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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
2

is continuously swept with a stream of nitrogen gas in a cartridge containing dinitro-


phenylhidrazine where it is collected. After elution the formaldehyde is analysed by
means of HPLC (see figure 1).

HPLC

N2
DNPH

gas
VV flow meter
tank
------
90 C
sample

Fig. 1: Schematic outline of sample preparation

The optimal sampling and sample preparation conditions were established experi-
mentally. So, e.g. 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.

The statistical evaluations of both sampling and analytical method were done in ac-
cordance to DIN 32625 6 and DIN 38402, part 51 7 and the specialized literature 8, 9, 10
as well. The calibration was carried out by means of an external standard over the
range 0.5 50 g/10 ml. Initially, the calibration was made over the whole procedure,
but ring trials showed that this attempt as not feasible in routine. In consequence
readily prepared commercial formaldehyde hydrazone solutions were used.

The internal validation experiments were followed by external ones. Several interla-
boratory trials on solid and fluid samples helped to improve both the robustness of
the procedure and the SOP.

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.
3

Two recipes (chrome and chrome-free tanning) that gave a certain formaldehyde
content served as a basis for scavenger investigations. Thus, the potential to bind
available formaldehyde in the leather matrix of different inorganic and organic sub-
stances was studied. In each experimental series three different concentrations (1 %,
2.5 %, 5 %) of the potential scavenger were used. 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. The assessment
of the scavenging potential of the different compounds bases on the results obtained
with the VDA 275 method. Additionally, leather properties such as touch and appear-
ance were considered.

Starting with South Germany raw hides from wet blue and wet white were produced.
After testing auxiliaries and assessing their formaldehyde release potential recipes
for the production of crust were developed. 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.

Two upholstery leathers (chrome and chrome-free tanned) with the lowest formalde-
hyde content were chosen. Four artificial ageing test series with different conditions
of temperature, relative humidity and time (see table 2) were performed. All samples
were conditioned (23 C/ 50 % rel. humidity) immediately after the test for 48 hours
and analysed according to the same procedures (VDA 275, draft DIN 53315 A).

Further, two leathers (chrome and chrome-free tanned) with a somewhat high for-
maldehyde content were tested periodically, at a four weeks interval, according to all
test procedures available. During the whole period the leathers were stored in well
defined conditions (23 C/ 50 % rel. humidity).

3. Results
3.1 Determination of free formaldehyde in tannins and auxiliaries
Using the dynamic diffusion procedure (LGR-method) free, molecular formaldehyde
was determined in more than 70 chemicals typical for the production of upholstery
leather (see Table 1). Because of its irrelevance for the manufacture it was re-
nounced to refer the results to dry matter. The reliable quantification limit (RQL) of
the test method was in all cases 0.5 mg/kg product.

Product classes Number of Free formaldehyde


tested (mg/kg)
products

Tanning and retanning agents 30 < RQL - 73


Fat-liquoring + waterproof. agents 16 < RQL - 939
Preservatives 5 < RQL - 280
Dyes and dyeing auxiliaries 5 < RQL - 12
Beamhouse auxiliaries 5 < RQL
Finishing materials 8 < RQL - 220
Other auxiliaries 6 < RQL - 51
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Table 1: Free formaldehyde in different product classes

As expected, the findings are situated within larger intervals. 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.

In laboratory practice the analytical method proved to be inappropriate in case of


tannins based on glutaraldehyde. Under the sampling conditions this aldehyde is
partly volatilized and reacts with DNPH, thus exhausting the capacity of the cartridge
(75 g carbonyl compounds).

3.2 Investigations in the production of formaldehyde-free leather

3.2.1 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.

In case of chrome tanned leather the following potential formaldehyde scavengers


were tested:
Inorganic compounds and products (sodium dithionite, sodium disulphite (see
fig. 2), sodium perborate, auxiliary A (fig. 3))
Organic compounds and products (melamine, dicyandiamide, mimosa, 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. 2: Effect of sodium disulphite (chrome tanned leather)


5

Formaldehyde (mg/kg dm) 80

70

60

50
Crust
40
Leather
30

20

10

0
0 1% 2,5%

Scavenger Amount

Fig. 3: Effect of auxiliary A (chrome tanned leather)

Comparing scavenging capabilities inorganic compounds proved to be very effective


(Fig. 5). The observed deviations from the tendency of decreasing the formaldehyde
content were attributed to the analytical procedure. Due to differences in thickness
and structure from one test specimen to the other considerable scattering of the re-
sults is possible.

90
Formaldehyde (mg/kg dm)

80
70
60
50 Crust
40 Leather
30
20
10
0
0 1% 2,5% 5%

Scavenger Amount

Fig. 4: Effect of auxiliary B (chrome tanned leather)


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Formaldehyde decrease (%) 120

100 Na-dithionite
Na-disulphite
80 Na-perborate
Melamine
60
Dicyandiamide
40 Auxiliary A
Mimosa
20 Auxiliary B
0
0 1% 2,5% 5%
Scavenger Amount

Fig. 5: Efficiency of the tested scavengers (VDA 275, chrome tannage)

As expected, only samples of the experiments with sodium perborate (oxidant) pre-
sented a detectable amount of chromium VI. In consequence, this substance is inap-
propriate for this purpose. The assessment of chrome tanned leathers showed that
only melamine deteriorated the touch significantly. But with respect to the dyeing
quality several of the scavengers produced alterations. So, sodium dithionite caused
a change of hue from brown to greenish. Sodium perborate produced a darkening
while the auxiliaries A and B gave rise to a slight lightening of the leather colour.

In case of chrome-free recipes the effectiveness of sodium disulphite and melamine


were tested. The observations made for chrome-tanned leather were fully confirmed.

3.2.2 Influence of product selection


The production of crust (see fig. 6., 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). Replacing products identified by means of
the LGR test procedure as formaldehyde sources with similar, low formaldehyde re-
leasers, a considerable decrease of the formaldehyde content was achieved (crust Cr
B). Repeatability trials with the same recipe showed deviations of the analyte content
determined according to DIN A and B up to 40 %.

After eliminating even minimal formaldehyde releasers from the recipe, 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). Part hydrolytic formaldehyde
releasable under the conditions stated by the extraction procedures (DIN A and B)
partly remained (persisted).

Trials to further reduce part hydrolytic formaldehyde completely failed. The addition of
scavengers caused a considerable increase of the analyte.
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For chrome-free leather recipe development the similar results were obtained (see
fig. 7). Product selection proved to be more effective than the use of formaldehyde
scavengers.

So, 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. That is a clue on the existence of synergistic effects.
Formaldehyde (mg/kg dm)

160
140
120 DIN A
100 DIN B
80 VDA
60 LGR
40
20
0
A

a
B

te

in

os
hi
st

st

st

am

im
lp
ru

ru

ru

su
C

el

m
C

m
di

+
C
a-

+
C

st
N

st

ru
+
C

ru

C
st

C
ru
C

Fig. 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. 7: Development of recipes for low formaldehyde release (chrome-free tannage)


8

Whilst in case of leather with relatively high formaldehyde values scavengers proved
to be very effective (VDA 275), with respect to recipes, which yield low values of free
formaldehyde, scavengers were not able to realise a further decrease of it.

3.2.3 Influence of ageing

Artificial Ageing
In order to reveal what happens with formaldehyde content during use two leathers
with a low content of formaldehyde, one for each tanning mode, were exposed to arti-
ficial aging, adequate conditions being chosen according to draft IUF 412 14 (see ta-
ble 2). The formaldehyde content of the examined upholstery leathers was deter-
mined according to DIN 53 315 A and VDA 275.

Parameter/ Rel. hum. Temp. 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, at least for the tested recipes and un-
der the applied conditions of humid heat, the formaldehyde release potential of recipe
components does not increase.

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 14,92 5,34 11,10 3,76 9,63 3,83 13,82 4,63
V2 15,48 3,81 10,83 2,95 10,83 3,09 11,28 3,94
V3 10,44 2,68 8,80 2,12 8,25 2,06
V4 10,98 3,39 6,53 2,40 3,67 2,43
Leather Cr C: Formaldehyde content according to DIN 53 315 A: 15,86 mg/kg;
VDA 275: 5,50 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 17,12 2,56 16,71 2,63 16,71 2,79 20,01 2,21
V2 23,81 1,32 22,35 1,48 20,39 1,34 19,68 1,42
V3 17,77 1,75 15,60 1,41 15,40 1,29
V4 16,32 1,48 21,52 1,39 16,86 0,95
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Leather II: Formaldehyde content according to DIN 53 315 A: 17,12 mg/kg;


VDA 275: 0,97 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. The formaldehyde values of the tested leathers showed slight varia-
tions during the tested period of time, but no noteworthy increase (see fig. 8 and 9).
In contrary, in case of chrome-free tanned leather an obvious tendency to diminish
was observed.

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. 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. of Weeks

Fig. 9: Variation of formaldehyde content during storage (chrome-free leather)


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4. 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.
The method is suitable to identify formaldehyde sources within the recipe.
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. However, the part hydrolytic releasable formalde-
hyde could not be completely eliminated. Synergistic effects in the leather ma-
trix are obviously existing.
The efficiency of formaldehyde-scavengers is also depending on the initial
formaldehyde content of the leather.
The artificial ageing of leathers with low formaldehyde content caused no sig-
nificant increase of the measurable formaldehyde.
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).

References

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11. LGR-intern SOP: Determination of free formaldehyde content of leather auxil-


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