Washing textiles which contain elastane

To finish textiles containing elastane it is necessary to first remove the silicone oil from the elastane fibre. Solvent-free removal systems are preferred for environmental reasons. We have pointed out those factors which are of importance for the washing process and which affect the washing results as well as the advantages of specially formulated surfactant systems.
Ms Silvia Held-Beller, Dipl. Eng. (Univ. for Applied Sciences) Mr Bernd Horrer, Dipl. Eng. (Univ. for Applied Sciences) CHT R. Beitlich GmbH, Division Pretreatment, D-72072 Tbingen

of all removed from the elastane fibre and then a stable oil/water emulsion is formed. Figure 1 shows the various phases of silicone oil removal. During stage 1 the textile substrate is brought into the washing liquor. The surfactants in the washing liquor form micelles. During stage 2 a spontaneous wetting of the textile takes place. The surfactant molecules decrease the interfacial tension between washing liquor and silicone layer. Now the surfactant molecules displace the oil contamination from the fibre (stage 3). This oil is removed from the fibre dropwise and emulsified into the washing liquor as micelles. Stage 4: The silicone oil is totally removed from the fibre. Surfacant molecules hold the emulsified oil drops in the washing liquor and prevent a reabsorption. This kind of silicone oil removal and formation of stable emulsion throughout the entire washing process can only be done by special surfactant systems. To visualize this, we tested various surfactant raw materials and surfactant formulations with regard to their emulsifying capacity, their emulsion stability and foaming behaviour. The foaming behaviour does not directly affect the silicone oil removal, but it is very important for the textile finisher that the applied detergent runs on the machine without any disturbances. Besides, silicone oil in the liquor can accumulate in the foam through the flotation effect and lead to stains when draining the liquor.

The continuously increasing consumption of elastane fibres over the last years shows that nobody wants to do without the advantages imparted to the textile substrates by these fibres. At first, elastane fibres were used to produce textile substrates with high stretching properties and high elastic force, but today these fibres are also used for womens and mens outerwear in order to impart a better and permanent form stability. Elastane fibres are prepared with 2 6 % polydimethyl siloxanes during production to make further processing easier. One requirement for finishing textile with elastane is the removal of these silicone oils.

Stains are the consequence if these preparations are not totally removed which are often not seen until after dyeing or printing and makes the removal of these stains normally impossible. That is why the washing process is of special importance for finishing fibres containing elastane.

How surfactants work

Removal of lubricants containing silicone during the washing process mainly depends on two procedures. The silicone oil is first

S ta g e 1

S ta g e 3

Experimental Part
These surfactant raw materials were chosen due to their good emulsifying properties (Table 1).

S ta g e 2

S ta g e 4

Petroleum ether extraction

H y d ro p h ilic p a rt o f th e s u rfa c ta n t F a b ric H y d ro p h o b ic p a rt o f th e s u rfa c ta n t S ilic o n e o il

Fig. 1: Performance of surfactants when removing silicone oil from materials containing elastane

The greige fabric and the washed fabric were extracted with a Solvent Extractor SER 148 from the VELP Scienticia Company with petroleum ether 40 60 C.

Side 1

Extraction with the Solvent Extractor is equivalent to an automatic extraction according to Soxhlet. The fabric is extracted for 30 minutes in a hot solvent. Then the extraction tubes are lifted out of the liquid and the fabric is again rinsed for 30 minutes with the solvent. The solvent is distilled after extraction and the extracts are weighed after cooling down.

Raw materials

Fatty alcohol ethoxylate Castor oil ethoxylate Fatty amine ethoxylate Fatty amine oxide Alkane sulphonate FELOSAN NOG LAVOTAN SE

C12/14-alcohol with 6 EO Castor oil with 7 EO Coconut fatty amine with 10 EO Bis(2-hydroxyethyl)tallow fat amine oxide C13/15-sek. Alkane sulphonate, Na-salt Synergetic surfactant system based on modified fatty alcohol ethoxylates Synergetic surfactant system based on nonionic- / anionic surfactants

Formulations

Determination of silicone oil

To judge the efficiency of the silicone oil removal it is not enough to extract the washed fabric with petroleum ether and to compare the extract of the washed fabric with the greige fabric because the petroleum ether extract is the sum of parameters for all substances which are soluble in petroleum ether. Methods are required with which the silicone oil itself can be quantitatively determined. Principally suitable for this are: Atomic Absorption Spectroscopy (AAS) Nuclear Magnetic Resonance Spectroscopy (1H-NMR)

For the washing process two different materials were used a) Polyamide/Elastane wovens (80/20) with a Silicium content of 3700 ppm (= 0,98 % Polydimethyl siloxane on the fabric) b) Cotton/Elastane wovens (91/9) with a Silicium content of 1300 ppm (= 0,34 % Polydimethyl siloxane on the fabric) The washing trials were done with a Mathis Labomat Typ BFA-12 in 300 ml beakers. The washing recipe is shown in Table 2.
Table 1: Applied surfactants

most by 20 % from the measuring value and thus supply a sufficiently exact possibility to judge the efficiency of silicone oil removal (Fig. 2).

2,0 g/l Surfactant 1,0 g/l Soda ash Liquor ratio Temperature Time Rinsing 1:20 80 C 30 min 1x 60 C, 1x 40 C, 2x cold

Emulsifying and Dispersion Test

The following is preset in a 600 ml beaker glass (high form): 3.0 g/l Auxiliary a) without electrolyte b) with 1.0 g/l Soda ash 5.0 g/l dyed Silicone Oil AK 2000 (Wacker) (50.0 g silicone oil are homogeneously stirred with 0,1 g Ceresred 7B.)

Table 2: Washing recipe

Determination of Silicium by means of AAS

To determine the silicone oil removal, the content of silicium in the petroleum ether extract is determined by means of atomic absorption spectroscopy. The silicone oil removal can be calculated by comparing with the greige fabric. Realization: The petroleum ether extract is reabsorbed in petroleum ether and led into a 50 ml measuring flask. The silicium content is then determined with the AAS directly from the petroleum ether solution.

Now 200 ml hot water (80 C) are added and the simulated washing liquor is treated for 1 minute with the Ultra-Turrax at 20 000 rpm. Now the liquor is refilled into glasses like shown in figures 7 and 8 and visually judged after 1 hour.

`~==~=== ==p=
16.0% 14.0% Si content in extract [%] 12.0% 10.0% 8.0% 6.0% 4.0% 2.0% 0.0% Sample 1 Sample 2 Sample 3
Fig. 2: Comparison of the measuring methods for determining the Si content
8.4% 6.7% 10.3% 9.0% 8.9% 9.2%

Si measuring with AAS

Si measuring with H-NMR

Determination of silicium by means of 1H-NMR

The above mentioned AAS method is checked and secured by means of a quantitative nuclear magnetic resonance spectroscopy. Results of the two methods deviate at the

Side 2

Results and Discussion

Silicone oil removal
The various surfactant raw materials show different degrees of efficiency with regard to the silicone oil removal.

factant formulation such as A general statement is that 80 to 90 % of the silicone oil preparation can be removed with a good detergent on polyamide/elastane fibres depending on the fabric quality. Contrary to this, it is not possible to get a silicone oil removal of more than about 50 % on cotton/elastane articles (Fig. 7).

By increasing the surfactant quantity and washing temperature it is possible to increase the silicone oil removal to about 54 % with a surfactant formulation using FELOSAN NOG (Fig. 7). The reason for the lower removal is the diffusion of the silicone oil into the cotton fibre during storage. Removal of the silicone oil from
Wasching recipe:
2 g/l Surfactant 1 g/l Soda ash LR 1:20 30 min at 80 C Rinsing

m~Lb~~=t=EUMLOMF
Greige fabric Without surfactant Fatty alcohol ethoxylate Castor oil ethoxylate Fatty amine ethoxylate Fatty amine oxide Alkane sulphonate FELOSAN NOG LAVOTAN SE 0,0%
0.22% 0.31% 0.34% 0.17% 0.29% 0.14% 0.17% 0.8% 1.1% 1.0% 0.8% 0.8% 1.2% 0.56% 0.98% 1.7% 1.6% 2.8%

m~Lb~~=t=EUMLOMF
Without surfactant Fatty alcohol ethoxylate Castor oil ethoxylate
43%

78% 68% 65% 83% 70% 86% 83%

Washing recipe:
2 g/l Surfactant 1 g/l Soda ash LR 1:20 30 min at 80 C Rinsing

Fatty amine ethoxylate Fatty amine oxide Alkane sulphonate FELOSAN NOG LAVOTAN SE

0,5%

1,0%

1,5%

2,0%

2,5%

3,0%

0%

20%

40%

60%

80%

100%

Content of silicone oil Petroleum ether extract

Silicone oil removal

Fig. 3: Results of the washing trials with polyamide/elastane wovens

Fig. 4: Results of the silicone oil removal with polyamide/elastane wovens

The fatty alcohol ethoxylate and fatty amine oxide give good silicone oil removal results on polyamide/elastane articles (Fig. 3). The castor oil ethoxylate, the fatty amine ethoxylate and the alkane sulphonate show poorer emulsifying properties and remove much less silicone oil. Compared with the fatty amine oxide, the petroleum ether extract of the fatty alcohol ethoxylate is much higher even though the silicone oil removal is also good. Fatty alcohol ethoxylates partially adsorb on the fibre surface and therefore have a higher petroleum ether extract. The temperature for the last rinsing baths shall be as low as possible when fatty alcohol ethoxylates are used in practice. Comparison of the petrol ether extracts and the content of silicone oil clearly show that the petroleum ether extract itself cannot give an exact statement about the degree of silicone oil removal. The quantitative silicone oil removal is absolutely necessary before making any statement. The results show that the silicone oil removal can be increased further by choosing an optimal sur-

When working with the same washing conditions as on polyamide /elastane articles, i.e. 2 g/l surfactant and a washing temperature of 80 C, the silicone oil removal is between 20 and 40 % (Fig. 5 and 6).

cotton is much more difficult than removal of silicone oil from the surface of elastane fibres. Fatty alcohol ethoxylates are an exception. This shows that there is a conjunction between the silicone oil removal of cotton/elastane articles and removal of cotton

`Lb~~=t=EVNLVF
Greige fabric Without surfactant Fatty alcohol ethoxylate Castor oil ethoxylate Fatty amine ethoxylate Fatty amine oxide Alkane sulphonate FELOSAN NOG LAVOTAN SE
0,37% 0,30% 0,25% 0,28% 0,28% 0,28% 0,27% 0,22% 0,23% 0,6% 0,7% 0,9% 1,0% 1,5%

Washing recipe:
0,9% 0,8% 0,7% 2 g/l Surfactant 1 g/l Soda ash LR 1:20 30 min at 80 C Rinsing 1,3%

0,0% 0,2% 0,4% 0,6% 0,8% 1,0% 1,2% 1,4% 1,6%

Content of silicone oil Petroleum ether extract

Fig. 5: Results of washing trials with cotton/elastane wovens

Side 3

`Lb~~=t=EVNLVF
Without surfactant Fatty alcohol ethoxylate Castor oil ethoxylate Fatty amine ethoxylate Fatty amine oxide Alkane sulphonate FELOSAN NOG LAVOTAN SE 0% 5%
24% 24% 24% 27% 41% 38% 19% 32% Washing recipe:
2 g/l Surfactant 1 g/l Soda ash LR 1:20 30 min at 80 C Rinsing

f==~===~== ~~=~=~==~= =`Lb~~=~

0,37%

Greige fabric

1,5%

2 g/l FELOSAN NOG 30 min at 80 C 4 g/l FELOSAN NOG 30 min at 98 C 0,0%

0,22% 0,9%

0,17% 0,8%

10% 15% 20% 25% 30% 35% 40% 45%

Silicone oil removal

0,2%

0,4%

0,6%

0,8%

1,0%

1,2%

1,4%

1,6%

Content of silicone oil Petroleum ether extract

Fig. 6: Results of silicone oil removal with cotton/elastane wovens

Fig. 7: Improving the washing results by increasing the application concentration and temperature

electrolytes. We therefore repeated the same trial and added 1 g/l soda soilings. Surfactans and surfactant formulations which are used for silicone oil removal on cotton/elastane articles must also be capable of removing cotton soilings besides emulsification of silicone oil. Removal of about 50 to 55 % silicone oil on cotton/elastane articles cannot be increased. Such results are sufficient for the following dyeings to achieve even and stainless results.

and the temperature of the first rinsing bath is to be avoided.

ash (see washing recipe). The results are shown in figure 9. The emulsion stability differences are very obvious here. The two detergent formulations FELOSAN NOG and LAVOTAN SE show stable emulsions even in the presence of electrolyte. All surfactant raw materials which were used more or less show separations or deposits. Through the addition of electrolyte, the insufficiently stable emulsion breaks and the silicone oil creams or deposits on the glass walls. In daily work this means residues on the machines as well as deposits of the silicone oil on the fabric, mainly when the liquor is drained prior to the rinsing phase and if rinsing is not done in the overflow. If a surfactant is used
Table 3: Summary of the Properties
Silicone oil removal Fatty alcohol ethoxylate Castor oil ethoxylate Fatty amine ethoxylate Fatty amine oxide Alkane sulphonate FELOSAN NOG LAVOTAN SE

Summary
In table 3 we have summarized the properties of the tested surfactant raw materials and formulations. This clearly shows that the right formulation is needed to meet the requested demands in practice. These requests could only be met to a certain extent with some surfactant raw materials. The surfactant system with synergetic effects presents the necessary application profile. The pretreatment expert can select the optimum products for his process from the detergents we introduced here. The main advantages of LAVOTAN SE are the low fibre affinity of the surfactants as well as the exEmulsion stability Foaming behaviour continuous discontinuous

Emulsifying and Dispersion Capacity

As already explained under point How Surfactants Work, for an optimal washing result in practice, not only the degree of silicone oil removal is decisive, but also the emulsifying and dispersing capacity of the applied surfactants. Oil/water emulsion are sensitive to electrolyte like all emulsions. Electrolytes are always present either through the addition of soda or alkali for the washing process, through the salt content of the water or the alkaline earth content of the fabric. We therefore compared the surfactant raw materials you know with FELOSAN NOG and LAVOTAN SE. Figure 8 shows the emulsion stability without electrolyte. It very clearly shows that all tested liquors except the one with castor oil ethoxylate and anionic alkane sulphonate form stable emulsions. These liquors are not relevant for practice because they do not contain any

+ + + + ++

+ + + + ++

++ which is insufficiently stable to electrolyte, it is important to either

++ + tremely high electrolyte and emulsion stability. LAVOTAN SE is

rinse in the overflow or again add small quantities of a surfactant to the first rinsing bath. Moreover, a high temperature difference between the washing temperature

preferably used as detergent for the silicone oil removal during the bleaching process. FELOSAN NOG is a special development for discontinuous application fields.
Side 4

Silicone oil deposits

Silicone oil deposits

Fig. 8: Emulsifying and dispersion capacity without electrolyte 1 = without detergent, 2 = fatty alcohol ethoxylate, 3 = castor oil ethoxylate, 4 = fatty amine ethoxylate, 5 = fatty amine oxid, 6 = alkane sulphonate, 7 = FELOSAN NOG, 8 = LAVOTAN SE

Fig. 9: Emulsifying and dispersion capacity with electrolyte 1 = without detergent, 2 = fatty alcohol ethoxylate, 3 = castor oil ethoxylate, 4 = fatty amine ethoxylate, 5 = fatty amine oxid, 6 = alkane sulphonate, 7 = FELOSAN NOG, 8 = LAVOTAN SE

Thanks to its outstanding silicone oil removal for all kinds of fibres together with very good emulsion stability and low foaming, FELOSAN NOG is excellently suitable for batch processes. To achieve good washing results which means a very high removal of lubricants, its worth using selected surfactant formulations such

as FELOSAN NOG and LAVOTAN SE. These are not only capable of emulsifying silicone oils, but can also hold the emulsified oil during the entire washing process in solution. This is the only way of

preventing a reabsorption of silicone oil on the fabric and deposits of silicone oil on the machine walls. And this is last but not least the most important requirement to prevent stains.

Side 5