Dye aggregation and interaction of dyes with a water-soluble polymer in ink-jet ink for textiles

Detailed understanding of the interaction between dyes and additives and the aggregation behaviour of the dye molecules in aqueous solutions is required to develop ink-jet ink for textiles. In the present study, the aggregation behaviour of three acid dyes (CI Acid Red 88, CI Acid Red 13 and CI Acid Red 27) containing different number of sulphonate groups in aqueous solutions was investigated by means of visible absorption spectroscopy. As a result, the higher the solubility of the dyes in water (the larger the number of sulphonate groups in the dyes), the lower are the aggregation constants of the dyes. For all the dyes, the aggregation constants decreased with increasing temperature, indicating the exothermic process of the dye aggregation. The thermodynamic process for CI Acid Red 88 with one sulphonate group is less enthalpic and more entropic than that for CI Acid Red 13, which contains two sulphonate groups. CI Acid Red 27, which includes three sulphonate groups, hardly forms any aggregates. To elucidate the effects of the polymer additive, the binding constants of the dyes with the water-soluble polymer, poly(vinylpyrrolidone) and the aggregation constants of the dyes in aqueous polymer solutions were also estimated. In addition, the binding constants were influenced by the number of sulphonate groups in the acid dyes: the larger number of sulphonate groups diminished the binding constants. The aggregation constants in the presence of poly(vinylpyrrolidone) were smaller than those in its absence at every temperature for all dyes. This suggests that poly(vinylpyrrolidone) has disaggregation effects. Furthermore, poly(vinylpyrrolidone) makes the aggregation process less enthalpic with a greater entropic change. Thus, the aggregation process of the dyes in the polymer solutions is thermodynamically different from that in water, reflecting the interactions between the dyes and the polymer.