4 Tekstilec, 2025, Vol. 68(1), 4–13 | DOI: 10.14502/tekstilec.68.2024077 Petra Forte Tavčer University of Ljubljana, Faculty of Natural Sciences and Engineering, Aškerčeva 12, 1000 Ljubljana Digital Printing Knitted Fabrics made of Polyamide, Cotton and Blends thereof Digitalni tisk poliamida in mešanic bombaž-poliamid Original scientific article/Izvirni znanstveni članek Received/Prispelo 6–2024 • Accepted/Sprejeto 12–2024 Corresponding author/Korespondenčna avtorica: Prof. Dr. Petra Forte Tavčer E-mail: petra.forte@ntf.uni-lj.si ORCID iD: 0009-0006-3621-9014 Abstract Knitted fabrics with different compositions, i.e. 100% cotton (CO), 100% polyamide (PA), and a blend of 50% cotton and 50% polyamide (CO/PA), were digitally printed with reactive dyes. The cotton fabric was pretreated with a conventional alkaline solution of alginate thickener, sodium carbonate and urea. The polyamide fabric was pretreated with an acidic solution of galactomannan thickener. The CO/PA blend was pretreated once with the alginate and once with the galactomannan preparation. The aim of the study was to determine whether the proposed preparation is suitable for printing polyamide with reactive dyes and which preparation is more suit- able for printing the cotton-polyamide blend. The CIE L*a*b* colour values, the colour depth (K/S) and the dye penetration of the printed samples were compared. It was determined that under the same printing conditions, the highest colour depth was achieved on cotton, while a lower depth was recorded on polyamide. The colour depth on the cotton-polyamide blend was lower than on the two pure fabrics. For some colours, the colour depth was higher with the alginate thickener preparation, for others with the galactomannan thickener, so that no definitive preference for one preparation over the other can be given for printing blends. The colour fastness of the prints to dry rubbing (crock test), light and washing at 40 °C was acceptable for all samples. Keywords: digital printing, reactive dyes, polyamide, cotton, preparations Izvleček Pletivo z različno surovinsko sestavo: 100-odstotni bombaž (CO), 100-odstotni poliamid (PA) in mešanica 50 % bom- baža in 50 % poliamida (CO/PA) je bilo digitalno tiskano z reaktivnimi barvili. Bombažno blago je bilo pred tiskanjem impregnirano z alkalno raztopino alginatnega zgostila, natrijevega karbonata in sečnine. Poliamidno blago je bilo impregnirano s kislo raztopino galaktomananskega zgostila. Mešanica CO/PA je bila impregnirana ali z alginatno ali z galaktomanansko apreturo. Namen raziskave je bil ugotoviti, ali je predlagana apretura primerna za digital- no tiskanje poliamida z reaktivnimi barvili in katera apretura je bolj primerna za tiskanje mešanice iz bombaža in poliamida. Na vzorcih, potiskanih s cian, magenta, rumeno in črno, so bili izmerjeni CIE L*a*b* barvne vrednosti, globina barvnih tonov (K/S) in pretisk barvila na hrbtno stran blaga. Ugotovljeno je bilo, da se pri istih pogojih tiskanja dosežejo najvišje K/S vrednosti na bombažu in nižje na poliamidu. Globina barve na mešanicah je bila nižja kot na obeh čistih pletivih. Za nekatere barve so bile K/S-vrednosti višje ob impregnaciji z alginatnim zgostilom, za nekatere Content from this work may be used under the terms of the Creative Commons Attribution CC BY 4.0 licence (https://creativecommons.org/licenses/by/4.0/). Authors retain ownership of the copyright for their content, but allow anyone to download, reuse, reprint, modify, distribute and/or copy the content as long as the original authors and source are cited. No permission is required from the authors or the publisher. This journal does not charge APCs or submission charges. Digital Printing Knitted Fabrics made of Polyamide, Cotton and Blends thereof 5 z galaktomananskim zgostilom, tako da za nobeno apreturo ne moremo reči, da je primernejša za tiskanje mešanic bombaž/poliamid. Barvne obstojnosti tiskov na suho drgnjenje (crock test), svetlobo in pranje pri 40 °C so bile ustrezne pri vseh vzorcih. Ključne besede: digitalni tisk, reaktivna barvila, poliamid, bombaž, mešanica, impregnacija 1 Introduction covalently to the amino group of polyamide fibres (–NH2). Under acidic conditions, the protonation Digital printing is the latest, but already fully estab- of the amino groups in the polyamide increases the lished textile printing technology. Dyes in the form affinity of the anionic dyes to the polyamide. At high of tiny droplets of dye solutions (ink) are sprayed pH values, the polyamide is anionic and essentially onto the fabric through numerous micrometre-sized no fixation occurs due to electrostatic repulsion nozzles [1]. between the strongly anionic dye and the anionic Reactive, disperse, acid and pigment dyes in the fibre, although the concentration of –NH2 groups, form of ink are used for digital textile printing. The the active nucleophilic species that react with the dyes must match the textile substrate, bond physical- electrophilic groups of the dye, is high. The pH value ly and chemically with the fibres, fix sufficiently and is one of the key parameters influencing the degree have the required fastness properties. of exhaustion and thus the final fixation of reactive Reactive dyes are a group of dyes with brilliant dyes to polyamide [2]. The optimum pH value for shades and good fastness properties that chemically good prints has determined to be 4–5 [2–6]. bind to textile fibres. They are most commonly used The textile material to be printed must be pre- for printing on cellulose fibres and are also suitable pared accordingly before printing, and the dye must for printing on silk, wool and polyamide [2]. They be fixed, washed and dried after printing. Absorp- are anionic, as one or more sulphonate groups are tion and capillary forces in the fibres cause spreading bound to the dye molecule (dye−SO- 3). Reactive and deteriorate the contour quality. Therefore, the dyes can bind to the hydroxyl groups of cellulose via fabric must be impregnated with a thickening agent the reactive system and form covalent bonds under and suitable fixing agents before printing. The com- alkaline conditions, usually through nucleophilic position of the impregnating bath and the steaming bimolecular substitution or nucleophilic addition time have a significant impact on the adsorption and mechanisms [3]. Reactive dyes also react with water fixation of reactive dye on both materials, cotton [7, molecules, a process known as hydrolysis. The hy- 8] and polyamide [9]. drolysed dye is no longer reactive and can no longer For printing on cotton, low-viscosity alginate chemically bond with the fibres. It must be removed thickeners in low concentrations are used, in which from the fabric in subsequent treatments [1]. auxiliaries, oxidizing agents and alkalis are dissolved Polyamides contain an amide functional group (– [10, 11]. Various pretreatments have been investigat- CO–NH–) in their backbone. The polyamide chain ed for polyamide: impregnation with hydroxypropyl ends on one side with an amino group (–NH2) and methylcellulose [10], impregnation with sodium on the other side with a carboxyl group (–COOH). alginate with alpha-olefin sulfonate [12], O2 plasma The amino end group is basic and can be proton- treatment [13] and non-thermal plasma in combina- ated to an ammonium ion (–NH₃+) under acidic tion with sublimation printing [14]. Several authors conditions. The carboxyl end group is acidic and suggested low-viscosity polygalactomannan ethers as can release a proton under basic conditions to form thickening agents for polyamide printing [3, 6, 15]. a carboxylate ion (–COO-). Reactive dyes can bind After printing and drying, the dyes are fixed on 6 Tekstilec, 2025, Vol. 68(1), 4–13 the textile. During fixation, the dyes diffuse from the basic colours were printed on fabrics made of cotton, thickening film into the interior of the fibre and bind polyamide and a blend of cotton and polyamide. The there. The most common fixation process is one-step CIE L*a*b* colour values, the colour depth (K/S) normal steaming at 100–103 °C. and the dye penetration (P) were compared on dif- Fixation is followed by post-treatments that give ferent materials printed under the same conditions. the prints their final appearance and improve wet The colour fastness of the prints to rubbing (crock fastness, handle and rub fastness. Non-fixed dyes, test), light and washing was measured. thickeners and chemical additives must be removed. Generally, the prints are first washed with cold water and then with hotter wash baths, sometimes with the 2 Experimental addition of dispersion soap [1]. The aim of this study was to investigate whether 2.1 Materials polyamide and blends thereof can be successfully Knitted fabrics from the manufacturer Inplet Pletiva printed digitally with reactive dyes, and which d.o.o., Slovenia, were used. Fabric data are presented preparation is best suited for this purpose. Four in Table 1. Table 1: Knitted fabric data Horizontal density Vertical density Mass per unit area Material Label (stiches/cm) (course/cm) (g/m2) 100% cotton CO 18 24 149.1 50% cotton/50% polyamide CO/PA 15 17 217.6 100% polyamide PA 13 18 100.8 2.2 Preparation of textiles for printing cotton-polyamide blended fabrics. The impregnated The fabrics were pretreated with an alginate thicken- samples were air dried at room temperature. ing preparation (A) or a galactomannan thickening preparation (GM). The recipes are presented in Table 2: Recipe for the preparation of the alginate Tables 2 and 3. thickener The following chemicals were used: CHT Additive Amount (g) alginate EHV (Bezema, Switzerland), alginate thick- CHT-alginat EHV 4% 400 ener; Prisulon DCA 130 (Bezema, Switzerland), Distilled H2O 525 polygalactomannan ether; sodium hydrogen car- NaHCO₃ 15 bonate (NaHCO₃) (Kemika, Zagreb, Croatia); urea CO(NH₂)₂ 50 (CO(NH₂)₂) (J.T. Baker, Netherlands), hydrotropic Rapidoprint XR 10 agent, Rapidoprint XR (Bezema, Switzerland), sodi- Total 1000 um m-nitrobenzenesulfonate, oxidising agent; and citric acid (C₆H₈O₇) (Kemika, Zagreb, Croatia). Table 3: Recipe for the preparation of galactomannan The fabrics were impregnated using a laboratory thickener two-roller padder (Mathis, Switzerland) with an impregnation effect of 88%. The alginate thickening Additive Amount (g) preparation was applied to cotton and cotton-poly- Prisulon DCA 130. 8% 910 amide blended fabrics. The galactomannan thick- Citric Acid 0.2% 90 ening preparation was applied to polyamide and Total 1000 Digital Printing Knitted Fabrics made of Polyamide, Cotton and Blends thereof 7 2.3 Printing, fixation and after-treatment and Δb* represents the difference on the yellow-blue Printing was performed using a digital piezo DOD axis. printer TextileJet Tx2-1600 from Mimaki with a resolution of 720 dpi and reactive dyes Jettex R The colour depth values (K/S) of the prints were (DyStar, England). The patterns were pre-processed calculated from the reflectance measurements using as squares in Adobe Photoshop. 100% cyan, 100% equation 2 [16]: yellow, 100% magenta and 100% black were printed. The printed fabrics were fixed in a laboratory (2) steamer DHE 20675 (Werner Mathis AG, Switzer- land) in 90% saturated steam at 102 °C. Cotton was where K represents the absorption coefficient (de- steamed for 10 minutes and polyamide for 20 min- pending on the dye concentration), S represents the utes, while the blends were steamed depending on the scattering coefficient and R represents the reflectance preparation: 10 minutes for the alginate preparation of the sample at a specific wavelength (R = 0 – 1). and 20 minutes for the galactomannan preparation. After fixation, the fabric was first rinsed with The penetration coefficient, P, indicates the cold water to remove residual thickeners, chemicals amount of dye that has reached the back of the and some unfixed dyes, then with warm water and fabric. It was calculated according to equation 3 [1]: finally with hot water. The next step was soaping for five minutes at 100 °C with 1 g/l CIBAPON R de- (3) tergent (CIBA, Switzerland) to remove all remaining dye residues. After soaping, the samples were rinsed with warm and cold water and air-dried at room where K/S(front) represents the colour depth on the temperature. front side of the sample and K/S(back) represents the colour depth on the back side of the sample. 2.4 Analyses The colour coordinates CIE L*a*b* and the reflec- Rub fastness was determined according to the tance R (%) of the printed samples were measured standard SIST EN ISO 105-X12:2002 – Colour using a SF 600 PLUS-CT spectrophotometer (Data- fastness to rubbing. Rubbing was carried out using color International, Switzerland). Ten measurements a Crockmeter (Electronic Crockmeter; SDL Atlas, were taken for each colour on each print. The mea- USA). surements were taken on the front and back of the Light fastness was determined according to printed fabric. The measurement conditions were: the standard SIST EN ISO 105-B02:2014 – Colour standard light D65, standard observer 10°, device fastness to artificial light: Xenon arc lamp test on a geometry d/8°, measuring range 400–700 nm, four Xenotest Alpha (Atlas, USA). fabric layers and a measuring aperture of 20 mm. Colour fastness to washing was determined ac- The colour difference (ΔE*) was calculated from cording to the standard ISO 105-C01:1989 – Textiles the CIE colour coordinates L*a*b* according to – Colour fastness tests – Part C01: Colour fastness equation 1 [16]: to washing: Test 1. Depending on the raw material composition of the sample, one accompanying fabric (1) was made of cotton and another of polyamide. The 10 x 4 cm samples were washed with the accompany- where ΔL* represents the difference in lightness, ing fabrics in a Launder-ometer LDH-HT B-S (Atlas Δa* represents the difference on the red-green axis Electric Devices, USA). 8 Tekstilec, 2025, Vol. 68(1), 4–13 3 Results and discussion that prints on cotton are darker than on polyamide and cotton-polyamide blended fabrics, regardless of Table 4 presents the results of the CIE L*a*b* colour the preparation used. The calculated colour differ- values of CMYK prints on cotton, polyamide and ences, ΔE*, show that the colours printed on various cotton-polyamide blended fabrics impregnated with materials differ significantly. The differences are different preparations. For all colours except magen- smallest for magenta, but even here they are greater ta, the CIE L* value is lowest on cotton, indicating than 1 and therefore visible to the naked eye. Table 4: CIE L*a*b* values on cotton (CO), polyamide (PA) and blended fabrics (CO/PA) impregnated with alginate (A) or galactomannan (GM) as thickener, and colour differences (∆E*) between prints on CO and other materials Colour Material L* a* b* ∆E* CO 53.14 -30.31 -28.11 - CO/PA (A) 69.10 -11.41 -26.97 24.76 C PA 69.61 -13.56 -26.64 23.54 CO/PA (GM) 75.05 -10.68 -24.82 29.60 CO 53.37 54.58 -3.05 - CO/PA (A) 53.49 58.73 -10.66 8.67 M PA 51.63 58.55 -6.92 5.81 CO/PA (GM) 57.22 56.23 -11.99 9.87 CO 79.07 5.77 87.53 - CO/PA (A) 86.52 -1.26 43.65 45.06 Y PA 85.93 -3.78 75.52 16.81 CO/PA (GM) 87.89 -8.25 70.19 23.98 CO 18.95 -2.14 -0.01 - CO/PA (A) 45.88 16.80 -1.63 32.96 K PA 33.02 23.25 4.56 29.39 CO/PA (GM) 33.60 24.78 6.24 31.28 Figure 1 shows the spectra of the K/S values as with alginate thickener. Conversely, the dye binds a function of the wavelength (360 nm to 700 nm). to PA and not to CO in the acidic preparation with The colour depth (K/S) is highest for cyan, yellow galactomannan thickener. The blends are therefore and black on CO, which again indicates that prints printed in lighter shades. on CO are darker than prints on PA and blends, regardless of the preparation used. The K/S values are similar for all fabrics for magenta. CO/PA blends have lower K/S values than CO and PA, regardless of the preparation used. The differences in the K/S values between the blends are small, so that the current measurements cannot confirm the superiority of one preparation over an- other. From this it can be deduced that the dye binds to CO and not to PA in the alkaline preparation Digital Printing Knitted Fabrics made of Polyamide, Cotton and Blends thereof 9 Figure 1: K/S values of CMYK prints on cotton (CO), polyamide (PA) and blended fabrics (CO/PA) impregnated with alginate (A) or galactomannan (GM) as a thickening agent Figure 2 shows the degree of penetration of the CMYK colours. The lowest penetration can be seen with CO. PA has a higher penetration than CO, which means that the dye solution migrates more to the back of the fabric. This can be explained by the fact that polyamide fibres are hydrophobic and absorb much less water than cellulose fibres, which leads to slower dye diffusion into the fibres and more difficult access to the available amino groups. The highest penetration is observed with blends, especially with CO/PA(A). The high penetration is CO CO/PA (A) PA CO/PA (GM) one reason for the low K/S values on the front side of the fabric. Dye that is transferred to the back of the fabric and binds there is less visible, resulting in a lower colour depth. Comparing the effects of Figure 2: Penetration degree (P) of CMYK prints on preparation, the prints on CO/PA (A) generally have cotton (CO), polyamide (PA) and blended fabrics higher penetration than on CO/PA (GM). impregnated with alginate (CO/PA(A)) or galacto- Table 5 presents the colour fastness values of mannan (CO/PA(GM)) as a thickening agent the prints for dry and wet rubbing according to the grey scale. The results show that all prints have good cyan, magenta and black, and for the blend CO/PA fastness to dry rubbing, with very high values of 4–5. (GM) with magenta and black. The values are lower The values for wet rubbing vary. The highest wet for CO and CO/PA (A), with the lowest rub fastness rubbing fastness is achieved for PA (grade 4) with being achieved for CO with cyan (score 1), and for 10 Tekstilec, 2025, Vol. 68(1), 4–13 the CO/PA (A) blend with cyan, yellow and black. cyan. Within the individual dyes, the values are bet- This can be explained by the fact that the absorption ter for CO and PA, and worse for blends, regardless of the dyes by the cotton is higher than their fixation. of the preparation used. The reason for this is that Cotton also absorbs hydrolysed dye, which cannot less dye is bound in blends, so that the dyes are more react with the fibres. Hydrolysed dye that was not accessible to light and the discoloration is therefore removed in final rinsing steps becomes visible during more visible. The highest rating is 7 for yellow on wet rubbing. PA, as a less absorbent material, absorbs PA, while the lowest is 1 for cyan on the blend CO/ less hydrolysed dye, and this can also be removed PA (GM). more easily during rinsing. The wet rubbing results are therefore better for PA. Table 6: Light fastness values of samples on cotton As the highest wet rubbing fastness applies to PA, (CO), polyamide (PA) and blended fabrics (CO/PA) this is also the case with the CO/PA (GM) blend, as impregnated with alginate (A) or galactomannan the dyes in this case are predominantly bound to PA (GM) as thickening agent and not to CO. Colour Material Light fastness CO 5 Table 5: Colour fastness values to rubbing on cotton CO/PA (A) 2 (CO), polyamide (PA) and blended fabrics (CO/PA) C PA 2 impregnated with alginate (A) or galactomannan CO/PA (GM) 1 (GM) as thickening agents CO 2 CO/PA (A) 3 Colour Material Dry rubbing Wet rubbing M PA 4 CO 4 1 CO/PA (GM) 3 CO/PA (A) 4 1 C CO 6 PA 5 4 CO/PA (A) 3 CO/PA (GM) 5 3 Y PA 7 CO 5 2 CO/PA (GM) 4 CO/PA (A) 5 2 M CO 4 PA 5 4 CO/PA (A) 2 CO/PA (GM) 4 4 K PA 3 CO 5 2 CO/PA (GM) 2 CO/PA (A) 4 1 Y PA 4 3 CO/PA (GM) 4 3 Table 7 shows the colour fastness values of the CO 4 3 prints when washed at 40 °C. The 100% CO and 100% CO/PA (A) 5 1 K PA fabrics recorded the best values for colour change, PA 4 4 although they are not excellent, which means that CO/PA (GM) 4 4 some of the dye (hydrolysed dye) is removed during washing. The values are lower for blended fabrics. The Table 6 presents the colour fastness values of the reason for this is the same as for light fastness. Less samples to light. From this it can be concluded that dye is bound on blended fabrics than on CO and PA light fastness depends primarily on the dye and less fabrics, so the reduction in the amount of dye on the on the fabric on which they are printed. Regardless fibres due to washing is more visible. of the fabric, the highest light fastness is for yellow, The ratings for dye transfer to cotton and poly- lower for magenta and black, and the lowest for amide adjacent fabric are similar for all dyes and Digital Printing Knitted Fabrics made of Polyamide, Cotton and Blends thereof 11 fabrics. The ratings range from 3 to 4–5. Staining that the washed-out dye does not stain the adjacent on the adjacent fabrics is relatively low, indicating fabrics. Table 7: Wash fastness values at 40 °C of cotton (CO), polyamide (PA) and blended fabrics (CO/PA) impregnated with alginate (A) or galactomannan (GM) as a thickening agent Washing fastness Colour Material Colour change Staining of CO Staining of PA CO 4–5 4 4–5 CO/PA (A) 2 3–4 4 C PA 4 3–4 4 CO/PA (GM) 3 4 4 CO 3–4 4–5 3–4 CO/PA (A) 3 4 3 M PA 4 3–4 4 CO/PA (GM) 2 4 4 CO 3–4 4–5 4 CO/PA (A) 2 4 3–4 Y PA 4 3–4 4–5 CO/PA (GM) 2–3 4 3–4 CO 4 4 4 CO/PA (A) 2–3 3–4 4 K PA 4–5 3 4 CO/PA (GM) 4–5 4 3 4 Conclusion galactomannan preparation, the dye binds well to polyamide but poorly to cotton. This means that one component of the blend is dyed poorly or not at all. The colour depth of prints is highest on cotton, low- The degree of dye penetration also influences est on polyamide and even lower on blended fabrics the K/S values. If the dye is transferred to the back for all colours. The lightness values (CIE L*) are side of the fabric, it is not visible on the front side. consequently lowest for cotton, slightly higher for In our cases, polyamide is more hydrophobic and polyamide and highest for blended fabrics. Visually, therefore absorbs less dye than cotton, so more dye the colours appear intense and bright on cotton and is transferred to the back and penetration is high. In polyamide, while they are significantly lighter and blends, one component is polyamide, which trans- less intense on blended fabrics. fers the dye to the back, while the other component Reactive dyes adhere well to cotton with the al- does not bind the dye due to the unsuitable pH kaline alginate preparation (pH 9) and to polyamide value. The penetration is therefore even higher. The with the acidic galactomannan preparation (pH 5.5). highest percentage of dye on the back of the fabric, is Good colour values were achieved in both cases. In found for all colours on the cotton/polyamide blend blends, the colours are lighter and the colour values impregnated with alginate thickener, and the lowest lower because the pH value of the preparation is on the 100% cotton fabric. only suitable for one component in the blend. In the All prints exhibit good fastness to dry rubbing, alkaline alginate preparation, the reactive dye binds while the fastness values to wet rubbing are mod- well to cotton but poorly to polyamide. In the acidic erate. The best fastnesses to wet rubbing value were 12 Tekstilec, 2025, Vol. 68(1), 4–13 recorded on polyamide and the cotton-polyamide 3. ŠOSTAR, S., SCHNEIDER, R. Guar gum as an blend impregnated with galactomannan thickener, environment-friendly alternative thickener in as these fabrics absorb less hydrolysed dye. Light printing with reactive dyes. 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