath pH>6.5). They have special affinity to polyamide; both natural & synthetic. They do give dyed substrate with bright shade having high light fastness.

Types of dye
Strong acid dye/dispersed dye/Levelling dye II. Weak acid dye/Partially aggregated dye/Milling dye III. Neutral acid dye/Super milling dye/Aggregated dye
I.

Dyeing mechanism:

By Ion Exchange Process/Coulombic Interaction: Dyeing of acid dyes on nylon involves the creation of positive sites at the end amino groups of the fibre macromoleculcs. This is done by the hydrogen ions supplied by the acid used in the dyebath, and adsorption and binding of the dye anions at these positive sites. The electrostatic bond formed between the dye anion and fibre positive site being fairly strong.
HOOC Nylon NH2 + H + + X HOOC Nylon NH3+X- + Dye=

HOOC Nylon NH3+XHOOC Nylon NH3+Dye- + X-

02. Hydrophobic Interaction

Dyeing is not solely a consequence of simple ionic interaction. Non-polarinteractions are also capable of playing an important role. Moreover, the amino group content of nylon is usually 45mmol/kg whereas wool posses 820mmol/kg The limited number of amino groups in nylon and its more hydrophobic nature, however, have a profound influence on its dyeing behaviourFor large hydrophobic dye molecules, other types of dye-fibre interactions become important besides coulombic attraction. These additional dye-fibre forces may involve dipole interactions, hydrogen bonding, and dispersion forces operating between groups in the dye molecule and appropriate groups in the nylon. Nylon have regions along the polymer chains that are quite hydrophobic, being void of ionic and polar groups. Dye-dye and dye-fibre hydrophobic interactions might be expected in such regions.

Important factors of Acid dyeing/Formation of Recipe

ACID? It is stated earlier that the reaction site in nylon is amino group for acid dye. And the creation of the positive site at the end of amino group is done by the donation of proton by acid. The dye uptake (or exhastion of the dyebath) depends on the nature of the acid (whether strong or weak). The dye uptake (or exhastion of the dyebath) depends on the concentration of the acid in the dyebath. So, we can say for dyeing some proton doner is mandatory.[26]-223

Acid or Acid liberating agent or Both? In practice acid is used where highly acidic medium is recommended, in case of leveling acid dye/low molecular wt dye. And the acid used is dilute sulphuric acid or formic acid. But formic acid is recommended as there is a possibility of hydrolysis of nylon in case of sulphuric acid. In case of milling or super milling dye/high molecular wt dye usually acid & acid liberating agent is used together. The reason behind this is, these type of dye require mild acidic to neutral medium at the start of dyeing & then slowly decrease of pH. Here acid liberating agent ensure mild acidic to neutral medium & slow dosing of acid ensure slower decrease of pH. Here as ammonium sulphate, ammoniaum acetate, sodium sulphate are used as acid liberating agent & actic acid is usually used as acid.

pH? This is stated earlier in types of dye as range from 3.0-7.0 depending on types of dye used.

Temperature?

The glass transition temperature (Tg) of water-saturated nylon probably not much greater than about 40oC. Once the temperature exceeds Tg the movement of polymer chain segments is then possible. As a result rate of dye absorption as diffusion of dye molecules into the polymer matrix becomes easier. The temperature at which the initial rate of dyeing begins to significantly increase is called the dyeing transition temperature (Td). This temperature, however, is often 20-30oC higher than Tg under the given dyeing conditions. At temperatures somewhat higher than Tg the voids between chains in the amorphous polymer are too small to accommodate large molecules. Therefore, in spite of the increased mobility at temperatures above Tg resulting from easier polymer chain rotation, there is little dye absorption. On the temperature exceeds the value of TD, however, the greater ease of chain mobility creates voids whose average volume has increased to the point that allows dye molecules to enter them. The increasing size and mobility of these voids, now containing dye molecules, allows a significant increase in the rate of diffusion of dye into the polymer matrix. These are the theoretical aspects. Practically no dyeing take places below 40 oC. Best dyeing results are obtained if the dyeing is started at about 40 oC & temperature gradually raised to the boil. Specially high temperature is recommended for high molecular wt dye / hydrophobic dye / aggregate dye, because they are converted to molecular dispersion (fine dispersion) from colloidal dispersion at high temperature.[25]-274

Levelling/Retarding agent?
Due to high initial color strike of acid dye on a substrate there occurs poor unlevelness or unevenness of dyeing. If once caused this unevenness, it is difficult to correct subsequently. To solve this problem some leveling / retarding agent have to be used. There are two main types of leveling agent anionic & cationic/non-ionic. Anionic leveling agent attacks the cationic site / positive site of nylon that is ammonium ion & blocked/masked this position. Thus they retard the high initial colour strike of dye on the nylon. As the dyeing proceed, the temp. increased & pH fall & cationic site release these leveling agent & dye anions got the chance to be bonded with fibre. Incase of cationic/non-ionic leveling agent, this agent forms complex with dye(Dye-Aux+),thus inhibits initial high colour strike. As dyeing proceeds, this comples dissociates to relese dyes to attack the cationic site of nylon

Application procedure[23]-225
Typical recipe Wetting agent =0.5-1.0 g/l Antifoaming agent =0.1-0.5 g/l Levelling agent=1.0-2.0 g/l Anticreasing agent =1.0-2.0 g/l Ammonium sulfate =2.0-4.0 g/l Or, Sodium acetate =1.0-2.0 g/l Acetic acid =Y g/l Acid dyes =X% Temperature =100C Time =30-50 min. M:L=1:8 to 1:10

Aftretreatment : Rinse twice with hot and cold water successively. For improvement of polyamide dyeing with acid dyes can improve by treating with a suitable fixing agent at 60 -70oC for 15 - 20 min at 4 - 5 pH level (with acetic acid). Rinse again to clean unexpected chemicals any more. Correction of shade/shade matching To correct unlevel dyeings on nylon, the goods are treated at pH 8.0-8.5 at the boil. At this pH, there are few ammonium ion groups and some of the dye desorbs. The bath can then be acidified and the dcsorbcd dye re-exhausted onto the nylon. This is less successful with high substantivity acid dyes. Chemical stripping requires the use of reducing agents such as sodium sulphoxylate-formaldehyde (NaSO2.CH2OH) but complete stripping may be difficult.[25]-227

Natural tanning agents This process is known as the full back-tan and involves treating the dyed nylon with tannic acid (2% owf), at pH 4.0 (CH3COOH) for 20 minutes at 80C, followed by a treatment in a separate bath containing potassium antimonyl tartrate (tartar emetic) (2% owf) at pH 4.0 for 20 minutes at 80 C. It is considered that the full back-tan results in the formation of a large sparingly watersoluble anionic complex, located at the surface of the dyed nylon, which restricts diffusion of anionic dye molecules out of the substrate during washing. Although the full back-tan often results in quite dramatic improvement in wash-fastness of acid dyes on nylon, the process suffers from the following disadvantages: The process is in two stages, and therefore time consuming; Tartar emetic is toxic; Tannic acid discolours on exposure to light; Back-tanning reduces the light-fastness of the dyes on nylon; The process is expensive; The effect can be partially lost on steam setting.

Manufacturer ACNA BASF Bayer Swiss-color Francolor

Country

Trade (brand name) Naphthol, Novamina Erganil, Lurazol Supramine, Supranol Benzyl, Kiton, Neonyl Supracid, Xylidine

Metal-Complex Dyes On Polyamide

What is Metal-Complex Dye?

Actually it comes from the concept of Mordanting where specific Metals are used as a bridge between the substrate and chromophore. Metals form complex ions by co-ordinate & covalent bonds with the chromophore & fiber structure, so the combined structure is termed as Metal-Complex.

Metal Complex Dyes on Nylon

What is the reason behind?

Scopes & Purposes of using Metallization in Nylon Dyeing

Some specific metals like - Chromium, Copper, Cobalt, Nickel, Tin etc. also Iron is used in modern developed process. The metal atom is supposed to form a complex with the dyestuff molecule already bonded with the substrate. Thus they improve the light & wash fastness of dyes. When Acid Dyes are used in Nylon Processing incorporated with Metal ion as complexion with dyestuffs Nylon gets some improve of fastness propertiesWash fastness scale of Nylon: if normal Acid dyed - 4 5 (ISO fastness test) if metal complex dyed - 5 6 (ISO fastness test) Light fastness Scale of Nylon: if normal Acid dyed - 5 6 (SDC test) if metal complex dyed - 6 7 (SDC test)

Metal-Complex Dyes for Nylon

Metals can be used in Nylon in two ways
1.

Acid-Mordant: where dyeing with Acid dyes & mordanting with metals are separately done. Pre-metallised: where dyes are premetallised with suitable metals & directly used for dyeing. Two classes 1:1 metal complex dyes 1:2 metal complex dyes

2.

Acid-Mordant dyes on Nylon

Mordant dyes combine with metallic oxides and hydroxides by forming both covalent and co-ordinate bonds to give metal dye complex also called LAKES. Salts of Chromium, Copper, Cobalt, Iron, Tin etc is suitable as Mordant. For nylon, Chromium is vastly used as mordant & among the salts of chromium, sodium or potassium dichromate is mostly used. Acid dyes having sulphontes groups in structures of specially o:o dihydroxy azo classes are suitable to use as acid mordanting.

Methods of application
a) Chrome-Mordant process. b) After-Chrome Process. c) Meta-Chrome process.

Advantages:

Disadvantages:

Good fastness properties. Low dyestuff cost. No risk of spoilage.

Good leveling properties.

Not applicable in commercially. After chroming always bring some change in color. If dye particles are present in the chroming bath dyes precipitate on the material surface, which results poor rubbing fastness. So complete exhaustion is required. Residual di-chromate, left in the nylon, promotes tendering on exposure to light. Dyeing process now restricted mainly to blacks, as shade correction & color matching is tough.

Pre-metallised Dye on Nylon

The process of separate dyeing & chroming are very lengthy & cumbersome, even though the Metachrome process is a single bath process many chrome dyes cannot be dyed in this process. As a logical extension of chrome dyes into the fiber, it follows that if chromium is incorporated with the dyestuff molecule by the manufacture, the pre-metallised dye then can be applied in the fiber in a very simple process. This would eliminate the chroming process by the dyer.

First pre-metallised dyes was achieved in 1915 when CIBA & IG produced Neolan & Palatine Fast dyes respectively.

Chemistry involved in Pre-metallised Dyes

1:1 metal complex dye only one dyestuff is attached with the central metal atom. The formation of co-ordination bonds with both the fiber and with dyestuff depends on the Sulphonic acid groups. Solubilizing action of Sulphonic acid depends on the properties of sulphonate ion which contain oxygen atoms which are strong acid donors. But this electron donors creates problems like Skittering & reduce Exhaustion.

1:2 metal-complex dyes

They have 2 dyestuff molecules associated with one metal atom. These have very good exhaustion properties.

Dye Fixation Mechanism

covalent bonds (through hydroxy groups of the fiber). co-ordinate bonds (through free amino groups of the fiber). electrovalent bonds (through protonated amino groups of the fiber).

Effect of Premetallized dyes on Polyamide fiber: They build up well on the polyamide fiber into Heavy shades. There affinity depends on the physical & hydrogen bonding. There wash & light fastness properties are extremely good.

Limitations: If the initial adsorption is not uniform, level dyeing will be very hard to achieve. They are the worst of all classes in case of covering yarn variation.

Application of metal-complex dyes (premetallised dye) on nylon

Typical recipe Wetting agent Leveling agent Anticreasing agent Borax Metal-complex dye Temperature Time M:L = = = = = = = = 0.5-1.0g/l 1.0-2.0g/l 1.0-2.0g/l Y g/l (for maintaining, pH 8 - 8.5) X% 100C 30-50 min 1:8 to 1:10

Dyeing Curve

Metal complex dyes have got some limitations

They have very few ranges of shades. Hard to produce light shades, so preferred for darker shades only. They are the worse than the other classes in case of covering the yarn variation. Hard to control the leveling of dyeing. Metal sometimes accused of being health hazardous & toxic to environment.

Modern Development
[According to the study of R. M. Shishtawy & M. M. Kamel of Textile Research division of National Research Center, Dokki, Cairo, Egypt (internet entry C.E.T 2002)]

The previously used Chromium and others are toxicologically & ecologically hazardous. The Chromium (III) is replaced by safer Iron (II) by the researchers using three commercial azo Acid mordant dyes & applied to Nylon Fabrics. This Showed very good fastness result especially in dye class Acid Mordant Orange 2Rwith Fe complex. It shows following Results: - excellent Wash Fastness ranging 4-5 - excellent Light Fastness ranging 5-6 - exhaustion is 98% to 90% under temperature Ranging from 60 to 90oC This Result demonstrate that it is possible to obtain more environmentally safe dyeing by Iron-complexed Acid Mordant dyes with a high affinity for both nylon & wool & good fastness properties.

Properties of dye:
They are organic chemical substance, non-ionic, insoluble & molecularly dispersed. Applied on substrate in mild acidic medium pH-4.5-5.0. Application require dispersing agent. There are available different dyeing method carrier, HTHP, thermosol. In the face of NO gas from electric heater, open gas fire, high temp burning there occurs the fading of colour. Possibility of dye sublimation due to low molecular size of dye, no ionic group, no sulphonated group & also due to high temp heating. Widely used in the colouration of synthetic fibre.

Dyeing mechanism
Generally dyeing of nylon disperse dye is of dye: We know disperse dye is non-ionic & water insoluble dye. So, in the first stecarried out in four distinct step1. Dispersion of dye Done by dispersing agent & rise in temp. 1. Absorption of dye
a) Carrier method: I. By structural relaxation: II. By film formation b) In HTHP method:
2.

Diffusion of Dye

4.

Fixation of Dye:
Fixation can be performed in three waysa.

b.

c.

By H-bonding: between dye & fibre By dipole-dipole bonding: In the dyed materials, dipoles originate due to difference of electronegativity of adjacent atom. Thus dipole-dipole bond is cerated between two dipoles by van-der-walls force. By mechanical trapping: In high temp. through large hole of substrate dye enter inside the substrate.At low temp. when hole are reduced in size, the dye can not come out or there occur the mechanical trapping.

Recipe formation

Dispersing agent? We know disperse dye is non-ionic & water insoluble dye. So, to increase the dye solubility & to make uniform dispersion of dye in the dye bath, dispersing agent is mandatory. Acetic acid? The application of disperse dye requires mild acidic medium (pH4.5 - 5.0). This is maintain by a mild acid. Most of the time actic acid is the best choice. Temperature? As the dyeing of disperse dye mostly occurred by structural relaxation of the substrate,so we need to maintain the dye bath temp above Tg. The Tg of nylon not less than 40oC .Best dyeing is obtained at above 80oC. Time? For performing distinct four stages it need time.Optimum

Application Of Dye
Typical recipe Dispersing agent = 0.5 - 1.0 g/l Sequestering agent = 1.0 - 2.0 g/l Levelling agent = 1.0 - 2.0 g/l Dyes = X% Acetic acid (50%) = 0.5 - 2.0 g/l (to maintain pH=4-5) Temperature = 80 - 100C (maximum 120C as vender recommendation) Time = 30 - 60 mins. M:L = 1 : 10 Afterteratment Rinse twice with howater.t and cold Treat the fabric with alkali solution at 70 - 80C for 10 - 15 minutes. Rinse twice with hot and cold water, and then Neutralize with acetic acid.

Dyeing Curve

Fastness property
Disperse dyes cover both physical and chemical variations in the fibre very well. However, wet and washfastness properties of these dyes on nylon is with the exception of 2:1 metal-complex disperse and reactive disperse dyes very poor, and consequently their use is restricted to applications where high wet- and washfastness properties are not required. The light-fastness of the dyeings is normally good.

Advantages of using disperse dye

Barre effect does not appear on nylon like in case of

dyeing with acid dyes. Good migration during dyeing. Level dyeing, so it is good for light shades. Economical and easy to apply.

Disadvantages of using disperse dye

Poor to moderate wet fastness, especially in heavy

shades. Limited shades, mainly pale shades for fabrics (e.g. lingerie fabrics and sheer hose) that do not require repeated or severe washing. Disperse dyes on nylon are sensitive to fading by ozone and nitrogen dioxide.

Reactive disperse dye

CI developed a range of reactive disperse dyes the Procinyls, specifically for nylon dyeing. These dyes were subsequently withdrawn from the market in the 1980s, but aspects of their chemistry and application to nylon are well worth recording. Scott and Vickerstaff [14] described the basic chemistry of this system. I Five dyes were marketed: Procinyl Yellow GS, Procinyl Scarlet GS, Procinyl Red GS, Procinyl Orange GS and Procinyl Blue RS. Structures were not widely published, but the patent literature indicates that a mixture of reactive groups were used, including chlorohydrin, chlorotriazine and chloro-ethyl-aminosulphone. A Russian paper [15] on dyeing wool with Procinyl Blue RS confirmed its structure.

Under alkaline conditions the unreactive chlorohydrin form eliminates HCl to form the highly reactive bisepoxide, which reacts covalently with nucleophilic sites.

In Japan, production has recently commenced, on a pilot scale, of reactive disperse dyes targeted at solving the important problem of producing dyed microfibre blends of polyamide and polyester with good wet-fastness properties.

Modification In Dyeing Properties Of Nylon

Modifications done-

Modification Of polymerisation process of nylon polymer.

Modification of specific polymer properties.

Modification of dyeing properties of polymer.

Advantage of Modification

Deep dyeing of Nylon. Application of Basic dyes on Nylon. Application of Reactive dyes on Nylon. Application of Direct dyes on Nylon.

Deep Dyeing of Nylon

This is done by the following modification

Modification of the polymerisation process to give a polymer with a higher amine end group (AEG) content consequent increased substantivity towards anionic dyes that is Acid dyes.

It can be achieved by(1) increasing the proportion of diamine in the reaction mixture[40]; (2) by adding p-toluene sulphonic acid derivatives to the system, which protects the free amino end groups during polymer and yarn manufacture, OR by adding phosphinic or phosphonic acid derivatives to prevent oxidative loss of diamine [41];

(3) by producing a branched-chain polymer for example, by copolymerisation with trimesic acid (1,3,5benzene tricarboxylic acid) (fig shown below); (4) by modifying the melt-spinning process such that the disposition of the polymer chains favours penetration of dye molecules for example, by co-extruding nylon 6.6 and polycaprolactam (nylon 6).

Application Of Basic Dyes On Nylon

The affinity of Basic dyes to nylon can be increased by the following way

by introducing strongly acidic groups (for example, SO3H) into the fibre during the polymerisation process. Such groups can be introduced either within a chain by copolymerisation with 3,5-dicarboxybenzene-1sulphonic acid or at the end of a chain by using 3,5disulphobenzene-1-carboxylic acid (fig shown below).

addition of acetylated caprolactam or butyrolactone to the polymerisation system.

Thus I.C.I, in Dutch Patent (07)67-1250 state that the affinity of nylon 66 for basic dyes is increased if there is included in the monomer (nylon salt) 0.5-5 molar per cent of disodium 9,9, bis-p-carbamethyl-fluorene-2,7-disulphonate, a body with the structure.[30]

 Basic dyestuffs can be used for nylon, but ordinarily give only poor fastness to light and to washing. Manufacturers are very cognisant of any dyeing deficiencies in their fibres and will go to a lot of trouble to put them right
Mixtures of different nylon types in a carpet give attractive multi-colour effects because of their differential dyeing behaviour.[01][25]

Application Of Reactive Dyes On Nylon.

Basic Concept About Reactive Dyes On Nylon

Reactive dyes contain fibre-reactive side-chains, capable of forming covalent bonds with nucleophilic sites in appropriate fibres during the dyeing process.

As a class, they have been extremely successful on cotton and wool fibres, since they are capable of producing a very wide gamut of shades with excellent wet-fastness properties.

 However, on nylon fibres Reactive dyes are not so successful, only giving sufficient covalent bonding in pale to moderate depths; in full depths the dye is present mainly as unfixed anionic dye and thus exhibits the indifferent wet fastness properties of acid dyes. In the light of renewed current demands for bright, full shades on nylon with good wet-fastness properties, the causes of this unsatisfactory situation are worth further investigation.

Cellulose reactive dyes such as Procion, Amaryl, Remajol, Drimarene, Reactone, Primazin etc. can be applied to polyamide fibre. These dyes are very sensitive to physical & chemical variations in the fibre, so they are not suitable for dyeing nylon filament. They produce bright shades of good wet fastness on spun nylon. The sulphonic acid group present in the rective dye is responsible for fixation of the dye on the polyamide fibre.

Application Procedure

Formic acid 4% and predissolved dyestuff is added to the bath. pH is maintained at 4 to 5. The temperature is raised slowly to 95oC and the material is dyed at this temp. Run for one hour. Then material is rinsed. soaped at 85oC for 15 minutes with 2 g/l Lissapol ND and 2 g/l soda ash.

Dyes which react by a nucleophilic addition reaction[01]

Fixation Mechanism Of Reactive Dye

Generally Remazol dye based on 2sulphatoethylsulphone precursor of vinyl sulphone or related species follow this mechanism.
Dyes which react by a nucleophilic substitution reaction

Hetero-cyclic ring bearing halogeno subtituents generally performs nucleophilic substitution reaction during fixation.

The MCT dye will fix to nylon 6.6 according to[01]

Cationic Reactive Dye

A Sandoz patent [16] has claimed vinylsulphonyl dyes containing a pendant cationic group as reactive dyes for nylon which give level dyeings of high wet-fastness. There are clearly potential advantages in using cationic reactive dyes since, under alkaline conditions, the fibre is negatively charged and the majority of the amino groups are deprotonated, thus enhancing the nucleophilic character of the fibre.

Application Of Direct Dye On Nylon

Some dyestuffs of this class are used successfully for dyeing nylon; others are of little use.

The useful colours are, in general, those which are similar in chemical structure to the acid dyes, and they may be applied to nylon by methods similar to those used for acid dyes.
Direct dyestuffs provide shades of good fastness to washing and to perspiration. The wash fastness of these dyestuffs on nylon is better than that of the same dyes on cotton or wool. [29]-226

Application Of Cross-linking Agents

In a series of papers, Ho and Lewis [18-21] considered the use of crosslinking agents, either as a means to increase the number of amino functional groups in nylon, or as a means to covalently link dyes. The first crosslinking agent to be studied was N,N,Ntriacroylaminohexahydro-s-triazine (FAP) [18].

This compound was prepared and applied to nylon from an aqueous anionic dispersion.

The three substrates (untreated nylon, nylon I and nylon II) were dyed with a monochloro-striazine dye.

Dyeings on substrate nylon I indicated that the majority of the original primary amine residues were no longer available for nucleophilic substitution reactions with the MCT dye.

Substrate nylon II gave the best exhaustion and covalent fixation of the MCT dye,confirming successful introduction of additional amine groups.

Problems Of Nylon Dyeing

Baree or stripiness.

Poor wet-fastness in full, bright shades.

Inadequate photostability of the base fibre.

The poor light-fastness of copper phthalocyanine-based turquoise blue shades.

Environmental problems, such as those related to the use of compounds of heavy metals.

Bare

visual difference in colour depth, and possibly of hue, along the length of dyed nylon filaments in a fabric caused by physical and chemical variations in the polymer. It gives a continuous pattern of colour stripes seen in the course direction in circular knits, as warp streaks in warp knits Many acid dyes tend to accentuate barr, some dyes being more sensitive to chemical variations in the polymer filaments and others to physical variations.

Reason of Chemical Variations

Due to non-uniform distribution of the polymer amino groups, which causes variations in the rate of dye up-take and particularly the equilibrium dye content of the filaments. Polyamide formation is reversible and the amino group content may change as additional polycondcnsation or hydrolysis occur when the nylon is at high temperatures during processes such as heat setting or texturing.

The number and distribution of amino groups may also vary because of their oxidation during processing.

Reason of Physical Variations

01.Due to variations in the
degree

of polymer orientation degree of polymer crystallinity.

02.Uneven treatment in processes as

texturising, fabric heat setting, filament tensions filament drawing

Solution of the problem BARR

Barre from physical variations in filaments can be minimised by using levelling acid dyes, or by promoting dye migration by dyeing above 100C. Pretreating the goods with an anionic blocking agent before the acid dyes are in the dyebath. Because of their good migration properties on nylon, disperse dyes, such as CI Disperse Blue 3, will uniformly cover most barre.

Pressure dyeing, dyeing with added benzyl alcohol, and dyeing with additions of, levelling agents, all minimise barre.

Pretreatment of the nylon material in a blank dyebath at a temperature around 85-90 C, above the prevailing dyeing transition temperature, is also beneficial.

Under these conditions, the movement of polymer chain segments allows the relaxation of tensions. A new dyeing process for nylon, developed by Du Pont and called the 'Infinity' process, uses this principle.

Running the goods in a blank bath containing the appropriate weak acid, at a constant temperature above the prevailing dyeing transition temperature, usually in the range 75-90 C. The dye solution slowly runs into the bath over about 45 min using a metering pump.
The conditions are such that the dye strike is so rapid that the actual concentration of dye in the bath is essentially zero during the entire dyeing operation. The name of the process comes from the condition of infinite exhaustion that prevails throughout dyeing. [01][25][26]

Concluding Comment

There is evidence that nylon dyeing processes are being reevaluated due to the demands of achieving better levelness and wet-fastness properties. It is also important because of the perceived environmental problems with pre-metallised dyes.

How to achieve high light-fastness dyeings from non-metallised dyes is an issue which researchers will have to address.
It is also interesting to reflect that despite its better textile properties, in terms of recovery from deformation, nylon has lost out in the automotive upholstery market, mainly to polyester. To regain this market, new research is undoubtedly required to improve the light-fastness of dyeings and the photostability of the base polymer.

Contributor Name
Md.Sazzad Bin Wahid
Md.Wakil Hasan Md.Rakibul Hassan Md.Rejaul Hasan Md.Imon Khan

Roll Number
013
029 033 049 054