Problems Solving In Dyeing Of Cotton

Textile Material with Reactive Dyes

1.     Problem Solving with Reactive Dyes:

Reactive dyes are one of the most commonly used application class of dyes for
cotton materials, Two important aspects of reactive dyeing, namely dye
variables and system variables, are discussed in this section, along with
important characteristics of reactive dyeing such as exhaustion, migration and
leveling, fixation and colour yield, and washing off and fastness. A significant
portion of this section also deals with the problem of the reproducibility and
difficulties in obtaining right-first-time dyeing.
1. 使用活性染料解決問題：
活性染料是棉材料最常用的染料應用類別之一，本節討論活性染色的兩個重要
方面，即染料變量和系統變量，以及活性染色的重要特性，如吸盡、遷移和流
平性、固色性和得色性、洗去性和牢度。本節的很大一部分還涉及重現性問題
和獲得一次正確染色的困難。

Dye Variable in Reactive Dyeing

The major dye variables that affect reactive dyeing are dye chemistry,
substantivity, reactivity, diffusion coefficient and solubility. Each of these will
be briefly discussed below.
活性染色中的染料變量
影響活性染色的主要染料變量是染料化學、直接性、反應性、擴散係數和溶解
度。下面將簡要討論這些中的每一個。

Dye chemistry: 染料化學：

Reactive dyes have a wide variety in terms of their chemical structure. The two
most important components of a reactive dye are the chromophore and the
reactive group. The characteristics governed by the chromophore are colour
gamut, light fastness, chlorine/bleach fastness, solubility, affinity, and
diffusion. The chromophores of most of the reactive dyes are azo,
anthraquinone, or phthalocyanine. Azo dyes are dischargeable. Dis-azo dyes
have the disadvantage of being much more sensitive to reduction and many of
them are difficult to wash-off. 活性染料的化學結構多種多樣。活性染料的兩個
最重要的成分是髮色團和活性基團。髮色團控制的特性是色域、耐光性、耐氯 /
漂白牢度、溶解性、親和力和擴散。大多數活性染料的髮色團是偶氮、蒽醌或
酞菁。偶氮染料是可放電的。雙偶氮染料的缺點是對還原更敏感，而且其中許
多難以洗掉。

Anthraquinone dyes exhibit relatively low substantively and are easier to

wash-off. Most of them possess excellent fastness to light and to crease-
resistant finishes, but they are not dischargeable. Phthalocyanine dyes diffuse
slowly and are difficult to wash off. 蒽醌染料的顯著性相對較低，更容易洗掉。
它們中的大多數具有出色的耐光牢度和抗皺性完成，但它們不可排放。酞菁染
料擴散緩慢且難以洗掉。

Metal complex dyes containing copper possess rather dull hues, but show a
high degree of fastness to light and to crease-resistant finishes. Their
substantivity is fairly high; 1:2 complexes diffuse relatively slowly, so a longer
time is needed to wash-out unfixed dye completely. 含銅的金屬絡合染料具有
相當暗淡的色調，但對光和抗皺飾面具有高度的堅牢度。它們的實體性相當高；
1:2 配合物擴散較慢，因此需要較長時間才能完全洗掉未固色的染料。

The dye characteristics governed by the reactive group are reactivity, dye fibre
bond stability, efficiency of reaction with the fiber, and affinity. Dyeing
conditions, especially the alkali requirement and temperature as well as the
use of salt also depend on the type of reactive group. Dyes based on s-triazine
do not have good wet fastness properties in acidic media and, due to their high
substantivity, have poor wash-off properties. 受反應性基團控制的染料特性是
反應性、染料纖維鍵穩定性、與纖維的反應效率和親和力。染色條件，尤其是
鹼要求和溫度以及鹽的使用也取決於反應基團的類型。基於 s-三嗪的染料在酸
性介質中不具有良好的濕牢度特性，並且由於它們的高直接性，具有較差的洗
去特性。

Similarly, dyes having a vinyl sulphone reactive system have poor alkaline
fastness. The chemical bond between the vinyl sulphone and the cellulosic
fibre is very stable to acid hydrolysis. 類似地，具有乙烯基砜反應體系的染料具
有較差的鹼性牢度。乙烯基砜和纖維素纖維之間的化學鍵對酸水解非常穩定。

The substantivity of hydrolysed byproducts of vinyl sulphone is low, so

washing off is easy. Monochloro triazines have good fastness to light,
perspiration and chlorine. The turquoise reactive dye shows an optimum
dyeing temperature that is generally about 20C higher than that of other dyes
with the same reactive group. The fluorotriazine groups form linkages with
cellulose that are stable to alkaline media. 乙烯基砜水解副產物的直接性低，
容易洗掉。一氯三嗪對光、汗和氯具有良好的牢度。綠松石活性染料的最佳染
色溫度通常比具有相同活性基團的其他染料高約 20℃。氟三嗪基團與纖維素形
成對鹼性介質穩定的鍵。

Reactive dyes of dichloroquinoxaline, monochlorotriazine and monofluo

triazine types show a lower resistance tendency to peroxide washing and dye-
fibre bond stability. A lower sensitivity to changes in dyeing conditions
(particularly temperature) is the most important characteristic feature of the
monochlorotriazine-vinyl sulphone hetero bi-functional dyes. Dyeing
properties of some important reactive groups have been discussed in detail by
various authors.
乙烯基砜水解副產物的直接性低，容易洗掉。一氯三嗪對光、汗和氯具有良好
的牢度。綠松石活性染料的最佳染色溫度通常比具有相同活性基團的其他染料
高約 20℃。氟三嗪基團與纖維素形成對鹼性介質穩定的鍵。
二氯喹喔啉、一氯三嗪和單氟三嗪類型的活性染料對過氧化物洗滌的耐受性和
染料-纖維結合穩定性較低。對染色條件（尤其是溫度）變化的敏感性較低是一
氯三嗪-乙烯基砜雜雙功能染料最重要的特性。一些重要的反應基團的染色特性
已被多位作者詳細討論過。

Substantivity:

Substantivity is more dependent on the chromophore as compared to the

reactive system. A higher dye substantivity may result in a lower dye
solubility, a higher primary exhaustion, a higher reaction rate for a given
reactivity, a higher efficiency of fixation, a lower diffusion coefficient, less
sensitivity of dye to the variation in processing conditions such as temperature
and pH, less diffusion, migration and levelness, a higher risk of unlevel
dyeing, and more difficult removal of unfixed dye. Substantivity is the best
measure of the ability of a dye to cover dead or immature fibres.

Covering power is best when the substantivity is either high or very low. An
increase in the dye substantivity may be affected by lower concentration of the
dye, higher concentration of electrolyte, lower temperature, higher pH (up to
11) and lower liquor to goods ratio.
實體性：
與反應體系相比，直接性更依賴於生色團。較高的染料親和性可能導致較低的
染料溶解度、較高的初級吸盡度、較高的反應速率對於給定的反應性、較高的
固色效率、較低的擴散係數、染料對加工條件（如溫度）變化的敏感性較低和
pH 值，擴散、遷移和勻染性較差，染色不勻的風險較高，未固色染料更難去除。
直接性是染料覆蓋死纖維或未成熟纖維能力的最佳衡量標準。
當直接性高或非常低時，覆蓋力是最好的。染料直接性的增加可能受染料濃度
較低、電解質濃度較高、溫度較低、pH 值較高（高達 11）和液料比較低的影
響。

Reactivity:

High dye reactivity entails a lower dyeing time and a lower efficiency of
fixation. (To improve the efficiency of fixation by reducing dye reactivity
requires a longer dyeing time and is, therefore, less effective than an increase
in substantivity.) Also there is a wider range of temperature and pH over
which the dye can be applied. Reactivity of a dye can be modified by altering
the pH or temperature, or both. By a suitable adjustment of pH and
temperature, two dyes of intrinsically different reactivity may be made to react
at a similar rate.

反應性：
高染料反應性需要較短的染色時間和較低的固色效率。 （通過降低染料反應性
來提高固色效率需要更長的染色時間，因此不如增加直接性有效。）此外，還
可以使用更寬的溫度和 pH 值範圍，在此範圍內可以使用染料。染料的反應性
可以通過改變 pH 值或溫度或兩者來改變。通過適當調節 pH 值和溫度，可以使
兩種本質上不同反應性的染料以相似的速率反應。

Diffusion coefficient:

Dyes with higher diffusion-coefficients usually result in better leveling and

more rapid dyeing. Diffusion is hindered by the dye that has reacted with the
fibre and the absorption of active dye is restrained by the presence of
hydrolysed dye. Different types of dyes have different diffusion characteristics.
For example, the order of decreasing diffusion is: unmetallised dyes, 1:1
metal-complex dyes, 1:2 metal complex dyes; phthalocyanine dyes. An
increase in the diffusion is affected by increasing temperature, decreasing
electrolyte concentration, adding urea in the bath and using dyes of low
substantivity.
擴散係數：
具有較高擴散係數的染料通常會產生更好的勻染性和更快的染色。與纖維反應
的染料阻礙了擴散，水解染料的存在抑制了活性染料的吸收。不同類型的染料
具有不同的擴散特性。例如，擴散遞減的順序是：非金屬化染料、 1:1 金屬絡合
物染料、1:2 金屬絡合物染料；酞菁染料。擴散的增加受溫度升高、電解質濃度
降低、在浴中添加尿素和使用低親和性染料的影響

Solubility:

Dyes of better solubility can diffuse easily and rapidly into the fibres, resulting
in better migration and levelling. An increase in dye solubility may be affected
by increasing the temperature, adding urea and decreasing the use of
electrolytes. 溶解性更好的染料可以輕鬆快速地擴散到纖維中，從而實現更好的
遷移和流平。染料溶解度的增加可能會受到影響
通過提高溫度、添加尿素和減少電解質的使用。

1.     System Variables in reactive Dyeing

Temperature:

A higher temperature in dyeing with reactive dyes results in a higher rate of

dyeing, lower colour yield, better dye penetration, rapid diffusion, better
levelling, easier shading, a higher risk of dye hydrolysis, and lower
substantivity. Raising the temperature appears to result in an opening-up of
the cellulose structure, increasing the accessibility of cellulose hydroxyls,
enhancing the mobility as well as the reactivity of dye molecules and
overcoming the activation energy barrier of the dyeing process, thereby
increasing the level of molecular activity of the dye-fibre system as well as dye-
fibre interaction. A comparison of hot and cold reactive dyes has been given in
along with some technical advantages of hot reactive dyes over cold reactive
dyes.
溫度：
用活性染料染色時溫度越高，染色率越高，得色率越低，染料滲透性越好，擴
散速度越快，勻染性越好，著色更容易，染料水解風險越高，直接性越低。升
高溫度似乎導致纖維素結構的開放，增加了纖維素羥基的可及性，增強了染料
分子的流動性和反應性，克服了染色過程的活化能壘，從而提高了染色的水平。
染料-纖維繫統的分子活性以及染料-纖維相互作用。已經給出了熱活性染料和
冷活性染料的比較以及熱活性染料相對於冷活性染料的一些技術優勢。
pH:

The intial pH of the dyebath will be lower at the end of dyeing by one half to a
whole unit, indicating that some alkali has been used up during dyeing. The
cellulosic fibre is responsible for some of this reduction, while a smaller part is
used by the dyestuff as it hydrolyses. In discussing the effect of pH, account
must be taken of the internal pH of the fibre as well as the external pH of the
solutior. The internal pH is always lower than the external pH of the solution.

As the electrolyte content of the bath is increased, the internal pH tends to

equal the external pH. Since the decomposition reaction is entirely in the
external solution, the higher external pH favours decomposition of the dye
rather than reaction with the fibre. pH influences primarily the concentration
of the cellusate sites on the fibre. It also influences the hydroxyl ion
concentration in the bath and in the fibre. Raising the pH value by 1 unit
corresponds to a temperature rise of 20oG. The dyeing rate is best improved
by raising the dyeing temperature once a pH of 11-12 is reached. Further
increase in pH will reduce the reaction rate as well as the efficiency of
fixation. Different types of alkalis, such as caustic soda, soda ash, sodium
silicate or a combination of these alkalis, are used in order to attain the
required dyeing pH. The choice of alkali usually depends upon the dye used,
the dyeing method as well as other economic and technical factors.
酸鹼度：
染色結束時染浴的初始 pH 值會降低二分之一至整個單位，這表明染色過程中已
經消耗了一些鹼。纖維素纖維負責部分還原，而染料水解時會使用較小的部分。
在討論 pH 值的影響時，必須考慮纖維的內部 pH 值以及溶液的外部 pH 值。內
部 pH 值始終低於溶液的外部 pH 值。
隨著電解液中電解質含量的增加，內部 pH 值趨於等於外部 pH 值。由於分解反
應完全在外部溶液中進行，較高的外部 pH 值有利於染料的分解，而不是與纖
維反應。 pH 值主要影響纖維上纖維素位點的濃度。它還影響浴液和纖維中的
氫氧根離子濃度。 pH 值每升高 1 個單位，對應的溫度升高 20oG。一旦達到
11-12 的 pH 值，通過提高染色溫度來最好地提高染色率。 pH 值的進一步增加
將降低反應速率以及固定效率。使用不同類型的鹼，例如苛性鈉、純鹼、矽酸
鈉或這些鹼的組合，以達到所需的染色 pH 值。鹼的選擇通常取決於所使用的
染料、染色方法以及其他經濟和技術因素。

Electrolyte:

The addition of electrolyte results in an increase in the rate and extent of

exhaustion, increase in dye aggregation and a decrease in diffusion. The
electrolyte efficiency increases in the order: KGI < Na2S04 < NaG!. There may
be impurities present in the salt to be used, such as calcium sulphate,
magnesium sulphate, iron, copper and alkalinity, that can be a source of many
dyeing problems. 電解質：
電解質的添加導致耗盡的速率和程度的增加、染料聚集的增加和擴散的減少。
電解液效率按以下順序增加：KGI < Na2SO4 < NaG!。要使用的鹽中可能存在雜質，
例如硫酸鈣、硫酸鎂、鐵、銅和鹼度，它們可能是許多染色問題的根源。

Liquor ratio:

At lower liquor ratios, Diffusion coefficient: Dyes with be lower at the end of
the dyeing by there is a higher exhaustion and higher exhaustion and higher
color strength. An increase in colour strength may be attributed to greater
availability of dye active species in the vicinity of the cellulose macro
molecules, at lower liquor ratio. Surfactants and other auxiliaries: It is
possible to enhance dye uptake on cellulosic fibres with the aid of suitable
surfactants. Amongst all the systems, the highest dye uptake is obtained with
anionic surfactants. 在較低浴比下，擴散係數：染料在染色結束時越低，吸盡
度越高，吸盡度越高，色強度越高。顏色強度的增加可能歸因於在較低浴比下
纖維素大分子附近染料活性物質的可用性更高。表面活性劑和其他助劑：借助
合適的表面活性劑，可以提高纖維素纖維的上染率。在所有系統中，陰離子表
面活性劑的上染率最高。
Non-ionic surfactants may result in a decrease in dye exhaustion and colour
yield, and a change in shade. Some non-ionic surfactants may slow down the
dye hydrolysis. Triethanolamine (TEA) is known to enhance colour strength
by enhancing the swell ability and accessibility of the cellulose structure. It
may also modify the state of the dye, thereby enhancing its reactivity and
increasing the extent of covalent dye fixation. 非離子表面活性劑可能會導致染
料吸盡和顏色產量下降，以及色調變化。一些非離子表面活性劑可能會減慢染
料水解。眾所周知，三乙醇胺 (TEA) 可通過增強纖維素結構的溶脹能力和可接
近性來增強顏色強度。它還可以改變染料的狀態，從而增強其反應性並增加共
價染料固定的程度。