I ndian Journal of Fibre & Texti le Research Vol. J I . June 2006, pp. 320-329

Susceptibility of cationized and aminized cotton fabrics before and after crossl inking towards wet transfer printing

A Hebcish, Mohamed M EL-Mol la", Z H E L- H i l w & H S EL-Sayad

Text i le Div is ion, National Research Cer.:re. Ookk i . Cairo. Egypt

Receil'ed 24 Seplelllber 2004; rel'ised received 31 jWlllarv 2005; ([c( 'epled 20 April 2005

The behaviour towards wet transfer pri nt ing of cation izcd and amin ized cottons having di fferent n i trogen contents before �ll1d after cross l ink ing was sllIdied. Cationizat ion was effected through rcaction of cotton w ith (3-chloro-2-hydroxypropy l)trimethylammon i um ch loride whereas amin ization was ach ieved by react ing cotton w ith 2-chlorocthyl d iethy lamine hydrochloride.Thc modified cottons were cross l inked using polyearboxy l ic acids, namely c itric acid and I . 2 .

3. 4 - butane tetracarboxyl ic acid. fol iowed hy wet transfer pri nt ing us ing algi n ate Fi lms contai n ing e i ther a react ive dye l l r a d irect dye without using electrolytes. Pri nts on cationizecl and amin ized cattails exhi bited s ign ificantly h igher colour strength than on the untreated colton. Cross l i nk ing of the cat ionized and amin ized cottons prior to wet transrer printi ng detracted Illuch frolll their greater amenabi l i ty to such print ing. The wash. rub and perspirat ion fastncss values of the reactive dye on cat ionized and amin ized cottons before and after cross l i nk:ng were found to be comparable or cven s l ightly higher than those for the untreated cotton. However. i n case of d irect dye, the colour fastness results disclose s ign ificant i mpro\'ement in wash. rub and perspiration fastness over the untreated colton.

Keywords: Amin ized cotton. Cat ionized colton. Colton fabric, Wet transfer pri n t ing

(PC Code: Inl. CI 8 O()I) P ! lJ8. D06P3/58

1 Introduction Chemical modification of colton to improve i ts dye

abi l i ty with anionic dyes, such as reactive, d irect. acid, sulphur and vat, has received considerable attention in recent years, Most, if not al l, of the chemical modifications were based on the in tro­duction of cationic groups in the form of quaternary, tertiary or secondary amino residues in the molecular structure of cotton cel lu lose. 1 · 1 , This causes anionic reactive dyes to be attn'tcteel by the cationic charges on the fibre, and as a result, a h igh degree of dye fibre fi xation is ach ieved. A reduced washing off proce­dure, reduced or no electrolyte use, and equivalent wet fastness properties with the untreated cotton can b� obtained. lo2 Unl ike dyei ng, only few research papers have been published on the print ing of cationized cotton fabrics. Mart in i,J has described a method about the production of pattern effects via cationization and oxidation. Tabba and HauserJ4 showed that the wash fastness and crock fa�tness of pigment prints can be improved and fixation time reduced by the cationization of cotton fabrics. The

"'I" 0 whom al l the correspondence shou ld be addressed. E-mai i : mel mol ia@yahoo.com

present work was ai med at the fol lowing two objecti ves : ( i ) to improve the performance of polycarboxyl ic '

acid fin ished cotton fabrics via pre-cationizat ion or pre-aminizat ion of the cotton fabrics; and

( i i ) to study the behaviour of cationizecl and amin ized cottons before and after fi n ishing towards wet transfer pri nt ing using reactive and direct dyes.

I t i s envisaged that the work wi l l contri bute to environment protection through the uti l ization of polycarboxyl i c acids instead of formaldehyde contai n ing fin ish ing agents with their hazardous effect ; the enhancement of the dye fixation and i ts d irect consequence on decreasing the pol lution load ; and minimizing the addit ion of electrolytes and salts during printing.

2 Materials and Methods 2.1 Cotton Fabric

Mil l scoured and bleached cotton fabric ( 1 50 g/m\ suppl ied by Miser Company, for spinning and weaving, EI-Mehala EI- Kubra, Egypt, was used. The fabric was further purifi ed i n the laboratory by washing at l OO°C for 60 min using a solution contain i ng 2g/L Na2C03 and 1 giL Egyptol@ (non-

HEI3E ISH el III.: S USCEPTIB ILITY OF CATIONIZED AND AM I N lZED COlTON FABRICS 32 1

ionic wetting agent based on ethylene oxide condensate). The fabric was then washed several times with boi l ing water followed by cold water and finally dried at ambient conditions.

2.2 Chemicals

Sodium hydroxide, sodium carbonate, acetic acid, citric acid (CA), 1 , 2 , 3 , 4- butane tetracarboxyl ic acid (BTCA), and sodium hypophosphite (SHP), al l of analytical grade, were used. Cationic reagent, namely (3-chloro-2-hydroxypropyl)trimethylammonium chloride (65 wt'io aqueous solution under a com mer­cial name Quat(il)- 1 88) was suppl ied by Dow Chemical Company, USA and (2-chloroethly)-diethylalll ine hydrochloride (DEAE), and commercial sodium alginate of high viscosity was suppl ied by BF Goodrich, Munich, Germany. The reactive dye Cibacron Red P-6B ( 1 50%, e . 1 . Reactive Red 2 1 8) and the direct dye Solophenel Red 3BL (e . 1 . Direct Red 80) were suppl ied by Ciba - Geigy, Switzerland.

2.3 Cationization of Cotton

The cationizat ion w;�s carried out according to the pad-batch method.'o The cation ic reagent and con·es­ponding sodium hydroxide concentrations used in the study are given below:

Chemical

Cationic reagent (Quat® - 1 XX ) Sodiulll hydroxide (50%)

Concentration (giL)

50. 75 and 1 00 3 1 . 46.5 anel 62

Sodium hydroxide concentrations were calculated according to the method given by Tabba:\ i

The fabrics were padded through the cationization baths containing the cationic reagent and sodium hydroxide at the above concentrations to - 1 00% wet pick-up. The padded fabrics were then wrapped in plastic bag and stored at room temperature (25nC) for 24 h. After the removal of the batched fabrics from the plastic bag, they were rinsed with warm water at 40°C, neutralized with 2 giL acetic acid, cold rinsed, and then dried on a conveyor type dry ing machine at 1 00°e.

2.4 Aminzation of Cotton

The cotton fabrics were padded to 1 00% wet pick­up with aqueous solutions contain ing (2-chloroethyl)­diethylamine hydrochloride (OEAE) at different concentrations (50, 1 00, 200 giL) and then dried at 60°C for 10 min. The fabrics were then i mmersed i n 8% aqueous NaOH solution a t 95°C for 1 0 min . At

the end, the fabrics were neutralized with di lute acetic acid, washed with water and air dried.

2.S Ester Crosslinking of CoUon

Ci tric acid and 1 , 2, 3, 4-butane tetracarboxyl ic acid were separately used as ester crossl inkers for both cationized and aminized cotton fabrics. The cationized or aminized cotton fabrics were padded to 1 00% wet pick-up with 8% aqueous solution of citric acid or 6 .3% BTCA along with 6.5% of SHP as catalyst, then dried at 85"C for 5 min and cured at 1 70°C for 1 .5 min . The fabrics are then washed at 50"C for 5 min , washed with tap water and dried at ambient conditions.

2.6 Printing Processes

The coloured fi lm was prepared from a pri nt paste using the following recipe:

Dye Sodium algi nate Disti lled water

30 g 30 g 940 g

1 000 g

The dyestuff used wa�; ei ther Cibacron Red P-6B or Solophenel Red 3BL.

2.7 Transfer Printing

Samples of the treated and untreated cotton fabrics were wetted in 2% sodium carbonate solution to give 1 1 .5 pH in case of using coloured fi lms contai ning Cibacron Red P-6B, whi le in case of using coloured fi lms containing solophenel Red 3BL the samples were wetted in water only, squeezed to a pick-up of 70%, then transfer printed with the coloured fi lms as a substitute for the printed paper. The heat source was a 40 x 25 cm flat bed press. Printing time was varied from 1 5 s to 60 s at 1 60"C and 1 80°e. The samples were allowed to cool at room temperature before the fi lm was withdrawn.

2.8 Washing off Procedures

Two different washing off procedures were used i n the study. The untreated printed samples were washed according to washing off procedure (I) , as shown below, throughout the study . In the first step, cationic cotton samples were also washed according to the same procedure, but for the second and third steps, washing off procedure (II), as shown below, was used for the cationic samples. The washed samples were dried on the conveyor dryer at 1 00°e.

322 INDIAN J. FIBRE TEXT. RES. , JUNE 2006

Washing step Temp., °C Time, min

Washing off procedure (1)- Liquor ratio 20: J Cold rinsing 25 5 Warm rinsing (neutralization

with 0.5 gIL acetic acid)

Hot washing (with Cibapon R, 2g/L)

Warm rinsing

50

95

50

Washillg off procedure (11)- Liquor ratio 20: 1 Warm rinsing (neutralization

with 0.5 gIL acetic acid

Hot washing (with Cibapon R, 2g/L)

Cold rinsing

2.9 Testing and Measurements

50

80

25

5

1 0

5

5

1 0

5

Nitrogen content of the cationized and aminized samples was determined by the Microkjeldahl method.35 Tensi l e strength and elongation-at -break were determined according to ASTM standard test method?6 Wrinkle recovery angles of the treated and untreated samples were determined according to AATCC standard test method.37 The colour strength (KIS) of the printed samples was determined by reflection measurements using data colour i nter­national 1 994 (ref. 38) . Fastness to washi ng, rubbing and perspiration were assessed according to standard methods.39

3 Results and Discussion 3.1 Cationization Mechanism

Modify ing the cotton fibre to i ncrease dye- fibre interactions is another route to overcome the lack of affin i ty of commercial dyes for cotton. Lewis and Lei40 reviewed numerous chemicals that can be used to provide cationic charges on cotton fibre. Since direct and reactive dyes cany anionic charges, cationically-charged cotton would be expected to have a high affin i ty for these dyes.

The cationic reactant used for fibre modification was 2, 3-epoxy propyl trirr.ethyl ammonium chloride (1) .4 1 This reactive material i s prepared ill situ by the reaction of (3-chloro-2-hydrox ypropy I )tri methy 1-ammonium chloride (I I) (Quat- I 88) wi th alkal i as shown in Scheme 1 .

Compound (I) reacts with alcohol under alkali ne conditions to form ethers (Scheme 2) and thus produces a modified fibre when i t reacts wi th cotton to form the structure ( I I I ) .

An unavoidable byproduct of the reactions of ( I ) in aqueous alkaline solutions i s 2, 3-dihydroxypropyl trimethylammonium chloride ( IV) ; a species that

CH3 CH3 I 011 I

?H2 - yH - CH2 - �' - CH3CI" --+ C�2 -PH - CH2 - �' - CHP -

CI OH CH3 0 CH3 ( 3- chloro-2- hydroxypropyl ) 2, 3 . epoxypropyl lrimelhyl-

trimethylammonium chloride ammonium chloride (Qual-188) (II

(II) Scheme 1

CH3 CH3 I OH' I

CH2. - CH - CH2 - N' -CH3CI' � CH2- CH - CH2 - N' - C�CI-" ! I ROH I I I

o CH3 · OR OH CH3 2, 3 - epoxypropyl lrimethyl -

(I) OH ammonium chloride

I -

( Collonl Cell - OH

Cell - 0 - CH2 - 0 - CH - CHZ- N' (CH3)3 CI-dH

Calionized callan (III) Scheme 2

(I) (IV) 2, 3 - epoxy propyl trimethyl­

ammonium chloride 2, 3 - dihydroxy propyl trimethyl ­

ammonium chloride

Scheme 3

./ C2HS

Cell - OH + Cl - CHz - CH2 - N' : H C I - 2Na0l-\ --- C2Hs Cotton ( 2-chloroethyl )diethylamine hydrochloride

./ C2HS + 2NaCI + 2H20

Scheme 4

cannot react wi th cotton under the condi tions used i n thi s study (Scheme 3) , Depending on the specific reaction conditions, 20-50% of the epoxy groups i ni ti al ly formed wi l l hydrolyze to this inact ive material . 3 1

A s a result o f i ts reaction with compound ( I ), cotton w i l l have cationic dye s i tes covalently bound to the polymer chains . These dye s i tes strongly attract anionic direct and reactive dyes.

3.2 Mechanism of Aminization

Aminization of cotton cel lulose via reaction of the cellulose with (2-chloroethyl)-diethylamine hydro­chloride i n presence of alkali occurs as suggested in Scheme 4 (ref. 42).

HEBEISH el aL.: SUSCEPTIBILITY OF CATIONIZED AND AMINIZED COTTON FABRICS 323

The diethylaminoethyl groups so i ntroduced in the molecular structure of cotton cellulose act as a site which attracts the anionic dyes, such as the direct and reactive dyes; they represent additional s i tes for dye accommodation.

3.3 Performance of Cationized Cotton Fabrics

Table I shows the dependence of the extent of cationization reaction (expressed as n i trogen content %) on the concentration of cationic agent. Table I also shows the crease recovery angle, tensile strength and elongation-at-break of the cationized cotton fabrics before and after crossl inking.

The results show that the i ncrease in cationic agent concentration from SOg/L to 1 00 giL is accompanied by a substantial increase in n itrogen content of cationized cotton. This could be associated w ith the greater availabi l i ty of the cationic reagent molecules in the vicinity of cotton cellulose at higher concen­trations of the former. It is understandable that the hydroxyl groups of cotton cellulose are i mmobi le and their cationization rel ies on the avai labil i ty of the cationic reagent molecules in their proxi mi ty.

The cationized cottons display practically the same n itrogen values after crosslinking with either CA or BTCA; a point which implies that the cationic groups remain almost i ntact after crosslinking. That is , cross­l inking via esterification using the two polycarboxylic acids in question has no significant adverse effect on the cationic groups of the cationized cotton irrespec­tive of the magnitude of cationization.

Table 1 also shows that the cationization i ncreases the crease recovery of the cotton fabric w ith l i ttle advantageous effect of using higher concentrations of the cationic reagent. Thi s situation persists even after crosslinking using either CA or BTCA, but with the certainty that the crease recovery angles display exceedingly higher values after crosslinking than before crossl inking. A crease recovery angle as high

as 269°C could be achi eved after crosslinking the cationized cotton w ith BTCA. This is against a value of I S8°C before crossl inking. I t i s further noted that the tendency, though l i ttle, of the cationized cottons having h igher degrees of cationization to acquire higher crease recovery is a manifestation of ionic crosslinking occurring between the residual unesteri­fied carboxyl groups of CA or BTCA and the cationic groups of the cationic agent during the crosslinking treatment in accordance with previous reports.43

The crosslinking of the cationized cottons and the untreated cotton decreases significantly the tensi le strength but with the certainty that the cationized cottons retain higher tensi le strength than the untreated cottons, particularly when BTCA along with SHP catalyst was used as the crosslinking agent. Meanwhile, the elongation-at-break also decreases after crosslinking but the decrease is higher with the cationized cottons, most probably due to the relat ively higher crease recovery observed with the crosslinked cationized cottons.

The decrement i n strength properties after cross­l inking is i n conformation with earlier reports44. 45

which ascribed i t to molecular degradation of cotton cellulose under the i nfluence of the acid. I n combination w ith this i s the rigidity conferred on the cellulose structure by crosslinking.

3.4 Performance of Aminized Cotton Fabrics

Table 2 shows the effect of amin iz ing agent con­centration on the extent of amin ization (expressed as %N of cotton fabric) . As is ev ident, the nitrogen content i ncreases as the aminizing agent concentration i ncreases within the range studied. Thi s can be interpreted i n terms of greater availabi l i ty of the aminizing agent molecules which are i n the proxi mity of the i mmobil ized cellulose hydroxy Is at h igher aminizing agent concentrations.

Table I-Properties of untreated and cationized cotton fabric using different levels of Quat- 1 88 before and after crossl inking with CA or BTCA

Cationic reagent N itrogen content Crease recovery angle Tensi le strength, kg.f (Quat- 1 88) conc. % (w+f), deg (elongation-at-break, %)

giL a b c a b c a b c

Untreated 0.0 1 1 0.0 1 1 0.0 1 1 140 250 260 40.6(28.5) 23.7(20.5) 25.3(23.4) 50 0.300 0.300 0.320 1 52 26 1 260 38.5(24.6) 2 1 .6( 1 9.3) 23.2(2 1 .3 ) 75 0.3600 0.360 0.350 1 55 264 265 35.3(23.4) 20.3( 1 8.5) 2 1 .3(20.5) 100 0.4300 0.440 0.420 1 58 268 269 30.0(22.8) 1 8 . 1 ( 17 .8) 1 9.8( 1 8.7)

a - Cationized cotton, b - Cross l inking of cationized cotton using 8% CA with 6.5 of S HP, and c- Crosslinking of cationized cotton using 6.3% BTCA with 6.5% of SHP as a catalyst.

324 INDIAN 1. FIBRE TEXT. RES., JUNE 2006

Table 2 also shows, the effect of crosslinking using either CA or BTCA on the nitrogen content of aminized cotton. Obviously none of the crossl inking agents used has any significant effect on the nitrogen content of aminized cottons as evidenced by the almost equal values of n i trogen content moni tored before and after crosslinking. Thi s concludes that the crossl inking of aminized cottons via esterification using CA or BTCA occurs without exerting any noticeable effect on the diethylaminoethyl groups of the aminized cottons.

It is revealed that the aminization enhances the crease recovery of the cotton fabric and there is a tendency that this enhancement i s related to the extent of aminization, expressed as %N. S ignificant effect i n crease recovery i s observed after crosslinking regard­less of the crosslinking agent used.

I t is further noted that the tensi le strength and elongation-at-break of the aminized cottons decrease

significantly after crossl inking with either CA or BTCA. No clear-cut relationsh ip between the extent of amin ization and decrement in strength properties i s observed. Decrements i n strength properties were compared with those observed with cation ized and untreated cotton and could be explained on s imilar basis .

3.5 Printability of Cationized Cotton Fabrics

Cationized cotton as well as cationized cotton crossl inked w ith either CA or BTCA having different n i trogen contents were subjected to wet transfer printing using coloured fil ms containing reactive dye (Cibacron Red 6-B) at 1 60°C and 1 80°C for different intervals of time. Results are shown in Table 3 .

I t is observed that for a given transfer temperature, the i ncrease in t ime of transfer enhances the colour strength of the prints of both cationized cotton and cationized cotton crosslinked with e ither CA or

Table 2-Properties of untreated and aminized cotton fabrics using different concentration of (2-chloroethyl)­diethylamine hydrochloride before and after cross l ink ing with CA or BTCA

(2-chloroethyl)-diethylamine Nitrogen content Crease recovery Tensi le strength, kg.f hydrochloride % angle (w+f), deg (elongation - at - break, %)

giL a b c a b c a b c

Untreated 0.0 1 1 0.01 I 0.0 1 1 1 54 275 273 40.6(28.5) 20.8(20.5) 22.2(20.2)

50 0. 1 09 0. 1 09 0. 1 09 1 66 270 270 35.2(28.0) 20.0( 1 9.3) 2 1 .3( 1 9.7) 1 00 0.2 1 1 0.2 1 I 0.2 1 1 1 73 275 275 34.5(27.3) 1 9.2( 1 8.7) 20.5( I 8.5) 200 0.430 0.430 0.430 1 80 280 280 30. 1 (26.2) 1 8 .9( 1 7 .8) 1 7 .5( 1 7 .3)

a - Aminized cotton. , b -Crossl inking of aminized cotton us ing 8% CA wi th 6.5% of SHP, and c -Crossl inking of aminized cotton using 6.3% BTCA wi th 6.5% SHP as a catalyst.

Table 3 - Effect of transfer print ing t ime on colour strength of printed cationized and cationized crossl inked cotton fabrics

[Dye- Cibacron Red P-6Bl

Ti me of transfer --:-c __ --:-___ =-:--:---:-____ C=-o::.c:�.=-ou=.:r....:s:..:::trc::.e;:..:,ng"-'tc.:.h'_(�K:.:.../S

=__=v=.:al-'--ue.:c.:s'-'-)--::-:-:--:-_

----:-:---:---:-

_____ _

Untreated ___ -'C--:a_tio_n

,-i_ze_d_c_o_tt...,..

o_n-,---__ Cotton cationized and crossl inked

1 5 30 45 60

1 5 30 45 60

')' max - 540 nm.

cation O.3N% 0.36 N% 0.43 N% With CA (8%) With BTCA (6.3%) 0.3N% 0.36 N% 0.44N% 0.3N% 0.35 N% 0.42N%

Transfer printing temperature - 160"C

1 .06 5.6 6.05 7.83 2.96 3 .2 3 .8 1 .6 1 .7 1 .75 1 .4 8 .2 1 0.6 1 3 .3 3.7 4.5 4.9 1 .8 1 .95 2. 1 2.3 1 3 .5 1 8.4 23.6 4. 1 5 .87 6.2 2.5 2 .8 2 .93 2.8 1 9.02 23.0 29.2 4.8 5.9 7.53 2.95 3. 1 3 .2

Transfer printing temperature - 180°C

1 .5 6.4 8.3 10.5 3 . 1 3.6 4.2 1 .7 1 .82 1 .9 2 1 0. 1 1 2 .3 1 4.2 4.3 4.9 5.6 2 .3 2.5 2 .8

3 . 1 1 6 .8 1 9.9 26 4.8 5 .7 7. 1 3 .5 3.6 3.8 3 .5 23.59 25.2 3 1 5.03 7 .0 1 7 .3 3 .8 3 .9 4. 1

HEBEISH et at.: SUSCEPTIBILITY OF CATIONIZED AND AMINIZED COTTON FABRICS 325

BTCA; and the enhancement however, depends largely on the degree of modification (O/ON) of the samples. For example, the prints of cationi zed cotton fabrics with n itrogen contents of 0.0, 0 .3 , 0.36 and 0.43% exhibit colour strengths (KIS) of 2 .3 , 1 3 .5 , 1 8 .4 and 23.6 when transfer pri nting was carried out for 45 s at 1 60°C. Thi s i ndicates that the enhancement i n colour strength i s essentially owing to cationization.

Crosslinking of the cationized cottons using ei ther CA or BTCA detracts s ignificantly from the abi l i ty of cationized cottons to wet transfer print ing using reactive dye. As can be observed from Table 3 , the crossl inked substrates display much less colour strength values compared to cationized cotton with comparable n i trogen content. This decrement i n colour strength i s much more noticeable i n case of cotton cation ized and crossl inked with BTCA as compared to that when CA was used.

S imi lar results are obtained when cationized cotton fabrics before and after cross l inking were printed with Solophenel Red 3BL as shown i n Table 4.

Table 4 also shows the colour strength of the prints of both cationized cotton and cationized cotton crosslinked with either CA or BTCA. Obviously the enhancement in colour strength depends largely on the degree of modification (O/ON) of the samples, owing to quat group (NH4 +) . This group offers significant potential for i mproving the speed and yield of printing in a non-polluting manner s imi lar to the use of quaternary ammonium cellulose (quat cellulose). The quat group has very high posit ive charge and can thereby lead to the formation of ionic

bonds with the negatively charged dye anionic groups. Thi s again i ndicates that the enhancement i n colour strength i s essentially owing to cationization.

Crossl inking of the cation ized cottons using either CA or BTCA detracts s ignificantly from the abi l i ty of cationized cottons to wet transfer printing using direct dye; s imi lar to the reactive dye as pointed out above. As can be observed from Table 4, the crosslinked substrates display much less colour strength values compared to cationized cotton with comparable n itrogen content. This decrement in colour strength i s much more noticeable i n case of cotton cationized and crossl inked with BTCA and CA.

I t could be concluded that cationization of cotton fabrics with Quat- 1 88 enhances their printabi l i ty towards reactive and direct dyes. On the other hand, the cationization followed by crossli nking decreases the dyeabi l i ty but with the certainty that the cationized-crosslinked cottons exhibit greater dyeabi l i ty than the cross l inked cotton.

3.6 Printability of Aminized Cotton Fabric

Tables 5 and 6 show the colour strength of prints obtained wi th aminized cottons having different aminization levels before and after crossl inking. Wet transfer print ing was applied using Cibacron Red P-6B and Solophenel Red 3BL. Transfer printing was carried out at 1 60°C and 1 80°C for different lengths of time.

I t i s revealed that the colour strength (KIS) increases by i ncreasing the t ime of transfer at a given temperature. Nevertheless, the colour strength IS

Table 4- Effect of transfer printing t ime on colour strength of printed cationized and cationized cross l inked cotton fabrics

[Oye-Solophenel Red 3BLI

Time of transfer Colour strength" (KIS values) s U ntreated Cationized cotton Cotton cationized and crossli nked

cotton O.3N% 0.36 N% 0.43 N% With CA (8%) With BTCA (6.3%) 0.3N% 0.36 N% 0.44 N90 0.32 N% 0.35 N% 0.42N%

Transfer printing temperature- 160·C

1 5 0.58 1 .25 1 .60 2.40 0.80 0.93 1 . 1 0 0.74 0.89 1 . 1 3 30 0.88 1 .39 2.23 3.63 0.98 1 .56 1 .98 0.98 1 .00 1 .20 45 0.94 1 .60 3.90 5 . 1 0 1 .63 1 .99 2 .39 1 .00 1 . 1 2 1 .74 60 1 .03 2.30 5 .30 6.75 1 .70 2 .30 2.90 1 .20 1 .34 1 .95

Transfer printing temperature - 180·C

1 5 0.63 1 .53 1 . 88 2.60 0.93 1 . 1 1 1 .20 0.79 0.95 1 .20 30 0.92 1 .75 2 .84 3.40 1 .40 1 .48 2.25 0.44 1 . 1 1 1 .28 45 0.99 2.25 5.39 6.80 1 .80 2 .30 2.98 1 .20 1 .39 1 .85 60 1 . 1 0 2 .84 7.76 9.45 1 .90 2.59 3.80 1 .40 1 .59 2 . 1 0

" A max - 530 nl11.

326 INDIAN J. FIBRE TEXT. RES., JUNE 2006

Table 5-Effect of transfer printing t ime on colour strength of printed aminized and aminized crossli nked cotton fabrics

[Dye- Cibacron Red P-6B]

Time of transfer -:-:-__ -:-___ --:--:--:-____ --'C:..:o:.:..lo:..:u:.:..r.::..st::..re:.:.n:.«g:.:.th:....." -'..:(K.::..I:::..S-=v.=al:..::u::.:ces:.!..)

--,-:--:---,_---:�--:------_

Untreated Aminized colton Cotton aminized and crossl inked cotton 0. 1 09 N% 0.2 1 1 N% 0.43 N% With CA (8%) With BTCA (6.3%)

0. 1 09 N% 0.2 1 1 N% 0.43 N% 0. 1 09 N% 0.2 1 1 N% 0.43 N%

Transfer printing temperature - 160°C 1 5 1 . 06 3.70 4.0 1 4.5 1 .00 1 .77 2. 1 1 . l 0 1 .30 1 .69 30 1 .4 5.25 8.20 10 . 1 1 .50 2.0 1 2.8 1 .50 1 .58 2.75 45 2.3 7 . 1 9 1 1 .90 1 6.8 1 .65 2.70 3.0 2.35 2.60 2.75 60 2.8 1 1 .83 14.30 1 8.3 1 .73 2.84 4.8 2.84 2.90 3.05

Transfer printing temperature - 180°C 1 5 1 . 5 4.80 5.52 6.73 1 .60 2.20 2.40 1 .55 1 .63 2 . 1 0 30 2.0 7.50 10.90 1 1 .9 1 .92 2.30 2.90 2. 1 0 2.36 2.60 45 3 . 1 12 .60 17 .40 19.6 2. 1 0 2.95 3 . 1 7 3.25 3.50 3.72 60 3.5 16.60 2 1 .00 23.5 2.35 3.05 4.98 3.60 3.79 3.85

a A. max - 540 nm.

Table 6-Effect of transfer print ing t ime on colour strength of printed aminized and aminized crossl i nked cotton fabrics

[Dye- Solophenel Red 3BL]

Time of transfer Colour strength" (KIS values) s Untreated Aminized cotton Cotton aminized and cross l inked

cotton 0. 1 09N% 0.2 1 1 N% 0.43N% With CA (8%) With BTCA (6.3%) 0. 1 09N% 0.2 1 I N% 0.43N% 0. 109N% 0.2 1 IN% 0.43N%

Transfer printing temperature - 160·C 1 5 0.58 0.9 1 1 .29 1 .83 0.62 0.68 0.72 0.63 0.68 0.95 30 0.88 1 . l 3 1 .90 2.43 0.93 1 .00 1 . l 5 0.89 0.9 1 l . l 0 45 0.94 1 .30 2.85 3.8 1 1 .05 1 .20 1 .39 0.96 1 .02 1 .32 60 1 .03 1 .90 3.35 4.63 l . l 5 1 .30 1 . 5 1 l . l 0 l . l 8 1 .60

Transfer printing temperature - 180·C 1 5 0.63 1 .2 1 1 .38 1 .70 30 0.92 1 .50 1 .94 2.74 45 0.99 1 .80 3.44 4.63 60 1 . 10 2.60 4.52 5.02

a A. max - 530 nm.

determined by the n i trogen content of the aminized cotton; a point which could be associated with the pendant DEAE groups i n the molecular structure of cotton. Most probably these groups perform ( i ) opening up the cellulose structure thereby faci litating diffusion and adsorption of dye molecules as well as accommodating more dye aggregates; (ii) altering the characteristic nature of cotton cellulose via imparting cationic surfaces which attract the oppositely charged dye anion; and ( i i i ) acting as built- i n catalyst for the reaction of reactive dye with the cotton cellulose.

DEAE cottons with different N% were given cross­l inking treatment with CA or BTCA under identical

0.69 0.73 0.95 0.67 0.79 l . l 2 1 . 1 1 1 .2 1 1 .20 0.93 1 .0 1 l . l 6 1 .70 1 .32 1 .89 l . l 0 1 .22 1 .53 1 .20 1 .39 2.70 1 .25 1 .38 1 .75

conditions. The results obtained are g iven i n Tables 5 and 6.

I t is observed that amin ization of cotton through the introduction of DEAE groups prior to crosslinking leaves the susceptibi l i ty of cotton towards cross­l inking partially unimpaired. It is certain, however, that the crossl inked DEAE cottons with CA or BTCA acquire much h igher colour strength than their mate prepared from untreated cotton.

3.7 Fastness Properties

Table 7 shows the colour strength and fastness properties of transfer prin ts obtained from cationized

HEBEISH et 01.: SUSCEPTIBILITY OF CATIONIZED AND AMINIZED COTTON FABRICS 327

Table 7- Colour strength and fastness properties of transfer printed modified cotton through cationzation and aminization before and after crossl inking with CA and BTCA

Cotton fabric

Untreated

Cationized cotton

Cationized cotton

crossl inked with

8% CA

Cationized cotton

crossl inked with

6.3% BTCA

Aminized cotton

Aminized cotton

crossl inked with

8% CA

Aminized cotton crosslinked with

6.3% BTCA

[Transfer temperature 1 60"C, Time of transfer 60 s, and Dye Cibacron Red P-6B]

Cationizing/aminizing KIS agent cone. values

giL

SO 7S

1 00

SO 7S

1 00

SO 7S

1 00

SO

1 00

200

SO 1 00

200

SO 1 00

200

2.8

1 4.02

23

29.2

4.8 S .9

7.23

2.9S

3. 1

3.2

1 1 .83

14.3

1 8 .3

1 .73

2.84

4.80

2 .84

2.9 3.0S

Wash fastness Rub fastness at 60"C --

D-r-y---

W-

e-t-

3-4

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S 4-S 4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

S

S

S

S

S

S

S

S

S

S

S S

S

S

S

S

S

S

3

3-4

3-4

4

4

4

4

4

4

4

4

4 4

4

4

4

4

4

4

Perspiration fastness Acidic Alkaline

Staining Alteration Staining Alteration

3

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

3

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

4-S

Table 8-Colour strength and fastness properties of transfer printed modified cotton through cationzation and aminization before and after crossl inking with CA and BTCA

Cotton fabric

Untreated

Cationized cotton

Cationized cotton crosslinked with 8% CA

[Transfer temperature 1 80°C, Time of transfer 60 s, and Dye Solophenel Red 3BL]

Cationizing/aminizing KIS agent cone. values

giL

SO 7S

1 00

SO 7S

1 00

1 . 1

2 .84 7.76 9.49

1 .9 2 .S9

3 .8

Wash fastness Rub fastness at 60°C --=

Dc:.r::":Y:""::':=:'='

W':':

e=-t-

2-3

3-4 4 4

4 4-S

4-S

3

4 4-S

4-S

4 4-5 4-5

2-3

3-4

4 4-S

4 4

4-5

Perspiration fastness Acidic Alkal ine

Staining Alteration Staining Alteration

3

4

4 4

4

4

4

4

4 S S

S

S

S

3

4

4 4

4

4

4

3

4 S S

S

5

5

COlltd

328 INDIAN J . FIBRE TEXT. RES., JUNE 2006

Table 8-Colour strength and fastness properties of transfer printed modified cotlon through cationzation and aminization before and after crossl inking with CA and BTCA---Collid

[Transfer temperature 180°C, Time of transfer 60 s, and Dye Solophenel Red 3BLI

Cotton fabric Cationizing/aminizing KIS Wash fastness agent conc. values at 60°C

gIL

Cationized cotton 50 1 .4 3-4 crossl inked with 75 1 .59 4

6.3% BTCA 1 00 2. 1 4

Aminized cotton 50 2.6 4 1 00 4.52 4-5

200 5.02 4-5

Aminized colton 50 1 .2 4 crossli nked with 1 00 1 .39 4-5 8% CA 200 2.7 4-5

Aminized cotton 50 1 .25 4 crossl inked with 100 1 .38 4-5 6.3% BTCA 200 1 .75 4-5

or aminized cotton fabrics before and after being crosslinked with CA and BTCA using Cibacron Red P-6B. It is observed that the colour strength (KIS) i ncreases by i ncreasing the extent of cationization or aminization, which, in turn, depends on the type and concentration of the modifying agent used. It is also observed that the wash, rub and perspiration fastness of the said reactive dye or cationized and aminized cottons before and after crosslinking are comparable or even sl ightly higher than those for the untreated cotton.

Table 8 shows the colour strength and fastness properties of transfer pri nts obtained from cationized or aminized cotton fabrics before and after cross­l inking with BT and BTCA using Solophenel Red 3BL. The results reveal that the printabil i ty as evident by colour strength increases by cationization or amini­zation of the cotton fabrics prior to wet transfer print ing. Thi s i s observed before and after cross­l inking of these modified cotton fabrics. The colour fastness results disclose signifi cant improvement i n wash, rub and perspiration fastness over the untreated cotton. However, the wash fastness ratings for the direct dye on untreated cotton is not typical of those seen in i ndustry s ince fixing agent based treatments are almost always used to get acceptable performance. In this work, the cationized and aminized dye sites are

Rub fastness Pers�iration fastness Dry Wet Acidic Alkal ine

Stain ing A lteration Stain ing Alteration

4 4 4 5 4 5 4-5 4 4 5 4 5 4-5 4 4 5 4 5

4 4 4 5 4 5 4-5 4 4 5 4 5 4-5 4 4 5 4 5

4 4 4 5 4 5 4-5 4 4 5 4 5 4-5 4 4 5 4 5

4-5 4 4 5 4 5

4-5 4 4 5 4 5 4-5 4 4 5 4 5

seemingly capable of binding direct dye to a h igh degree.

4 Conclusions

4.1 Cotton treated with reactants such as (3-chloro-2-hydroxypropyl)trimethylammonium chloride or (2-chloroethyl)-diethylamine hydrochloride, that provide cationic dye sites can be wet transfer printed without electrolytes to give excellent colour yields with direct and reactive dyes.

4.2 The colour fastness of these prints i s superior to that of the same dyes on untreated cotton.

4.3 The prints obtained on cationized cotton show better colour yield than the prints obtained on aminized cotton fabrics, being dependant on the extent of chemical modification, which, in turn, rely on the modifying agent concentration.

4.4 Crossl inking of the cationized cotton or aminized cotton using citric acid or 1 ,2,3,4-butane tetra carboxylic acid prior to wet transfer printing signifi cantly decreases the colour strength of the prints.

4.5 The wrinkle recovery angle (WRA) increases by i ncreasing the degree of cationization or aminization of cotton fabric but the outstanding enhancement I n WRA is observed after crossl inking.

HEn[1�H et al. : SUSCEPTIBILITY OF CATIONIZED AND AMINIZED COTTON FABRICS 329

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