Properties of Novel Reactive Transfer Printing of Silk

LI Qing ( )，WANG Yong ( )，XING Tie-ling ()，CHEN Guo-qiang ()*

1 National Engineering Laboratory for Modern Silk，College of Textile and Clothing Engineering，Soochow University，Suzhou 215123，China

2 Changzhou Hanyuan New Printing Co.,Ltd.，Changzhou 213000，China

Introduction

Textile printing is the most versatile and important method endowing fabrics or garments with colored patterns[1].Most textile prints are produced via traditional printing approaches，namely screen printing and roller (gravure) printing[2].Nevertheless，transfer printing，as a kind of technology combining textile printing with carrier printing，is concerned increasingly due to its gradual elevated market competitiveness.Moreover，comparing with traditional methods，transfer printing can offer a more flexible production mode，faster production speed，and higher-quality pattern[3].

The well-known transfer printing，heat transfer printing，is a process of the sublimation and diffusion of volatile disperse dyes when the fabric is in contact with the transfer paper and is heated to the temperature over 200 ℃[4- 6].This process gains a rapid acceptance in the market as a means of printing polyester fabric.However，the attempt of widening its application in natural fiber fabrics has been limited because disperse dyes lack the affinity toward natural fibers.In contrast，reactive dyes can react with natural fibers forming covalent bonds and have excellent washing fastness[7].Consequently，the reactive transfer printing has a broad potential application，among which the wet transfer printing receives widespread attentions[8-13].As the name implies the fabric must be pre-wetted in a determined paste before printing.Since the fabric humidity has a great influence on the dissolution，migration，and fixation of dyes，the moisture content is quite crucial to the effect of printing.However，a uniform and appropriate humidity is difficult to control due to different fabric structure and external environment.

To avoid the control problem of the humidity，as a kind of novel transfer printing method，the dry transfer printing is investigated in this paper.As the wet pretreatment is omitted in the process，the transfer of dye crucially depends on the performance of transfer printing paper.

In this study，the paste mainly containing high-substituted hydroxypropyl cellulose (H-HPC) and carboxymethyl cellulose (CMC) was coated to prepare the special transfer paper (Scheme 1).One of the most important natural protein fiber fabrics，silk fabric，was trialed as the printing substrate.The tentative mechanism of dye transfer and fixation was stated first.The impacts of each component in the paste on the printing properties expressed as color yield of the prints and dye penetration were discussed in detail.Besides，the serviceability of the printed silk in terms of the color fastness，clarity，and handle were evaluated.This work aims at providing a better understanding of the impact factors on the printing properties，and obtaining the silk prints with high color depth and good serviceability.

Scheme 1 Structures of H-HPC and CMC

1 Experiment

1.1 Materials

Low viscosity H-HPC (substitution degree 2.5) and medium viscosity CMC (substitution degree 1.05) were the industrial products，and were supplied by Changzhou Hanyuan New Printing Co.，Ltd.(China).Three commercial inks based on bi-functional reactive dye，namely Everjet?Magenta RT-E5，Yellow RT-E5，and Cyan RT-E5，were generously provided by Everlight Chemical Industrial Co.，Ltd.(Taiwan，China).

Other chemical additives，sodium carbonate (Na2CO3)，sodium bicarbonate (NaHCO3)，trichloroacetic acid (CCl3COOH)，and dicyandiamide (C2H4N4) were of analytical reagent grade; sodium trichloroacetate (CCl3COONa)，urea (H2NCONH2)，physical sorbent nano-silica (SiO2)，and soap flakes were of commercial grade.SiO2can accelerate the drying of ink and improve the paper smoothness[14-15].

And 100% degummed and bleached plain woven silk fabric (44 g/m2) and the original paper (40 g/m2) were supplied by Suzhou Huasi Silk Printing & Dyeing Co.，Ltd.(China) and Changzhou Hanyuan New Printing Co.，Ltd.(China)，respectively.

1.2 Preparation of the paste

H-HPC，CMC，and other chemical additives were successively added into deionized water at ambient temperature according to certain recipes，stirred with a mixer for 30 min，and left in a refrigerator for 2-4 h to attain a fully swollen paste.

1.3 Preparation of the transfer paper

The transfer paper was prepared by coating the paste using a coating and baking machine (Mathis，Type LTE-S,Switzerland) under the following conditions: coating speed of 1 m/min，coating thickness of 0.4 mm，baking temperature of 65 ℃，baking time of 20 min，and fan speed of 2 000 r/min.

1.4 Process of the transfer printing

The whole transfer printing process is illustrated in Fig.1.The detail conditions about the major steps are described as follows.

Fig.1 Whole transfer printing process

As shown in Fig.1: (1) the reactive dye ink is printed on the transfer paper using an ink-jet printer equipped with a continuous ink supply system (Epson stylus photo，Type R230,Japan) to obtain the pattern with single color; (2) the hot-press process is performed by a transfer calender (Rapid，Type LC-250,China) at 115 ℃，with pressure of 3 MPa and roller speed of 10 r/min; (3) the fixation is carried out in a steaming machine (Mathis,Switzerland) adjusted to the saturation steam mode at 102 ℃ for 10 min; (4) the transfer paper is peeled off; (5) the silk prints are washed with cold water for 4 min，soaped at 90-95 ℃ for 5 min，and rinsed with cold water; (6) the printed silk fabric is obtained.

1.5 Methods of measurements

The color yield (K/Svalue) of the printed silk was measured with an UltraScan PRO reflectance spectrophotometer (Hunter Associates Laboratory) using illuminant D65 and 10° standard observer.An average of four readings was calculated for each sample.The dye penetration (P) meaning the extent of dye diffusion in the fiber interior was determined using Eq.(1).

(1)

where (K/S)fand (K/S)bare the faceK/Svalue and backK/Svalue of the printed silk，respectively[16].

Coating quantity (C) on the transfer paper was determined using Eq.(2).All the samples had the same areas and were dried in an oven for over 2h.

(2)

whereW1andW0are the qualities of the unprinted transfer paper and blank paper，respectively.

The prints were washed according to GB/T 3921—2008 at 60 ℃ for 30 min using a soaping tester (Roaches，Type Washtec-P，England).The degree of color change was evaluated by ISO 105-A05 and the degree of color staining was evaluated by ISO 105-A04.Rubbing and daylight fastness of the prints were tested according to GB/T 3920—2008 and GB/T 8426—1998，respectively.

The handle of prints were assessed by the surface property which was measured using an automatic surface tester (KES FB- 4,Japan)[17]with test size 20 cm×20 cm.

2 Results and Discussion

2.1 Tentative mechanism of dye transfer and fixation

Hot-melt adhesive H-HPC can achieve a tight adhesion between silk fabric and transfer paper in the hot-press shown in Fig.1(b)[18-20].This adhesion indicates that the paste film carrying reactive dyes forms on the surface and superficial layer of the fabric.

During the steaming revealed in Fig.1(c)，the dry paste film begins to absorb and hold moisture from the saturation steam.Meantime，the highly aggregated dyes in the paste are dissolved and then able to transfer，indicating that the current paste film seems like a very concentrated miniature dyebath on the fiber surface.By the drive of the affinity between fiber and dye as well as the heated steam，the dyes are continuously released from the paste and diffuse into the silk.Once the dyes make contact with the dye sites on the fiber，the fixing reaction will arise immediately，meaning that the color patterns are firmly transferred onto the fabric.Whereas，partial dyes permeate into the paper interior or still remain in the paste，leading to some side reactions and decreasing the utilization ratio of dyes.

2.2 Effect of each component on the printing properties

2.2.1EffectofH-HPCcontent

Based on the above-stated mechanism，it can be known that the adhesion between the silk and transfer paper is the precondition of dye transfer，thus adhesive H-HPC as the most essential component in the paste plays a key role in the dye transfer.The content of H-HPC was varied in the range of 2.0%-4.5%.Other components were added according to the following recipes: CMC 0.7%，Na2CO31%，trichloroacetic acid (TCAA) 1%，urea 5%，dicyandiamide 0.5%，and SiO20.5%.The obtained results of color depth of the prints，dye penetration，and coating quantity are shown in Fig.2 (all the recipes are calculated by weight percentage).In this paper，the ink-jet printing was carried out using Everjet?Cyan RT-E5.

Fig.2 The effects of H-HPC content on face K/S value of the prints，dye penetration and coating quantity on the transfer paper

It is evidently seen in Fig.2 that，the increasing H-HPC content brings about an ascending coating quantity，as well as a gradual improvement in the faceK/Svalue of the prints.Because the more H-HPC coated on the transfer paper is，the higher adhesion extent will be，thereby being more conducive to the dye transfer.

Figure 2 also reveals that the penetration is improved by the increasing H-HPC，which is related to the ascending coating quantity.On one hand，the more coated paste with dyes is pressed into the fiber interior，contributing to a higher penetration.On the other hand，the more coated paste enhances the moisture absorption，thereby facilitating the swelling of fiber and diffusion of dyes.However，further increase in the H-HPC content，i.e.,beyond 3%，has a practically slight impact on theK/Svalue and penetration，and makes the separation of the transfer paper difficult.Therefore，H-HPC 3%，is used in the following experiments.

2.2.2EffectofCMCcontent

Although H-HPC possesses a certain viscosity suitable for the paper coating[18]and has been used as the printing thickener to maintain the pattern sharpness[21]，it cannot be used solely due to its special solubility.The swollen H-HPC occurs gel in the heated medium (over 50 ℃) along with a sharp decline in the paste viscosity[18].The viscosity is so low that the paste flows unduly during the drying of transfer paper，thereby resulting in an uneven or failing coating.Consequently，another printing thickener CMC[22-24]is admixed into H-HPC to retain a required viscosity.The content of CMC was varied in the range of 0.3%-1.3%.Other components were added according to the following recipes: H-HPC 3%，Na2CO31%，TCAA 1%，urea 5%，dicyandiamide 0.5%，and SiO20.5%.The obtained results of color depth of the prints，dye penetration，and coating quantity are shown in Fig.3.

As presented in Fig.3，with the modestly increasing CMC，both the coating quantity and dye penetration improve slightly.It further indicates that more coating quantity on the transfer paper is favorable to the enhancement of the penetration.

Fig.3 The effects of CMC content on face K/S value of the prints，dye penetration，and coating quantity on the transfer paper

As also shown in Fig.3，the increase in the CMC content brings about an obviously increasing color depth of the prints，while further increasing CMC，i.e.beyond 0.7%，has an adverse influence on the depth.This finding is most probably ascribed to the excessive CMC content.More dyes may be trapped in the CMC macromolecule and/or occur side reaction with CMC[25]，thereby declining the ratio of dye transfer.Considering the printing properties and a suitable viscosity for coating，CMC，0.7%，is used in the following experiments.

2.2.3Effectoftypesoffixingalkalineagent

The fixation of reactive dye on the silk fiber is usually carried out in a weak alkaline medium suitable for the formation of dye sites，mainly the free amino groups[26- 27]，thus fixing alkaline agent is another essential component in the paste.To choose the most appropriate fixing alkaline agent，conventional alkali Na2CO3and NaHCO3，as well as TCAA and sodium trichloroacetate (STCA)[28]，2%，were individually added into the paste.Other components were added according to the following recipes: H-HPC 3%，CMC 0.7%，urea 5%，dicyandiamide 0.5%，and SiO20.5%.The obtained results of color yield and dye penetration are shown in Fig.4.

Fig.4 The effects of different fixing alkaline agent on face K/S value of the prints and dye penetration

Figure 4 evidently shows that theK/Svalue still reaches to 10.7 in the absence of fixing alkaline agent.One reason is that a number of amino groups in the neutral medium can react with reactive dyes in virtue of the hot steam[29].The higher reactivity of bi-functional dye used is another reason.In contrast，the printed silk exhibits a deeper color after adding the fixing alkaline agent，and the highestK/Svalue is attained when using TCAA which has been applied in the reactive printing paste[30- 32].

TCAA gives an acid medium to the paste at ambient temperature due to its complete dissociation; whereas，the acid medium will gradually convert into alkaline (pH 8-9) after its decomposition at about 100 ℃，as illustrated in Scheme 2.That is to say，the transfer paper will present acidic until it is subject to steaming.Therefore，compared with the other fixing alkaline agents，reactive dyes nearly undergo no hydrolysis before steaming，which is the main cause of the deepest color obtained upon TCAA.

Scheme 2 Decomposition of TCAA at about 100 ℃

As also shown in Fig.4，different fixing alkaline agent has a slight impact on the penetration.Hence，TCAA is used as the fixing alkaline agent in the following experiments.

2.2.4EffectofTCAAcontent

To further discuss the effect of TCAA，its content was varied from 0.5% to 5.0%.Other components were added according to the following recipes: H-HPC 3%，CMC 0.7%，urea 5%，dicyandiamide 0.5%，and SiO20.5%.The obtained results of color depth and dye penetration are shown in Fig.5.

Fig.5 The effects of TCAA content on face K/S value of the prints and dye penetration

As shown in Fig.5，the increasing TCAA content up to 3% leads to a gradual increase in theK/Svalue.This is because the pH value during the printing is adjusted by TCAA and becomes more suitable for the dye uptake and fixation.Before steaming，the equilibrium shown in Scheme 3(a) will move to the left in the acid medium，leading to the dominant protonated amino groups，as the potential dye sites capable of attracting the anionic reactive dye by ionic bonding，which will increase the dye absorption into the fiber.During steaming，with the pH raising，the protonated amino groups gradually transform into NH2capable of covalently reacting with the reactive dye，thereby resulting in a higher fixation，as shown in Scheme 3(b)[32].

(a)

(b)

(c)

Scheme 3 Action mechanism of TCAA during the fixation between
silk fiber and reactive dyes

As also shown in Fig.5，further increasing TCAA content is accompanied with a slightly decreasingK/Svalue.The probable reason is that partial potential dye sites，i.e.,protonated amino groups，are occupied by TCAA anions，thereby restricting the dye anions of larger size to sites of lower substantivity[33]，as illustrated in Scheme 3(c).Besides，TCAA content has a slight influence on the penetration.Therefore，TCAA 3%，is used in the following experiments.

2.2.5Effectofureacontent

Both the highly concentrated dyes and the dry paste require sufficient dissolution to ensure the free migration of dyes during steaming process.At the same time，the fabric should be wetted and swollen to accelerate the diffusion of dyes.Therefore，urea as the common humectants is used to prepare the paste[34- 35].The content of urea was varied in the range of 0-9%.Other components were added according to the following recipes: H-HPC 3%，CMC 0.7%，TCAA 3%，dicyandiamide 0.5%，and SiO20.5%.The obtained results of color depth and dye penetration are shown in Fig.6.

Fig.6 The effects of urea content on face K/S value of the prints and dye penetration

As shown in Fig.6，the increasing urea content leads to an apparent improvement in the penetration，especially its content exceeds 5%，and theK/Svalue of the prints increases sharply when adding 1%-5% urea.These phenomena are attributed to the favorable influences of urea on the swell of the paste，as well as the dissolution，release，and diffusion of dyes[34- 35].

As also shown in Fig.6，further increasing urea，i.e.beyond 5%，contrarily leads to a decline in the color depth.Because the water content of the transfer paper increases simultaneously with the increasing urea，the more dyes permeate into the paper，the less dyes transfers into the fabric.In addition，when urea content is over 7%，the transfer paper will attract moisture excessively，resulting in an inconvenient use，especially when it is printed.Therefore，urea 5%，is used in the following experiments.

2.2.6Effectofdicyandiamidecontent

In several studies on reactive printing or dyeing，dicyandiamide is used as a type of urea alternatives owing to its hygroscopic function，which can decrease the urea dosage in the paste[36- 37].It also acts as the fixation activator since it can expand the fiber gap after combining with urea in co-dissolved form and improve the fixation after forming the intermediate complexes with reactive dyes[38-39].The content of dicyandiamide was varied in the range of 0-5.0%.Other components were added according to the following recipes: H-HPC 3%，CMC 0.7%，TCAA 3%，urea 5%，and SiO20.5%.The obtained results of color depth and dye penetration are shown in Fig.7.

Fig.7 The effects of dicyandiamide content on face K/S value of the prints and dye penetration

As shown in Fig.7，theK/Svalue changes slightly with the increasing dicyandiamide content，signifying that there is no obvious promotion in fixation after adding dicyandiamide.Probably because a higher fixation has already been gained in the presence of 5% urea and 3% TCAA.However，an increase in the penetration is quite remarkable when adding only 1% dicyandiamide，reflecting the positive influence of dicyandiamide on the penetration，which is the direct consequence of the highly swollen fiber structure.Meanwhile，the separation becomes easier when its content exceeds 3%，which is favorable to the practical operation.Consequently，dicyandiamide，3%，is used in the following experiments.

2.3 Evaluation of the serviceability of prints

According to the experiments’ results above，it can be concluded that a higher color yield has been gained when coating the paste containing 3% H-HPC，0.7% CMC，3% TCAA，5% urea，3% dicyandiamide，and 0.5% SiO2.In this section，the color fastness，clarity of patterns，and handle，as the most important serviceability of the printed silk，were evaluated based on the above recipes.Three dye inks，i.e.,

Everjet?Magenta RT-E5，Yellow RT-E5，and Cyan RT-E5，were used for the ink-jet printing.The assessment results of color fastness，clarity of patterns，and handle are presented as follows.

2.3.1Colorfastnessoftheprints

As shown in Table 1，the washing，rubbing，and daylight fastness of the printed silk all reach up to grade 3 or above，indicating a good or excellent color fastness，regardless of the reactive dyes used.Hence，it can be stated that a stable dye-fiber bond is achieved by the novel transfer printing method.

Table 1 Washing，rubbing，and daylight fastness of the printed silk

2.3.2Clarityofpatterns

To assess the clarity of patterns directly，the digital photos of the transfer paper and face silk prints with three different colors are shown in Fig.8.The pixel of the digital camera (Canon IXUS 80 IS) is 800.The thinnest lines can be seen evidently in Fig.8 (a)，verifying a clear pattern printed on the transfer paper.After steaming，the pattern on the separated transfer paper is still relatively clear (Fig.8 (b))，meaning that pattern can be well maintained during fixation.Furthermore，the printed silk also exhibits a clear design in Fig.8 (c).Consequently，it can be concluded that the clarity of pattern is good in the whole printing process，regardless of the reactive dyes used.This is mainly owing to H-HPC and CMC macromolecules can effectively restrict the migration of dyestuff in the desired area[24，40].

Fig.8 Digital photos of transfer paper and printed silk (a-transfer paper; b-separated transfer paper after steaming; c-washed printed silk; 1-Yellow; 2-Magenta; 3-Cyan)

2.3.3Handleofprints

The paste is inevitably adhered onto the fabric in the hot-press process，and the side products also deposit on the fabric during the steaming，which will result in a poor handle.Surface property of the fabric is employed to assess the prints’ handle，and the results of dynamic friction coefficient (MIU)，friction coefficient average deviation (MMD)，and surface roughness (SMD) are shown in Table 2.

Table 2 Surface property of the printed silk

MIU，MMD，and SMD of the fabric are smaller; the fabric handle will become smoother and softer.As shown in Table 2，MIU，MMD，and SMD of the washed prints are lower than those of the unwashed prints，and comparable with those of the unprinted original fabric，suggesting that the handle of the prints increases apparently after washing and nearly reaches to the level before printing.These results also prove that the paste has been almost totally removed from the fabric through a simple washing，regardless of the reactive dyes used.

3 Conclusions

The novel reactive silk transfer printing was studied，and the special transfer paper was prepared by coating the paste mainly containing hot-melt adhesive H-HPC and printing thickener CMC.Effects of each component in the paste on face color yield and dye penetration were investigated，and the prints’ serviceability in terms of color fastness，pattern sharpness，and handle was measured.The major results are concluded as follows.

Color yield of the prints is governed by the adhesive property of transfer paper and fixation efficiency of reactive dyes.The adhesive property depends on the H-HPC coated on the transfer paper，and the increasing H-HPC improves the color yield but makes a hard separation of the transfer paper.The fixation efficiency is affected by the CMC content，type of fixing alkaline agent and its content，hygroscopic extent of paste and fabric.The excessive CMC content declines the fixation.TCAA exhibits the highest fixation efficiency compared with Na2CO3，NaHCO3，and sodium trichloroacetate，and its content should be well controlled at 3.0%.Urea as the humectants enhances the color yield obviously，but its content ought to be lower than 5% to avoid excessive moisture absorption of the transfer paper.

Dye penetration is related to the coating quantity on the transfer paper，and the contents of urea and dicyandiamide.More coating quantity is favorable to the enhancement of penetration.Both urea and dicyandiamide improve the penetration markedly，especially when their contents exceed 5% and 1%，respectively.

The paste containing 3% H-HPC，0.7% CMC，3% TCAA，5% urea，3% dicyandiamide，and 0.5% SiO2is used to prepare the transfer paper.The obtained printed silk possesses a higher color yield，color fastness of grade 3 or above，clear printing pattern，and good handle.

The novel printing method realizes the reactive transfer printing of silk without wet pretreatment，and avoids the control problem of humidity，which is operated conveniently and has a wide potential application.

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