J.Chem.Soc.Pak., Vol. 31, No.

1,2009

145

Effect of Crosslin king in Textile Pigment Printing and Enhancement of Fastness Properties
MUHAMMAD WARIS, MANSOOR IQBAL *, AUSAF ALEEM AND FARAZ ALI.
Applied Chemistry Research Centre (Textile Section), PCSIR Laboratories Off University Road, Karachi-75280, Pakistan.
(Received II th October 2007, accepted in revised form 20th September 2008) Summary: Pigment printing was carried out on lab scale by simple screen-printing techniques. By the application of acrylate based binder and melamine based fixative the crocking, perspiration and dry-cleaning fastness properties of Red, Navy and Black prints were evaluated. It has been found that, as the concentration ratio between pigment applied and fixative increases, the fastness properties also increase and reach to an optimum value of I :2.5; beyond this value the fastness properties decrease and resultant print become stiff The fastness properties of Red print were found to be better as compared to Navy and Black prints.

Complex,

Introduction Pigment print merits a separate treatment because of its extensive use and technically different characteristics from printing dyes. About half of the 20 Billion meters of cloth which are printed annually world wide are pigment printed though there are significant variations in different countries [1]. In pigment printing, insoluble pigments, which have no affinity for the fiber are fixed on to the fiber with binding agents in the pattern required. A good quality pigment print is characterized by brilliance and high color value relative to the pigment concentration in the paste, minimum stiffening in the handle of textile and generally acceptable fastness properties. Successful pigment printing systems are based upon three equally important components: Pigment dispersions, binders and crosslinking agents, thickener and auxiliary agents giving the required rheology [2]. The binder film in pigment print is a 3-dimensional structure, the third dimension is rather less important than the other two. The binder is a film-forming substance made up of long chain macromolecules, which when applied to the textile together with the pigment produce a 3-dimensionally linked network The links are formed during some suitable fixing process which usually consists of dry heat and change in pH value, bringing about either self-crosslinking or reaction with other suitable crosslinking agents. The important criteria which ensure that the pigment within the crosslinked binder film is fast to external agencies like water, chemicals and rubbing, are elasticity, cohesion and adhesion to the substrate [3]. The binders used are all addition polymers, preferably copolymers such as following structure;
'VVV'-CH-2

o
I

CH--CH --C~
2

I

CO-o--C4H9

(Styrene-butyl Acrylate copolymer) Depending upon the properties required in the binding film (softness, elasticity, plasticity, solvent stability), binders can be tailor-made by choosing suitable base product. It is necessary to copolymerize different monomers. Typically, unsaturated monomers are used such as vinyl chloride, dichloroethene, acrylic acid, acrylonitrile, acrylic acid esters and ethers. Nowadays, acrylate based copolymer are most widely used [4J. Elasticity and improved adhesion of the film to the substrate is achieved by crosslinking. The crosslinking reaction must produce covalent bonds which are insensitive to hydrolysing agents (washing liquor, perspiration, industrial atmosphere). The
reaction should be activated in dry hot air. St@am can

have adverse effect on cross-linking and consequently on the fastness of the print [5). If B is the principal part of the binder the crosslinking of N-methylolamide group takes place under mild conditions and in acid medium:
B-CHzOCHz-B + HOH

or BCHrOB +HOH

To whom all correspondence should be addressed.

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Crosslinking increases the crocking, washing and dry cleaning fastness properties, but detrimentally affects the handle of the fabric. When the binder molecule have no self-crosslinking groups, an additional crosslinking agent such as urea formaldehyde or melamine formaldehyde condensate, methylolated urethane compounds etc, having at least two reactive groups per molecule are added in the binder system (6). Fixatives are used in the smaller quantities even when the binder contains the self-crosslinking groups. Typically the pigment printing paste formulation includes; water, pigments, binder, white sprit, synthetic thickening agent, water retaining agent, cross linking agent, adhesion promoters, catalyst, handle modified, antifoaming agent, plasticisers and ammonia. All these components are not always required, their availabilities depend on the conditions under which printing is being carried out [7). The present research work demonstrates the crosslinking effect of acrylate based binder, which is self-crosslinked copolymer and melamine based fixative. Their influence on the crocking, perspiration and dry-cleaning fastness properties has also been investigated. Results and Discussion Three different pigment prints Red, Black

Colour Fastness to Crocking

(Red)

5 4.5

'e
~

gp

4 3.5 .... --_.-3 2.5

.E

II

2
1.5 0.5

O~--~------~~=---~-----r---=~
0.0% 1.0% 1.5% 2.0% 2.5% 3.0%

Concentration

/-+-Ory
Fig. lea):
Colour fastness to Crocking

Wet

I

Colour fastness to Crocking (AATCC-08).
(Navy)

.~ 3,~

""

5 4.5 4

£

S

~

2.5

2
1.5 1 0.5

The cross-linking effect of acrylate based binder and melamine based fixative were investigated. The enhancements in the crocking, perspiration and drycleaning fastness properties of final print caused by above crosslinking agents were also studied. Fastness properties largely affected by taking a constant concentration of binder 90 glkg (w/w) and by varying the concentration of fixative from 1 % to 3 %. A relationship between varying concentration of fixative and fastness properties shown in Figs. 1-3. From the results given in Tables 1-3 at initial using a constant concentration of binder 77N), which is a self-cross linking agent, copolymer system, at this stage the fastness is due to the crosslinking of copolymer Colorfastness to Crocking (AATCC-08).
Red Wet D~ 3-4 2 2-3 3-4 2-3 4 4-5 3 3-4 4-5 3-4 4 Navy Da: Wet 2 1-2 2-3 2 3 2
3-4 2-3

o+----~------~----~---__,___--~
0.0% 1.0% 1.5% 2.0% 2.5%

3.0%

Concentration

I-+- Dry--Fig. 1 (b):

Wet

I

Colour fastness to Crocking (AA TCC-08).
Colour Fastness to Crocking (Black)

stage by (Printofix having a achieved Table-I:

.i

E £

en 3.5 ::: 3 ~ 2.5 2 ... 1.5 __ -1 0.5

4.: 1

--~r__ r-

Concentration of fixative Withont fixative 1.0% 1.5% 2.0% 2.5% 3.0%

4 3-4

3 3

Black Da: Wet 1-2 2 1-2 2 2 2-3 3 2 2-3 3-4 2-3 3

O+-----~----_r----~---__---__
0.0% 1.0% 1.5% 2.0% 2.5% 3.0%

Concentration

i-+-Dry
Fig. I (c):

Wet

I

Colour fastness to Crocking (AATCC-08).

MANSOOR IQBAL

et al.,

J.Chem.Soc.Pak.,

Vol. 31, No.1, 2009

147

molecule with each other or with the hydroxyl (-OH) group of cellulosic substrate. The cross linking ensures the optimum fastness properties at this stage [8]. The reaction between the binders and the cellulosic substrate may be represented as follows: Binder - CH2 - OR + HO - Cellulose

Table-2: Color fastness to Dry-cleaning DOl).
Concentration of fixative Without fixative
1.0% 1.5 % 2.0% 2.5% 3.0%

(lSO-

105-

Shade change Shade change Red Nav~
2-3 2-3 3 3-4 4 3-4 1-2 2-3 3 3-4 4 3-4

Shade change Black
1-2 2 3 3-4 4 3-4

Binder - CH2 - 0 - Cellulose + ROH where R is CH3 or H By increasing the amount of fixative (Printofix fixative WB), the fastness properties remarkably increased as shown in Figs. 1-3 and Tables 1-3. Additional improvement in fastness properties is mainly due to the reaction of fixative with binder, this actually reduced the water solubility of print thickener paste which ultimately results in the improved fastness properties. The reaction may be represented as the following:

1~

Table-3(a): Colour fastness to Perspiration (ISO- 105E04) (Acidic).
Colour Red Concentration of Fixative Without fixative
1.0 °/0

Change Staining on Multi fiber in Shade CO CA PA PES PAC WO
3 3-4 4 4-5 4-5 4 2-3 3 3 3-4 4 4 3 3 3-4 4 4-5 4 3-4 3-4 4 4 4-5 4 2 2-3 3 3 4 3-4 2 3 3 3-4 4-S 4-5 3-4 3 3-4 4 4 3-4 2 3 3 2-3 2-3 2-3 3-4 3 4 3-4 3-4 3-4 2-3 2 2-3 2-3 3-4 3 4 4 4-5 4-5 4 4 3 3-4 3-4 4 4 3-4 2-3 3 3 3-4 4 3-4 3 3 3-4 4 4-5 4 2-3 2-3 3 3-4 4 3-4 3 3-4 3-4 4 4-5 4 2-3 3 3 3-4 4 3 3-4 3-4 3-4 4 4-S 4 3 3-4 4 4-5 4-5 4 2 3 4 4 4-5 4 2-3 3 3 4 4-S 4

1.5% 2.0% 2.5 % 3.0%

Navy

Without fixative
1.0% 1.5% 2.0% 2.5 % 3.0%

Black Without fixative
1.0 % 1.5% 2.0% 2.5% 3.0%

+

IIO-~-{
Carboxylated Polymer

Hexamethoxymethyl

Melamine

Reduced water solubility increased mechanical stability

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Table-3 (b): Colour fastness 105- E04) (Alkaline).

to Perspiration

(ISO-

Colour fastnessto perspiration (change in shade)
e

1.0% 1.5% 2.0 % 2.5% 3.0% Navy Without fixative 1.0% 1.5 % 2.00/0 2.5 Ufo 3.0%

4·5 3-4 2-3 3 3-4 3-4 4 3-4 2·3 3 3 3-4 4 4 2-3 3-4 3-4 4 4-5 4 3 3 3-4 4 4-5 4-5

3 3-4 3-4 4 4 3-4 2 2·3 2·3 3-4 4 4 2 2 3 3-4 4 4

4-5 4-5 4 1-2 2-3 3 4 4 3-4 2 2-3 2-3 3-4 4 3-4 3 3 3-4 4 4 4 2-3 3 3-4 3-4 4 3-4 2·3 3-4 4 4 5 4·5 3 3-4 4 4 4·5 4 2 2-3 3 3 4 3 3 3 3-4 4-5 5 4-5

IU)'};,

1.11%

1.5% Concentration

2.0%

2.S%

3.0%

Black Without fixative 1.0% 1.5 % 2.0% 2.5 OAt 3.0%

I-l:r- Acidic --Fig. 3 (a): Colour fastness E04).

Alakline

I
(lSO-105-

to Perspiration

Colour Fastness to Orycleaning
5 4.5
4

Colour fastness to perspiration (change in shade) Navy

~3.5 .~ 3 ~ 2.5 J...-__

_" ... -:;;:;-r
Concentration

g
'"

2

~ 15

1
0.5

O~-----r------__-----r------~----~
0.0% 1.0% 1.5% 2.0%

2.5%

j--i.t--

Acidic

~

3.0%

Concentration

I-+- Red -

Navy _._

Black

I
DOl).

F·ig. 3 (b) : Colour fastness to Perspiration E04).
Colour fastness to perspiration (change in shade)

(ISO-l 05~

Fig. 2: Colour fastness to Dry-cleaning

(ISO-105-

As indicated in Tables 1-3 and Figs. 1-3 the optimum value of pigment: fixative concentration ratio is achieved at 1:2.5, above this i.e. at 1:3.0; the fastness properties decrease and fabric becomes stiff. By the addition of certain compounds, usually termed as plasticisers into the pigment printing composition, the distance between individual molecules can be increased. This gives an increased mobility of the fixative with a consequent softer handle. The swelling of the fixative film unfortunately decreases some aspects of the fastness properties particularly the crocking and the amount of the softener added must always result in compromises between handle and fastness. Our experimental results showed as indicated in Figs. 1 (a-c) that by the use of extra concentration of fixative beyond 2.5 %, dry crocking decreases but wet becomes stable. It was also

.J Ii
~ I~ 05

(1

()~-----------------1).0% 1.0%

'e

Black

:~~
'-5% 2.0% 2_5%

Concentration

I--i:r- Acidic

._._

Alakline

I
(ISO-l 05-

Fig. 3 (C): Colour fastness to Perspiration E04).

observed from tables and figures that the fastness properties of Red print are better as compared to the Navy and Black prints.

MANSOOR IQBAL

et ai;

J.Chem.Soc.Pak.,

Vol. 31, No.1, 2009

149

Experimental Material Scoured and bleached, optical brightener free 100 % woven cotton fabric (150 g/rn", 111 plain weave) have an absorbency 2.3 em was used for pigment printing purpose. Three commercial pigments Zycron Blue CBR, Zycron Red F4R and Zycron Black were used. World chern product Flow print TA160 used as thickener, printofix binder 77N liquid (acrylate based copolymer) used as binder and printofix fixative WB liquid (methylol melamine based) used as a fixative. All auxiliaries were of commercial grade. Equipment Printing was carried out by laboratory hand screen-printing. Samples were cured on curing machine of Rapid. Crocking evaluated on AATCC Crockmeter (CM-5 SDL Atlas), Perspiration carried out on Perspirometer (SDL Atlas England) and Drycleaning tests were carried out on HT Dyeing Machine of Rapid. Fastness rating was evaluated on colour matching cabinet by comparing with grey scale. The viscosity of the thickener paste was determined by Brookfield viscometer (DY -E model) with spindle number 6. Printing Process Stock Thickener Paste Preparation Stock thickener Paste was prepared by dissolving 3 % Flow print TA 160 thickener in soft water by heavy stirring and also add 1 % liquor ammonia to achieve a pH 8-9. The viscosity of the resulting thickener paste was 32000 cps. Print Paste Preparation Print paste was prepared by adding the required amount of pigment, thickener paste, binder and fixative to achieve the print paste viscosity 26000 cps. The general recipe prepared is given by, Pigment (3 %) Printofix Binder 77N Printofix fixative WB Thickener paste For Red Shade: Zycron Red F4R 30 glkg 90 glkg y glkg zglkg 1 kg 30 glkg

For Black Shade: Zycron Black For Navy Shade: Zycron Blue CBR Zycron Black MD Print Procedure

30 glkg

30 glkg 10 g/kg

The printed fabric dried at 120°C for 2 min and cured at 155°C for 5 minutes. Fastness Testing The fastness properties were determined

specific tests used were ISO-I05-E04 (color fastness to perspiration), ISO-105-DO 1 (color fatness to drycleaning), AATCC-08 (color fastness to crocking). Conclusions In the present work, investigations have been carried out to evaluate the fastness properties of pigment printed fabric by the use of acrylate based binder and melamine based fixative. By the above investigation the following conclusions have been drawn. The fastness properties like crocking, drycleaning and perspiration of the final print increases progressively and attain a maximum value at pigment and melamine fixative ratio up to 1:2.5. It is also evident that further application of the fixer results in poor fastness rating. Above 1:2.5 ratio the fabric becomes stiff or harsh handle, which is not the desired quality of the final print. The excessive amount of fixative normally used in textile industry is unnecessary. The results also indicate that the fastness properties of Red pigment print are found to be better as compared to the Navy and Black print. The improvement in the fastness properties up to I:2.5 ratio is due to the fact that acrylate based binder contains self-cross linking groups, these groups reacts with each other or with the hydroxyl group of cellulosic substrate. Fastness enhancement is also due to the extra crosslinking reaction of melamine fixative with acrylate based copolymer binder. As a result of the reaction between fixative and binder, an increase in the mechanical stability and decrease in the water solubility of the final print is also the main contributing factor for the improvement in the fastness properties.

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Reference 1. R. M. Christie, The Chemistry of Colour Application, Blackwell Science Ltd. London, p. 167 (2000). W. C. Miles, Textile Printing, Society of Dyers and Colourist Bradford England, p. 140 (2004). A. C. Nuessle, J. Chem. Ind., 49, 1580 (1966). W. Schwindt, Rev. Prog. Coloration, 2, 33 (1971). W. C. Miles, Textile Printing, Society of Dyers and Colourist Bradford England, p. 145 (2004). v. A. Shenai, Chemistry of Textile Auxiliaries,

2. 3. 4. 5. 6.

Sevak Publisher Mumbai, p. 231 (2002). R. M. Christie, The Chemistry of Colour Application, Blackwell Science Ltd. London, p. 169 (2000). 8. V. A. Shenai, Technology of Textile Printing, Sevak Publisher Mumbai, p. 338 (1990). 9. Colour Fastness to Perspiration, ISO-105-E04 (1994). 10. Colour Fastness to Crocking, AATCC Test Method-8 (2005). II. Colour Fastness to Dry-Cleaning, ISO-lOS-DO I (1990). 7.

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