Reactive dyeing of silk using commercial acid dyes based on a three‐component Mannich‐type reaction

Acid dyes are employed for commercially dyeing silk, which results in ionic bonds between the silk fibroin and the dye. This generally leads to low wet fastness properties for dyed silk fabrics. In this work, three commercial acid dyes with aromatic primary amine structures were selected to dye silk using a Mannich‐type reaction, resulting in improved wet fastness of dyed silk by forming covalent bonds between silk fibroin and dye. The Mannich‐type reactive dyeing was applied to silk fabrics at both 30 and 90°C in trials. Dyeing at 90°C can shorten the dyeing time compared with dyeing at 30°C, even although dye exhaustion and relative fixation at 90°C were a little lower. The dyeing process was optimised when the dyeing temperature was 90°C, dyebath pH 4, dye‐to‐formaldehyde ratio 1:30 and holding dyeing time 60 minutes. The results showed that the dye exhaustion on silk fabrics for the three aromatic primary amine‐containing acid dyes exceeded 94% and their relative fixation was over 80%. Their washing and rubbing fastness reached grade 4 or higher. Hence, the colour fastness properties of dyed silk fabrics using the Mannich‐type reactive dyeing method is superior to the conventional acid dyeing method using the same aromatic primary amine‐containing acid dyes. The Mannich‐type reactive dyeing for silk fabrics at 90°C can be developed into a novel and rapid reactive dyeing method, promising an effective dyeing process with excellent colour fastness.     

The accelerating effect of a small cationic quaternary ammonium compound and the adsorption kinetics in the dyeing of silk with reactive dyes

In order to develop an eco‐friendly method for silk reactive dyeing that uses a lower accelerant dosage to achieve a higher dye fixation, hexyl dimethyl octyl ammonium chloride was synthesised as an accelerant for the dyeing of silk with reactive dyes. The accelerating effect, corresponding adsorption kinetics, and interaction mechanisms among hexyl dimethyl octyl ammonium chloride, reactive dyes, and silk were investigated. At hexyl dimethyl octyl ammonium chloride concentrations of 10.8–14.4 mm , the dye fixations for three reactive dyes were much higher than those achieved with sodium sulfate, even though the required dosages of hexyl dimethyl octyl ammonium chloride were 30–40 times lower than those of sodium sulfate. The wash fastness, rub fastness, light fastness, K/S, and colour difference values after dyeing with hexyl dimethyl octyl ammonium chloride were similar to those obtained using sodium sulfate, and silk can be dyed uniformly. The adsorption kinetics followed a second‐order kinetic model. The activation energies of surface adsorption for the three reactive dyes were lower than those of sodium sulfate. The high fixation of reactive dyestuffs and the low required dosage of hexyl dimethyl octyl ammonium chloride demonstrate that the use of this new accelerant provides a novel, highly efficient method for silk dyeing. A possible acceleration mechanism of hexyl dimethyl octyl ammonium chloride for reactive dyes adsorbed on the surface of silk was proposed, based on a series of activation parameters of the adsorption process.     

活性染料用于拉细羊毛染色的研究

研究了四类活性染料染拉细羊毛的工艺条件和十二个染色配方。与媒介染料相比，用活性染料对拉细羊毛染色可获得更好的效果。染料的溶解度、匀染性、上色率、固色率均好于媒介染料，颜色的批差小。研究结果表明：除煮呢沾色牢度外，染色羊毛的各项牢度均优于媒介染料。     

Synthesis and dyeing properties of polyvinylamine dyes for cotton

Novel polyvinylamine dyes were designed and synthesised from poly(N‐vinylformamide‐co‐vinylamine) and reactive dyes, then used to dye cotton fibres by the dip‐pad‐steam process, with the dyeing methods being examined in detail. Each polyvinylamine dye was fixed to cotton without a crosslinking agent through covalent bonds formed between the reactive group of the dye and the cotton fibres. A fixation of 99% was achieved, with grades of 4 and 4‐5 wash and dry‐rub fastness, respectively.     

Foam properties and application in dyeing cotton fabrics with reactive dyes

The foam dyeing of cotton fabric with CI Reactive Red 120 has been studied as a low‐add‐on technology. The foamability of different types of foaming agent and the stability of foam stabilisers were compared. Factors influencing foam dyeing, including wet pick‐up, fixation agent, foam stabiliser, and blow ratio, were evaluated by colour strength and dye fixation rate. Wet pick‐up, fixation agent, and foam stabiliser were found to be the main factors in the foam dyeing process. The comparative build‐up properties, dyeing properties, and total consumption between foam dyeing and conventional dyeing were assessed. The results indicate that, in foam dyeing, the dyestuff has a better build‐up property, the dyed fabric has excellent wash and rub fastness, and large amounts of water and energy are saved. Moreover, foam dyeing requires smaller dosages of chemical agents and reduces the difficulty of effluent treatment.     

Synthesis and application of KM‐type reactive dyes containing 2‐ethoxy‐4‐chloro‐s‐triazine

A new kind of hetero‐bifunctional reactive dye containing 2‐ethoxy‐4‐chloro‐s‐triazine, with better activity matching with β‐hydroxyethyl sulphone sulphate at a low fixation temperature, was successfully synthesised and characterised. An ethoxy group was designed to be introduced into triazine to increase the substantivity and the reactivity of the dyes. Thereby, the fixation of mono‐s‐chlorotriazine/hydroxyethyl sulphone sulphate (KM‐type) bifunctional reactive dyes on cotton was improved, and dyeing under mild conditions with high fixation was realised. Nineteen dyes with orange, red and blue colours were synthesised and characterised by UV‐Vis and infrared spectroscopy and mass spectrometry. Synthesised dyes were dyed at 60, 75 and 90°C, respectively. Exhaustion and reactivity for all of the ethoxy‐containing KM‐type dyes was over 90% at the optimal temperature, and fixation was over 87%, which was higher than the ethoxy‐free comparative dyes. The optimal fixation temperature of ethoxy‐containing dyes was initially reduced to 75°C, and then to 60°C. Compared with comparative dyes, the wash fastness and light fastness were basically unchanged, and the wet rub fastness of the H‐acid series was reduced by one grade.     

Synthesis,spectral and dyeing properties of phenylazopyrazolone‐containing acylamide disperse dyes designed for poly(lactic acid)

A series of phenylazopyrazolone disperse dyes containing an acylamide moiety were synthesised from carboxyl‐containing acid dyes via chlorination and amidation with different sorts of amines. The structures of these new dyes were confirmed by Fourier Transform–infrared, proton nuclear magnetic resonance, mass spectroscopy and elemental analysis. Their solvatochromic properties in different solvents were also investigated and the absorbance spectra of the acylamide dyes in solution exhibited a red shift when dissolved in dimethylformamide, compared with acetone. Their dyeing behaviour, including dye sorption, colour build‐up and colour fastness properties on poly(lactic acid) fibres, was also determined, whereupon it was found that the tertiary acylamide dyes simultaneously exhibited high dye sorption and satisfactory colour build‐up and fastness properties on the poly(lactic acid) fabric.     

Synthesis and application to cellulose of reactive dye precursor of anti‐bacterial N‐halamine

To achieve textile dyeing and functional finishing in one process, a bleach‐resistant reactive dye precursor to anti‐bacterial N‐halamine was synthesised by reacting a type of dichlorotriazine reactive dye with 4‐amino‐2,2,6,6‐tetramethylpiperidine. The synthesised compound, which can be transformed to an N‐halamine molecule by exposure to dilute bleach solution, was used to dye cotton fabrics. After exposure to a dilute sodium hypochlorite solution, dyed cotton fabrics showed excellent anti‐bacterial properties against Staphylococcus aureus and Escherichia coli O157:H7, facilitating a ca. 6‐log reduction in bacteria within a short period of contact. Compared with the dichlorotriazine reactive dye, the reactive dye precursor demonstrated comparable dyeing properties including exhaustion and fixation values. No differences in rub fastness, wash fastness or bleach fastness were detected between fabrics dyed with, respectively, dichlorotriazine reactive dye and the reactive dye precursor to N‐halamine.     

Deep‐coloured polyester/cotton blends with low concentrations of polymethylol dyes by a one‐pass continuous dyeing process

An obvious limitation of the one‐pass continuous dyeing process for polyester/cotton blends is its inability to achieve deep colour depth, which is caused by the low dye fixation yields of commercial reactive dyes. In this study, the performances of polyester/cotton blends dyed with high‐fixation polymethylol dyes and disperse dyes were compared with those of polyester/cotton blends dyed with a mixture of reactive dyes and disperse dyes. Polymethylol dyes were observed to be suitable for dyeing polyester/cotton blends when used in low concentrations; the required concentrations of polymethylol dyes were only 23–58% of the concentrations of commercial reactive dyes required to reach a given colour level on polyester/cotton blends. The wash and crocking fastness of polyester/cotton blends dyed with polymethylol dyes were similar to those of polyester/cotton blends dyed with reactive dyes.     

活性染料对莲纤维的染色性能研究

为了了解活性染料对莲纤维的染色性能,采用单因素分析法,在改变温度、浴比、时间、元明粉浓度、纯碱浓度等工艺条件下,分别采用两种不同类型的活性染料对莲纤维进行染色,并测试其上染率、固色率、耐皂洗色牢度和耐汗渍色牢度。结果表明:活性大红X-3B上染莲纤维的最佳染色工艺为染色温度40℃,染液浴比1∶40,染色时间60 min,元明粉质量浓度20 g/L,纯碱质量浓度30 g/L;活性嫩黄X-7G上染莲纤维的最佳染色工艺为染色温度40℃,染液浴比1∶50,染色时间60 min,元明粉质量浓度10 g/L,纯碱质量浓度20 g/L;活性染料耐皂洗色牢度和耐汗渍色牢度都在3级以上。     

Improving the environmental and economic aspects of cotton dyeing using a cationised cotton†

One approach to improve the affinity of anionic dyes for cotton is to add cationic dye sites to the fibre. The dyeing behaviour of cotton that had been rendered cationic by reaction with 2,3‐epoxypropyltrimethylammonium chloride was examined. Dye yields and fastness properties are reported for a number of direct, reactive and acid dyes with the modified fibre. Excellent dye yields and colour fastness properties were obtained without the use of electrolytes, multiple rinsings or fixation agents which are normally employed in cotton dyeing.     

Innovation and application of dyes with high fixation

Reactive dyes are the main species for cotton dyeing due to their wide range of hue, satisfactory color fastness and facile application method. Aiming at increasing fixation on cotton fibers, benzimidazolone yellow reactive dyes, sulfonamide red reactive dyes and anthraquinone azo blue reactive dyes are designed. The preparation, characterization and application properties of these dyes with high fixation are introduced in detail. In order to achieve dye fixation to near 100%, macromolecular cro...     

Dyeing of N-modified viscose rayon fibres with reactive dyes

Modified viscose rayon fibres were produced by incorporation of different doses of a polydiallyldimethylammonium chloride based additive in the viscose dope prior to spinning. On dyeing the modified fibres with different reactive dyes, excellent dye exhaustion and total dye fixation above 90% were obtained without the use of electrolyte and with low salt concentration. Exhaustion and total dye fixation showed an exponential relationship. The wash fastness properties of the dyed fibres were excellent and the light fastness showed a slight drop in the modified fibres. The presence of the amino groups along with low density and crystallinity of the modified fibres may be responsible for the enhanced dyeability.     

Fixation of reactive dyes using radio-frequency energy

Radio-frequency (r.f.) energy has been used to increase the fixation rate of reactive dyes on cotton fabric in pad-batch dyeing. A parallel-plate r.f. applicator was used to heat batches of fabric containing reactive dye formulations. The time required for fixation of the dyes was reduced from several hours to a few minutes by heating the fabric in the radio-frequency field. Reactive dyes incorporating three different types of reactive groups, vinylsulphone, nicotinic acid, and mixed vinylsulphone/ monochlorotriazine were studied and found to be applicable using the hot pad-batch method. The colour yield and wash fastness of dyeings with the vinylsulphone/monochlorotriazine bifunctional dyes using r.f.-assisted fixation was equal or superior to those of dyeings performed by conventional cold pad-batch dyeing methods.     

Synthesis of methine dyes derived from indol‐2‐ones and their dyeability on polyester fibres

Three series of methine dyes were synthesised by the condensation of indol‐2‐ones with aryl acroleins. The structures of these dyes were confirmed by ¹H nuclear magnetic resonance spectroscopy, infrared spectrometry and elemental analysis. The ultraviolet‐visible absorption spectra of the dyes were examined in different solvents. The maximum absorption wavelength ranged from 386 to 495 nm. The dyes were applied to polyester fibres, and the colour gamut and dyeing properties were investigated. Results showed that the dye uptake (percentage exhaustion) was 86.9–92.0%, with the hue changing from yellow to red. The rubbing fastness, wash fastness, and sublimation fastness were between 4 and 5.     

Treatment of cellulose with cationic,nucleophilic polymers to enable reactive dyeing at neutral pH without electrolyte addition

Reactive dyeing of cotton requires very high concentrations of salt, which pollutes freshwater courses. The dyeing effluent is highly colored as a result of high levels of hydrolysis of the dye, and high volumes of water are used in the wash‐off process to remove the hydrolyzed dye in order to achieve the excellent wash‐fastness levels expected. A substantive cationic, nucleophilic polymer was applied to cotton as a pretreatment agent prior to dyeing. This enabled salt and alkali to be completely eliminated from the dyeing process, significantly reducing the duration of the dyeing process and requiring less than 50% of the volume of water compared with those of the standard reactive dyeing processes. Dyeings secured using the pretreatment method required one simple washing stage to give wash‐fastness values equal to those observed for the standard reactive dyeings that required several wash‐off stages. The color strength of the pretreated dyeing was also slightly higher than that of the standard dyeings, and this was attributable to a reduction in dye hydrolysis and hence a higher fixation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1026–1031, 2003     

Pretreatment of cotton with poly(vinylamine chloride) for salt-free dyeing with reactive dyes

Poly(vinylamine chloride) has been investigated as a pretreatment for the salt-free dyeing of cotton with reactive dyes. Dye fixation was found to be much higher than by conventional dyeing without pretreatment, even in the presence of a large amount of salt. The influence of pretreatment conditions on dye fixation, such as pad–bake variables and the concentration of poly(vinylamine chloride), has been studied. The dyeing behaviour of CI Reactive Red 2 on pretreated cotton was examined and found to follow a Langmuir-type adsorption curve. Dyed cotton pretreated with poly(vinylamine chloride) showed excellent wash fastness and good rub fastness. It is concluded that poly(vinylamine chloride) is effective as a pretreatment for salt-free dyeing with reactive dyes.     

Synthesis and properties of poly(styrene-co-maleic acid) macromolecular reactive dyes

To obtain a new type of macromolecular reactive dye with high fixation and good light fastness, poly(styrene-co-maleic acid) was synthesised by co-polymerisation of styrene and maleic anhydride, then, through nitration, reduction, diazotisation and coupling reaction, novel macromolecular reactive dyes were prepared with a solubility greater than 60 g/L. The dyes were used to dye cotton fabrics; the results showed their fixation was more than 92%, and both the rub and wash fastness of the dyes were good. The light fastness of the red and blue dyes with the ethoxy group on melamine was grade 4, and for the yellow dye reached grade 5. The poly(styrene-co-maleic acid) macromolecular reactive dyes exhibit very good application prospects in practice.     

Dyeing and fastness properties of polyamide fabrics using some acid‐based monoazo disperse dyes

A series of monoazo disperse dyes derived from naphthalimide containing butyric acid has been applied on polyamide fabrics. The build up and dyeing properties of these dyes such as leveling property, wash, light, perspiration for alkaline and acidic conditions, and rubbing fastnesses on polyamide fabrics have been investigated. The results showed that the applied dyes are capable of producing red to bluish red hues on polyamide fabrics. Because of the presence of both carboxylic acid and hydroxyl groups on the molecular structure of Dye 3, it showed desired and more strength in respect to other used dyes. Comparing the build up of these dyes to commercial dyes such as disperse red 60 and disperse red 73 revealed that most of the used dyes have higher build up in comparison to the commercial ones. Measurement of fastness properties of dyed samples indicated that they have good wash (4–5), rubbing (4), perspiration (4–5), and heat fastnesses (4–5) and they possess less than moderate light fastness (3–4) on polyamide fabrics. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Continuous dyeing of cationised cotton with reactive dyes

Cotton fabrics pretreated with cationic starch have been dyed with reactive dyes by a continuous dyeing method and the pretreatment conditions influencing dyeability of the treated cotton investigated. Cationised cotton has been found to give level dyeing without the presence of salt and dye fixation is improved compared with untreated cotton. The dyeings show good wash and rub fastness.