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“Formaldehyde-free leather” – a realistic objective?

Renate Meyndt, Heinz-Peter Germann
Lederinstitut Gerberschule Reutlingen (LGR, Germany)

1. Introduction
Recent market investigations reveal an increasing demand for “formaldehyde free”
leather. Probably this situation will become more critical due to the results of the re-
evaluation of the hazardous potential of formaldehyde and in consequence, its classi-
fication as a proven carcinogenic substance. Presently no regulation by law exists for
this chemical compound in the EU. But in lots of areas of application the amount of
formaldehyde contained in leather is limited by technical specifications or
eco-labels1, 2, 3.

Formaldehyde is used in large quantities as a starting material for the production of
synthetic aromatic and resin-tanning agents. During the production of these com-
pounds formaldehyde acts as a condensation agent, helping to get larger molecules.
Presenting different hydrolytic stabilities, the resulting condensation products are po-
tential sources of formaldehyde. Some dyeing auxiliaries, fat liquors and finishing
products are able to release formaldehyde as well.

However, high quality requirements cannot be met renouncing to use different tan-
ning and retanning agents and a wide range of dyeing auxiliaries and fat-liquors.
Therefore it seems to be necessary to develop a leather producing technology, which
meets the high quality requests and at the same time guarantees a minimal potential
of formaldehyde release of the resulting product.

Attempts to selectively bind free and part hydrolytic releasable formaldehyde in
leather with suitable compounds (scavengers) have been already reported4. The utili-
zation of most recently developed, in relation to this issue improved products and the
modification of some of the technological steps have also been investigated5.

Another modality to reduce the formaldehyde content of leather is to select the com-
ponents of the recipe on the basis of their potential to release formaldehyde. The
practicability has not been fully given yet because of the lack of an adequate analyti-
cal method capable to determine the free formaldehyde in tanning agents and auxil-
iaries. The development and validation of such a method was an essential part of this
research work. Further, it was investigated, if the interaction of chemicals and leather
matrix generates synergistic effects. In this context it was interesting to elucidate the
influence of the ageing process on the formaldehyde content of the leather. Addition-
ally, several compounds were tested to reveal their suitability for being used as for-
maldehyde scavengers.

2. Materials and Methods
On the basis of the preparatory work done within the TEGEWA-group a dynamic dif-
fusion method (in-house LGR-method) was developed and validated. This method is
conceived to determine free formaldehyde in products used in leather production and
ensures that no hydrolysis occurs.

In principle, the sample is placed in an U-tube and is heated at a temperature of 90
°C with an oil bath and kept at this level for 30 minutes. Released free formaldehyde

The internal validation experiments were followed by external ones. 1: Schematic outline of sample preparation The optimal sampling and sample preparation conditions were established experi- mentally. So. 2 is continuously swept with a stream of nitrogen gas in a cartridge containing dinitro- phenylhidrazine where it is collected. but ring trials showed that this attempt as not feasible in routine. In consequence readily prepared commercial formaldehyde hydrazone solutions were used. .g. HPLC N2 DNPH gas VV flow meter tank ------ 90 °C sample Fig. e. After elution the formaldehyde is analysed by means of HPLC (see figure 1). 9. were determined: • The formaldehyde content of all reagents and auxiliaries used in the method • The way of collection of free formaldehyde out of the sample (static or dy- namic) • The adequate parameters of sampling as Flow rate of the inert carrier gas Optimisation of the washing steps with inert gas Heating duration (sampling time) Heating temperature • Optimal elution conditions of formaldehyde-derivative from the cartridge • Stability of the analyte on the collection medium and in the final measuring so- lution. part 51 7 and the specialized literature 8. The calibration was carried out by means of an external standard over the range 0. The statistical evaluations of both sampling and analytical method were done in ac- cordance to DIN 32625 6 and DIN 38402. Initially.5 – 50 µg/10 ml. 10 as well. The most important products used in upholstery leather manufacturing were tested with the newly developed procedure 11 and their content of free and under the condi- tions of the method releasable formaldehyde was determined. the calibration was made over the whole procedure. Several interla- boratory trials on solid and fluid samples helped to improve both the robustness of the procedure and the SOP.

Results 3. agents 16 < RQL . All samples were conditioned (23 °C/ 50 % rel. During the whole period the leathers were stored in well defined conditions (23 °C/ 50 % rel. 3 Two recipes (chrome and chrome-free tanning) that gave a certain formaldehyde content served as a basis for scavenger investigations. The reliable quantification limit (RQL) of the test method was in all cases 0. molecular formaldehyde was determined in more than 70 chemicals typical for the production of upholstery leather (see Table 1).5 mg/kg product. Because of its irrelevance for the manufacture it was re- nounced to refer the results to dry matter. humidity) immediately after the test for 48 hours and analysed according to the same procedures (VDA 275. Two upholstery leathers (chrome and chrome-free tanned) with the lowest formalde- hyde content were chosen. two leathers (chrome and chrome-free tanned) with a somewhat high for- maldehyde content were tested periodically.73 Fat-liquoring + waterproof. relative humidity and time (see table 2) were performed.1 Determination of free formaldehyde in tannins and auxiliaries Using the dynamic diffusion procedure (LGR-method) free.939 Preservatives 5 < RQL . 2.5 %. the potential to bind available formaldehyde in the leather matrix of different inorganic and organic sub- stances was studied. Thus. The assessment of the scavenging potential of the different compounds bases on the results obtained with the VDA 275 method.51 . After testing auxiliaries and assessing their formaldehyde release potential recipes for the production of crust were developed. according to all test procedures available.280 Dyes and dyeing auxiliaries 5 < RQL .12 Beamhouse auxiliaries 5 < RQL Finishing materials 8 < RQL . at a four weeks interval. Further. 3. Additionally. Four artificial ageing test series with different conditions of temperature. draft DIN 53315 A). leather properties such as touch and appear- ance were considered. Resulting crusts and leathers were tested according to four different analytical procedures: two extraction procedures (draft DIN 53315 A and B 12) and two gas phase methods (VDA 275 13 and LGR-method) aim- ing at partly different bonding states of formaldehyde.220 Other auxiliaries 6 < RQL . 5 %) of the potential scavenger were used. Product classes Number of Free formaldehyde tested (mg/kg) products Tanning and retanning agents 30 < RQL . Starting with South Germany raw hides from wet blue and wet white were produced. humidity). In each experimental series three different concentrations (1 %. Formaldehyde scavenger addition occurred in a last step of leather production. For comparison leather produced ac- cording to the same recipe but without adding scavenger was used.

1 Formaldehyde scavenger The possibility to reduce the formaldehyde content in leather by means of selective reacting substances is known and was confirmed once more by the experiments per- formed. 3)) • Organic compounds and products (melamine. auxiliary A (fig.2 Investigations in the production of formaldehyde-free leather 3. the findings are situated within larger intervals. 3. auxil- iary B (fig. 4)) 80 Formaldehyde (mg/kg dm) 70 60 50 Crust 40 Leather 30 20 10 0 0 1% 2.5% 5% Scavenger Amount Fig. In case of chrome tanned leather the following potential formaldehyde scavengers were tested: • Inorganic compounds and products (sodium dithionite. mimosa. 2). dicyandiamide. In laboratory practice the analytical method proved to be inappropriate in case of tannins based on glutaraldehyde. thus exhausting the capacity of the cartridge (75 µg carbonyl compounds). sodium perborate.2. 4 Table 1: Free formaldehyde in different product classes As expected. It has to be mentioned that the formaldehyde content of a given product varies to some extent from one con- tainer to the other and can alter during storage as well. sodium disulphite (see fig. Under the sampling conditions this aldehyde is partly volatilized and reacts with DNPH. 2: Effect of sodium disulphite (chrome tanned leather) .

The observed deviations from the tendency of decreasing the formaldehyde content were attributed to the analytical procedure. 5). 3: Effect of auxiliary A (chrome tanned leather) Comparing scavenging capabilities inorganic compounds proved to be very effective (Fig. 4: Effect of auxiliary B (chrome tanned leather) .5% 5% Scavenger Amount Fig.5% Scavenger Amount Fig. 90 Formaldehyde (mg/kg dm) 80 70 60 50 Crust 40 Leather 30 20 10 0 0 1% 2. Due to differences in thickness and structure from one test specimen to the other considerable scattering of the re- sults is possible. 5 Formaldehyde (mg/kg dm) 80 70 60 50 Crust 40 Leather 30 20 10 0 0 1% 2.

5% 5% Scavenger Amount Fig. chrome tannage) As expected. The observations made for chrome-tanned leather were fully confirmed.2 Influence of product selection The production of crust (see fig. 3. Part hydrolytic formaldehyde releasable under the conditions stated by the extraction procedures (DIN A and B) partly remained (persisted). free formal- dehyde of the resulting crust Cr C dropped off in the area of the quantification limits of the two gas phase methods (VDA 275 and LGR). In case of chrome-free recipes the effectiveness of sodium disulphite and melamine were tested. The addition of scavengers caused a considerable increase of the analyte. sodium dithionite caused a change of hue from brown to greenish. But with respect to the dyeing quality several of the scavengers produced alterations. a considerable decrease of the formaldehyde content was achieved (crust Cr B). After eliminating even minimal formaldehyde releasers from the recipe. Repeatability trials with the same recipe showed deviations of the analyte content determined according to DIN A and B up to 40 %.2. 6 Formaldehyde decrease (%) 120 100 Na-dithionite Na-disulphite 80 Na-perborate Melamine 60 Dicyandiamide 40 Auxiliary A Mimosa 20 Auxiliary B 0 0 1% 2. this substance is inap- propriate for this purpose. 6.. So. crust Cr A) according to a well-experienced up- holstery leather recipe resulted in a considerable increase of formaldehyde content compared to the raw material (wet blue). In consequence. The assessment of chrome tanned leathers showed that only melamine deteriorated the touch significantly. low formaldehyde re- leasers. 5: Efficiency of the tested scavengers (VDA 275. . only samples of the experiments with sodium perborate (oxidant) pre- sented a detectable amount of chromium VI. Trials to further reduce part hydrolytic formaldehyde completely failed. Sodium perborate produced a darkening while the auxiliaries A and B gave rise to a slight lightening of the leather colour. Replacing products identified by means of the LGR test procedure as formaldehyde sources with similar.

Product selection proved to be more effective than the use of formaldehyde scavengers. 7). That is a clue on the existence of synergistic effects. 7 For chrome-free leather recipe development the similar results were obtained (see fig. So. 6: Development of recipes for low formaldehyde release (chrome tannage) Formaldehyde (mg/kg dm) 450 400 350 300 DIN A 250 DIN B 200 VDA 150 LGR 100 50 0 Crust I Crust II melamine Crust I + 1% Fig. Formaldehyde (mg/kg dm) 160 140 120 DIN A 100 DIN B 80 VDA 60 LGR 40 20 0 A e a B C te in os hi st st st am im lp ru ru ru su C el m C C m di + C a- + C st N st ru + C ru C st C ru C Fig. even the selection of low-formaldehyde products was not able to fully reduce hy- drolysable formaldehyde in resulting leathers. There is no simple mathematical rela- tionship between the free formaldehyde content of the used leather auxiliaries and that of the ensuing leather. 7: Development of recipes for low formaldehyde release (chrome-free tannage) .

83 2.39 1. Time UV Experiment % °C h h V1 50 38 24 96 168 48 V2 90 38 24 96 168 48 V3 50 50 24 96 168 V4 90 50 24 96 168 Table 2: Artificial ageing parameters The results (see tables 3 and 4) indicate that. adequate conditions being chosen according to draft IUF 412 14 (see ta- ble 2).40 1.60 1.21 V2 23.82 4.25 2.12 8.3 Influence of ageing Artificial Ageing In order to reveal what happens with formaldehyde content during use two leathers with a low content of formaldehyde.83 13.76 9. The formaldehyde content of the examined upholstery leathers was deter- mined according to DIN 53 315 A and VDA 275.32 22. Trial Formaldehyde (mg/kg) 24h 96h 168h 168+48h UV DIN A VDA 275 DIN A VDA 275 DIN A VDA 275 DIN A VDA 275 V1 14.63 V2 15.41 15.29 V4 16.09 11.80 2.44 2. with respect to recipes.68 8.48 3. which yield low values of free formaldehyde.34 11. one for each tanning mode.06 V4 10. VDA 275: 5.81 10.77 1.81 1.52 1.35 1.63 16.98 3.86 0.48 21. 8 Whilst in case of leather with relatively high formaldehyde values scavengers proved to be very effective (VDA 275). hum.53 2.68 1.50 mg/kg Table 3: Results of artificial ageing experiments on chrome tanned leather Trial Formaldehyde (mg/kg) 24h 96h 168h 168+48h UV DIN A VDA 275 DIN A VDA 275 DIN A VDA 275 DIN A VDA 275 V1 17.2.92 5.95 10.75 15.48 20.71 2.39 6.79 20.94 V3 10. Parameter/ Rel.34 19.39 16.56 16.95 . 3.28 3. Temp.32 1.43 Leather Cr C: Formaldehyde content according to DIN 53 315 A: 15. were exposed to arti- ficial aging.83 3.10 3. scavengers were not able to realise a further decrease of it.40 3.63 3.42 V3 17.71 2.86 mg/kg.12 2. at least for the tested recipes and un- der the applied conditions of humid heat.67 2. the formaldehyde release potential of recipe components does not increase.01 2.

8 and 9).12 mg/kg. VDA 275: 0. in case of chrome-free tanned leather an obvious tendency to diminish was observed.97 mg/kg Table 4: Results of artificial ageing experiments on chrome-free leather Storage Storage experiments were performed on two leathers with a relatively high content of formaldehyde. 9 Leather II: Formaldehyde content according to DIN 53 315 A: 17. of Weeks Fig. 8: Variation of formaldehyde content during storage (chrome tanned leather) 450 Formaldehyde (mg/kg dm) 400 350 300 DIN A 250 DIN B 200 VDA 150 LGR 100 50 0 0 4 8 12 16 20 24 No. but no noteworthy increase (see fig. The formaldehyde values of the tested leathers showed slight varia- tions during the tested period of time. 200 Formaldehyde (mg/kg dm) 180 160 140 DIN A 120 DIN B 100 VDA 80 LGR 60 40 20 0 0 4 8 12 16 20 24 No. of Weeks Fig. In contrary. 9: Variation of formaldehyde content during storage (chrome-free leather) .

. N. 98. B. DIN 38 402.& Häutemarkt. 8. Leder. 7. Leather. • The repeated analysis of leathers with a relatively high formaldehyde content stored in standard climate conditions over a period of 6 months did not result in any significant increase of the analyte (DIN 53 315 B). • The efficiency of formaldehyde-scavengers is also depending on the initial formaldehyde content of the leather. 1966. Doerffel. Cape Town. Funk. 5. 65. G. Teil 42: Auswertung von Ringversuchen (1984). Weinheim. JALCA. p. Leather International. G.03. References 1.: Formaldehyde – the final straw?. Synergistic effects in the leather ma- trix are obviously existing. 9-2002. 2001. 1992.. Conclusions The results of the performed investigations may be summarised as follows: • The analytical procedure for the determination of free formaldehyde in prod- ucts used in leather manufacturing provides reproducible results. p.: Qualitätssicherung in der Analyti- schen Chemie. Wood. Hueffer. . S. However. VEB Deutscher Verlag für Grundstoffindustrie. Novem- ber 2001. Erfassungs. 25. 4. Damann. 9.: Scavenging of analysable formaldehyde in woolskins tanned with phosphonium compounds. G. Cory. VCH Verlagsgesellschaft. Wolf. 6. DIN 32 625: Nachweis-. 07. und Pabst. 10 4. J. • The method is suitable to identify formaldehyde sources within the recipe. Lampard.01 – Session 2.und Bestimmungsgrenze (1994). the part hydrolytic releasable formalde- hyde could not be completely eliminated. F. • The artificial ageing of leathers with low formaldehyde content caused no sig- nificant increase of the measurable formaldehyde. 2. G. K. W. 3. p. and Donnevert. Allsop.: Bildung von Formaldehyd im Leder .: An update on environmental constraints. T. Proceedings XXVI IULTCS-Congress.: Statistik in der analytischen Chemie. 2002. • By selecting recipe chemicals on the basis of free formaldehyde content de- termined with the LGR-method leathers with considerably low formaldehyde contents were produced. 496. Teil 51: Kalibrierung von Analysenverfahren (1986). April 2001. 97.Ur- sachen und Vermeidung. DIN 38 402. p. V. 10.: Is the level of environmental testing for leather necessary?.

draft: Bestimmung des Formaldehydgehaltes in Leder (1996). IUF 412. 13. (2002). VDA 275: Bestimmung der Formaldehydabgabe – Messverfahren nach der modifizierten Flaschen-Methode (1994). draft: Fastness tests – Change in colour with accelerated aging. DIN 53 315. 14. 11 11. LGR-intern SOP: Determination of free formaldehyde content of leather auxil- iaries. . 12.