TEXTILE FINISHING WITH MCT--CYCLODEXTRIN

J.-P. MOLDENHAUER, H. REUSCHER Wacker-Chemie GmbH, Johannes-He-Str. 24, D-84489 Burghausen, Germany Wacker Biochem Corp., 3301 Sutton Road, Adrian, MI 49221-9397, USA

Abstract Monochlorotriazinyl--cyclodextrin (CAVASOL W7 MCT) is a reactive cyclodextrin derivative that can be covalently fixed to nucleophilic substrates by a condensation reaction. This new type of surface modification means a permanent transfer of cyclodextrin properties to the treated materials. An important application field of CAVASOL W7 MCT is the textile finishing process. Analogues to reactive dyes the MCT-cyclodextrin can be fixed to the fabric by well known methods and with common equipment. Cellulosic fibres are most suitable for the MCT-CD modification. Detailed fixation parameters have been worked out for cotton, but also mixed fibre materials like cotton / polyurethan or cotton / polyamide can be finished with CAVASOL W7 MCT in good yields. MCT-CD modified textiles can either absorb unpleasant odour by complexation of sweat components or release included guest substances like fragrances or pharmaceuticals over a long period of time.

1.

Introduction

Monochlorotriazinyl--cyclodextrin (CAVASOL W7 MCT) was presented in 1996 as the first reactive CD derivative for permanent surface modification manufactured on an industrial scale [1-3]. OR R = H or
O

Fig.1:

Molecular formula of CAVASOL W7 MCT

ONa N O N

RO

OR

Cl

The favourable CD properties like odour masking and slow release of guest compounds can be transferred to different substrates by a finishing process well known from the dyeing technology. Cellulosic materials are especially suitable for the modification with CAVASOL W7 MCT. The investigation of application methods revealed a successful fixation of CAVASOL W7 MCT to cotton textiles either by a Foulard process with dry heat or contact heat or by a printing process [4]. Details of the dry heat fixation process on cotton have been worked out in this study.

2.

Materials and Methods

Materials: CAVASOL W7 MCT is a product of Wacker-Chemie GmbH, Munich, Germany. The cotton fabric to be treated with CAVASOL W7 MCT is a product of Testfabrics, Inc., Middlesex, NJ, USA. Methods: CAVASOL W7 MCT was applied to cotton samples by a process comprising dipping in aqueous solution of CAVASOL W7 MCT, squeezing (solution uptake 80 100% of dry fabric), drying, heating and rinsing. The amount of fixed CD (in % by weight) was determined by exact weighing (gravimetric method) or was calculated via the increase of the nitrogen content measured by elemental analysis of the treated and untreated fabric.

3.

Results and Discussion

3.1 Fixation process Analogues to many reactive dyes CAVASOL W7 MCT is fixed to cotton by a nucleophilic substitution reaction of the fibre Hydroxy-groups at the Chlorotriazine s ring, induced by elevated temperature.
CD O N N N ONa Cl + HO-Fibre - HCl T CD O N N N ONa O Fibre

The fixation process can be run either under alkaline conditions (pH 10-11) by adding Na2CO3 or NaOH to the CAVASOL W7 MCT solution or under acidic conditions (pH 5), achieved e.g. by the addition of HCl. The highest fixation yield is usually reached by the alkaline procedure (s. 3.2), whereas the acidic process is preferred for white fabric due to minimized yellowing during the CD modification.

3.2 Fixation parameters Five main parameters for the fixation of CAVASOL W7 MCT to cotton have been investigated: temperature, time, concentration of the CAVASOL W7 MCT solution, moisture content of the fabric and pH value. 3.2.1 Fixation temperature / Moisture content

Pieces of cotton were finished at different temperatures between 90 and 170C for 5 minutes under alkaline conditions, comparing the MCT finish reached with samples predried at room temperature before fixation and with samples immediately finished after squeezing.

Fig. 2: Fixation temperature

8 drying RT (1) drying RT (2) without drying step

MCT finish [%]

Fixation conditions: 10% MCT, 2% Na 2CO 3, 5 min. 90 110 130 150 170

Fixation Temperature [C]

The MCT finish of pre-dried samples increases with the fixation temperature in a linear way from 1.5 to about 7% by weight (Fig. 2). When finishing cotton samples at 130 170C without pre-drying the amount of fixed CD is significantly lower due to partial hydrolysis of the Chlorotriazin moiety. A similar effect is observed with the acidic procedure. 3.2.2 Fixation time / pH value

Pieces of cotton were exposed after pre-drying to dry heat of 150C for 1 - 15 minutes under alkaline and acidic conditions in order to evaluate the influence of the pH value on the fixation process. Fig. 3: Fixation time
7 alkaline (1) alkaline (2) pH = 5 (1) pH = 5 (2)

MCT finish [%]

1 0 1 3 5

Alkaline conditions: Acidic conditions: 10% MCT, 10% MCT, pH = 5, 2% Na 2CO 3 , 150C 150C 7 10 15

Fixation time [min.]

With very short times of heat exposure the acidic fixation is less effective than the alkaline one. However, a comparable MCT finish can be reached either by an extension of the fixation time (Fig. 3) or by an increase of the fixation temperature.

3.2.3

Fixation yield

A very good fixation yield of 80 85% is achieved with CAVASOL W7 MCT by the application of dry heat (150C) for 5 minutes under alkaline conditions (Fig. 4). The same yields are observed for the acidic process at 170C. Fig. 4: Fixation yield
100

Fixation Yield [%]

80 60 40 20 0 80 100 120 140 160 180 Fixation conditions: 10% MCT, 2% Na 2CO 3, 5 min.

Fixation Temperature [C]

3.2.4 Concentration of CAVASOL W7 MCT

The amount of fixed CD on the fabric at certain fixation conditions (temperature, time, pH) can be controlled by the concentration of CAVASOL W7 MCT in the dipping bath. A linear relation is observed between the MCT concentration and the MCT finish to be reached (Fig. 5). However, the fixation yield is independent from the concentration of the solution, it only depends on the fixation conditions. Fig. 5: MCT concentration
8

MCT finish [%]

6 4 2 0 0 5 10 15

Fixation conditions: 2% Na 2CO 3, 150C, 5 min.

MCT concentration in solution [%]

Fixation yield: 80 - 85%

3.3 Fastness of the MCT--CD finish against washing Cotton T-shirts and socks with a finish of about 5% of CAVASOL W7 MCT were washed ten times with washing powder at 60C in a common washing machine and the MCT finish was analysed after 1, 5 and 10 washing steps. No significant decrease of the amount of fixed CAVASOL W7 MCT by this procedure was detected (Fig. 6).
6 5

MCT finish [%]

1 Washing step
3 2 1 0

5 Washing steps 10 Washing steps

T-shirts

Socks

Fig. 6: Fastness of the MCT finish against washing 3.4 Application of actives to MCT--CD finished textiles Two main procedures for the application of actives, e.g. fragrances, to textiles finished with CAVASOL W7 MCT have been worked out. On a laboratory scale the moist CD modified fabric is stored in an atmosphere of the active at 60C for some hours (vapour method). For technical applications the active is sprayed onto the CD finished fabric as a diluted aqueous solution or suspension. After drying at low temperature a controlled release of the active can be achieved by re-wetting the textile. 4. Conclusion

Cotton textiles can be finished with CAVASOL W7 MCT in good yields according to common technical procedures transferring the useful CD properties permanently to the fabric. The finish is fast against washing and the CD cavity is still accessible for guest compounds, which can be applied easily. References [1] [2] [3] [4]
H. Reuscher, R. Hirsenkorn, BETA W7 MCT New ways in surface modification, Proceedings of the 8th Intern. Symp. on Cyclodextrins, Budapest 1996, p. 553 558. Consortium fr elektrochemische Industrie GmbH, Cyclodextrinderivate mit mindestens einem stickstoffhaltigen Heterocyclus, ihre Herstellung und Verwendung, Offenlegungsschrift DE 44 29 229 A1 (1996). Consortium fr elektrochemische Industrie GmbH, Cyclodextrin derivatives having at least one nitrogen-containing heterocycle, their preparation and use, US 5728823. U. Denter, H.-J. Buschmann, D. Knittel, E. Schollmeyer, Textilveredlung 32 (1997), Nr. 1/2, p. 3339.