Application of Formaldehyde-free Finishes to Man-

made Fibre Fabrics and Performance Evaluation of the

Finished Fabric
Source: New Cloth Market

By: D. H. Joshi, H.D. Joshi, M.G. Patel and S. R. Naik

Introduction

Resin finishing, particularly easy-care finishing, of cellulosic textiles has developed over the last 70 years.
The demand for easy-care textiles with highly durable press ratings has resulted in significant advancements
in easy-care finishing. The treatment of cellulose to improve crease recovery and provide highly durable
press ratings is based on cross-linking of cellulose molecules through the finishing agent. Resin finishing
was initially carried out using products based on phenol-formaldehyde condensates, methylol melamine or
dimethylol urea.

These products led to high formaldehyde emissions. Owing to the varying opinions concerning the
probability that formaldehyde is a carcinogen, finishing agents with high formaldehyde emission are
undesirable. In many countries, legal regulations have been introduced and upper limits set for free and
releasable formaldehyde (formaldehyde limits).

Formaldehyde in Finishing and on the Finished Fabric

Cross-linking agents based on N-hydroxy methyl derivatives of ureas, carboxylic acid amides, carbamates
and aminotriazones contain small amounts of free formaldehyde. The chemically bonded formaldehyde in
the finishing agent, in the finishing bath and on the finished fabric can be present with different types of
bondings, each of which has a different stability to hydrolysis.

The hydroxy (alkoxy) methyl compounds, as well as some free HCHO, are transferred to the fabric during
impregnation. During drying and curing, cross-linking takes place with the hydroxyl groups of cellulose and
there is further release of HCHO by thermal or hydrolytic cleavage.

Some free formaldehyde is removed with the exhaust gas during drying and curing, some reacts with the
hydroxyl groups of cellulose and the rest remains on the fabric.

The factors which influence the presence of free formaldehyde during and after finishing are:

1) Free formaldehyde content of finishing agent or bath.

2) Type and amount of catalyst.
3) Application conditions.

It is possible to reduce the free formaldehyde content of finished fabrics by:

1) Addition of HCHO scavengers in the finishing bath.

2) After treatment of the fabric with scavangers.
3) After wash of the finished fabric.
4) Careful control of concentration of CLA, catalyst and control of reaction conditions.

Experimental Work

Fabrics

The study of the finishing trials with formaldehyde and non-formaldehyde finishing agents was carried out on
the following fabrics:

i) 100% cotton fabric.

ii) 100% viscose fabric.
iii) Blend of PET/ V.
iv) Tencel fabric.
The unprocessed grey fabrics were procured from the market, about 10 metres of each fabric type.

All the fabrics were tested for the following physical properties:

i) Count
ii) Breaking strength
iii) Elongation at break
iv) Fabric construction/weave
v) Weight per sq.m
vi) Width of the fabric
vii) Yarn denier
viii) Twist
ix) Reed/Pick
x) Total ends

Finishing Chemicals

Finishing trials were carried out using various finishing recipes. The chemicals used were of commercial
quality. The following chemicals were used in the finishing trials:

i) Dimethyl dihydroxy ethylene urea (DMDHEU).

ii) Fixer CCL ethylene urea)
iii) Finish FC (ethylene urea)
iv) Binder SLN (acrylic binder)
v) Polyethylene emulsion
vi) Polysol
vii) Stiffnol
viii) Silicon oil
ix) Natrium NFO - Non-formaldehyde finishing agents
x) Natrium Conc. – Non-formaldehyde finishing agents.
xi) Citric acid
xii) Urea
xiii) Chitosan

Solid Content

The solid contents of some of the above mentioned chemicals were determined. A known weight of the
compound was taken in a petri dish, placed in an oven at 100°C and weighed to constant weight. The solid
content was calculated from the difference between the initial and final weights.

Fabric Pre-treatment

The grey fabrics, viz., cotton, viscose and polyester/viscose blend were given treatments for desizing,
scouring and bleaching.

(A) Viscose
2 g/I Nonionic detergent
2 g/I Soda ash
2 g/I Hydrogen Peroxide (30%)

Boiled for 1 hour

(B) Cotton
Desizing : 0.5% HCI solution
Temperature raised to boil for 30 mins.

Scouring

10 g/I Sodium hydroxide

2 g/I Nonionic detergent

The temperature was gradually raised to boil for 40 mins, MLR 1:30
Bleaching

3 Vols Hydrogen Peroxide

2 g/I Sodium hydroxide
2 g/I Soda ash]
7 g/I Sodium silicate

(C) Polyester/Viscose

2 g/I Nonionic detergent

2 g/I Soda ash

Boiled for 1 hour

(D) Tencel

5 g/I Enzyme powder

2 g/I Sodium hydroxide
2 g/I Nonionic detergent

The M:L ratio was 1:10, pH = 9 and the fabric was treated at 80°C for 90 mins.

All the fabrics were desized, scoured, bleached and dried for finishing trials.

Wet Pick-up/Padding Mangle Expression of fabrics

Before the finishing trials, the wet pickup or the Padding Mangle expression of the fabrics was kept as
follows:

100% cotton =87.45%

100% viscose = 96.21%
PET/Vis = 59.38%
Tencel = 61.44%
Padding mangle pressure = 3 Kg/sq.in
Roller speed = 3-4

Finishing Trials

Different finishing formulations were prepared, based on formaldehyde finishes and formaldehyde free
finishes, to be applied to the four substrates. Each finishing formulation varied in the content of the cross-
linking agent and other reactants.

The finish was applied by the pad-dry-cure method to all the fabrics (cotton, viscose, PET/V and Tencel).
Different finishing recipes were formulated for the finishing trials.

Recipe 1

DMDHEU : 100 g/I

Magnesium chloride catalyst : 10 g/I
PE emulsion : 20 g/I
Wetting agent : 1 g/I
+ H20 (total 10%/lit)

The fabrics were cut into pieces of 20 cms x 40 cms for padding. The fabric was dipped in the padding
solution, dried at 85°C for 5 mins and cured at 160°C for 3 mins.

Recipe 2

DMDHEU : 100 g/I

MgCI2 : 10 g/I
Polysol : 20 g/I
Acrylic Binder : 40 g/I
PE emulsion : 20 g/I
Wetting agent : 1 g/I
Water to total volume : 1 lit.

Recipe 3

Recipe 2 + 3 g/I urea (as formaldehyde scavenger)

Recipe 4

Recipe 2 + 5 g/I citric acid (as formaldehyde scavenger).

The pad-dry-cure conditions are as mentioned above (in recipe 1).

Recipe 5

(With commercial non-formaldehyde finishing agent)

1) Natrium NFO Water: 100 g/I Total vol. 1 litre

2) Natrium Conc. Water: 100 g/I Total vol. 1 litre

The pH was adjusted to 5 with acetic acid. The fabrics were cut into pieces of 20 cm x 40 cm and padded
through the solution. Curing was done at 170°C for 1 min.

Recipe 6

Chitosan : 1% (owf)
Acetic acid : 1% (owf)

Fabric samples were first treated with the above solution and then given the following treatment:

Chitosan : 0.5%
Acetic acid : 1%
Sodium acetate: 1%
Water : 350ml

The fabric samples were padded through the above solution and dried at 80°C for 10 mins.

Cotton, viscose and polyester/viscose fabrics were given this treatment. All the treated fabrics were divided
into two parts and given the following two treatments.

Recipe 6 A

DMDHEU : 60 g/I
MgCI2 : 6 g/I
Polysol : 10 g/I
Acrylic Binder : 10 g/I
PE : 10 g/I
Wetting agent : 1 g/I

Cured at 1600C for 3 mins.

Testing of finished samples

All the finished samples were tested for the following properties:

Whiteness/Yellowness

The reflectance of the finished samples was measured on the ColorEye 7000 spectrophotometer (Gretag
Macbeth) and the whiteness and yellowness values of the untreated substrates and all the treated samples
was determined. Whiteness was evaluated by the CIE 1982 Whiteness Index and Yellowness by the
Yellowness Index ASTM 01925 and OSTM E313.

Crease Recovery Angle (CRA)

The Crease Recovery Angle was determined by the Method B.S. 3086: 1959 (British Standard) using a
Sasmira Crease Recovery Angle Tester. The samples were kept at 25°C ( ± 2°C) and R + I 65% (± 2%)
before measuring the CRA. Three readings were taken per sample and the average of the three readings
was noted.

The CRA of the untreated substrates and all the finished samples were measured, as described in BS 3086:
1959.

Tensile Strength and Elongation at Break

The tensile strength of the untreated substrate and some of the treated samples were measured on the
NEXYGEN Tensile Strength Tester from Lloyd Instruments. The samples were conditioned (kept at) 25°C (±
2°C) and 65% (± 2) RH prior to measurement.

Test of Formaldehyde Release by Japanese Law 112 Method

The samples treated with formaldehyde based finishing agent were tested for free formaldehyde and
formaldehyde released by partial hydrolysis by the JL 112 Method. The fabric samples were kept in distilled
water at 40°C for 1 hour. Colour was developed using Nash Reagent and the absorbance at 412.0 nm was
recorded on GBC 918 UV-VIS spectrophotometer. From the calibration graph, the amount of formaldehyde
was determined.

To test durability to laundering, the finished samples were given domestic wash cycle by the following
method:

Synthetic detergent : 4.5 g/I

Sodium carbonate : 2 g/I
M:L : 1:50
Sample size : 10 cm x 4 cm

After the laundering trial, the laundered samples were tested for crease recovery angle to check the
durability of the finish.

Soiling Test

The soiling property of the unfinished substrates and the finished samples were tested by the ASTM
recommended formula for soiling (Water Garner, old volume).

Soiling of the samples was carried out using:

Natural Road dust : 24 g/l

Mineral oil : 1.5 g/I

Each sample was kept in the above solution for 30 mins. with continuous stirring and then drip dried. After
drying, the samples were assessed for whiteness/yellowness.

FlammabilityTest

The flammability of the untreated substrate .and the treated samples were measured on the Flammability
Tester based on ASTM 0-1230 test method.

The samples to be tested were cut to the required size (2 cm x 100 m) and then placed in the flammability
tester. The Burning Time of each sample was recorded and the average of three readings was taken for
each sample. The ignition time and Burning time of all the samples were recorded.

Results and Discussion

The results of various tests carried out on the finished fabrics, viz., crease recovery angle, tensile strength,
white-ness index, formaldehyde release by JL 112, soiling behavior and flammability are given here.

Measurement of Crease Recovery Angle (CRA)

The conditioned CRA of the untreated substrates and all the treated samples were determined by the BS:
1959 method on the Crease Recovery Angle Tester (SASMIRA). The values of CRAs of all the samples are
given in Table 1.

It can be seen from the results in Table 2 that the CRA of the low formaldehyde finish (DMDHEU + Acrylic
binder) is the highest value for all four substrates. The CRAs with commercial non-formaldehyde finishes are
less as compared to other formulations. The CRA of chitosan based formulations have comparable values
with the low formaldehyde finishes. PET/V does not show a great difference in the CRA with the change in
finish. The largest variation is observed in 100% cotton where the CRA varies from 199 to 295. This is
probably due to variation in the extent of cross-linking with the cotton substrate - the cross-linking increasing
with the increase in concentration of DMDHEU.

In all the substrates, maximum value of CRA is for Rec.1 (DMDHEU) with the non-formaldehyde
formulations having lower values. PET/V substrate has a CRA of 240 even in the untreated substrates owing
to its fabric construction.

Thus, fabrics treated with DMDHEU + Acrylic Binder impart higher crease recovery. But, chitosan
formulations with CRA of 220, 226 and 276 for cotton, viscose and PETN are comparable.

The CRA of the samples after 10 home laundering cycles have decreased slightly than those of un launched
samples in all the three recipes which shows that durability and washing of all the recipes is the same.

Tensile Strength

The tensile strength values of the untreated substrate and the treated samples are given in Table 2.

It can be seen from these values that there is a decrease in tensile strength in the fabrics finished with low
formaldehyde (DMDHEU) finishes (Recipe 2), particularly in case of cotton. In the PET/V samples, the
tensile strength is almost unaffected even after formaldehyde finishing; while in the viscose, there is again a
slight decrease in the tensile strength.

The chitosan-treated fabrics, both with DMDHEU and acrylic binder, show either no change in the tensile
strength or a marginal decrease, in case of cotton and cotton. In the PET/V samples, the tensile strength
remains unchanged.

Normally, the loss of strength after durable press finishing is due to acid damage and the restriction of stress
distribution within the fabric. This is seen in the DMDHEU-based finishes, particularly in 100% cotton fabric.

The cellulosic linkages in cotton are affected by the acid catalyst and, hence, there is a decrease in tensile
strength. Viscose is less affected while PET/Viscose is almost unaffected by the acid catalyst in DMDHEU-
based finishes.

The tensile strength does not decrease but remains the same in case of all substrates treated with chitosan-
based finishes.

Whiteness and Yellowness Index

The Whiteness and Yellowness Index of all the samples, both treated and untreated, are given in Table 3.

As compared to the untreated substrates, the Whiteness Index of all the treated samples is generally less,
while the Yellowness Index increases slightly or remains almost the same. The commercial non-
formaldehyde finishing agents have better whiteness values (~75) than the untreated substrate (~74) for
100% cotton.

The DMDHEU-based finishes show a marginal decrease in whiteness. In case of Tencel, there is a slight in-
crease in whiteness after finishing, while the yellowness decreases.
The chitosan-based finishes show a distinctive decrease in whiteness as compared to the untreated
substrate for all the three substrates. This shows that chitosan causes a definite yellowing of the substrate
as compared to DMDHEU and even citric acid.

The whiteness index of the DMDHEU-based finishes is better than that of chitosan-based formulations.

The commercial non-formaldehyde formulations give improved whiteness values after finishing as compared
to the other formulations.

Formaldehyde released by Japanese Law 112

The releaseable formaldehyde from the DMDHEU-based formulations on all the substrates was determined
by the JL 112 Method. The fabrics were not washed after finishing and, hence, the result include free
(unbound) formaldehyde, formaldehyde from unreacted resin as well as that from finish degradation as a
result of hydrolysis during storage.

The formaldehyde released from the DMDHEU-based finish, DMDHEU + scavengers and the Chitosan
DMDHEU combination was determined by the JL 112 Method. This method is based on the extraction of an
accurately weighed one gram fabric sample for 1 hour with 100 ml of distilled water at 40°C. Formaldehyde
release was evaluated by the colorimetric method using freshly prepared Nash Reagent. (Nash reagent was
prepared after every 3 days).

Each sample was analysed twice to ensure repeatability of the results and the average values are reported
here. The values of formaldehyde evolved from the tested samples are given in Table 5.

The formaldehyde release results for Recipe2 are within the prescribed limits for outerwear clothing for
100% cotton and PET/V. Viscose has higher values. In case of Tencel, it has been generally observed that
with the particular fabric quality employed, crease resist finishing is ineffective. Hence, the higher values of
formaldehyde are probably due to unreacted cross-linking agent remaining on the fabric.

The addition of scavengers to the padding bath is in effect for reducing the release of formaldehyde from the
finished fabric. However, in this case the converse takes place. The addition of urea and citric acid actually
increases the values of formaldehyde released. In case of urea, the formaldehyde released is almost four
times that of the DMDHEU-finished samples.

The formaldehyde release values of Recipe 6A are well within the limits prescribed for clothing worn next to
the skin, in spite of the use of DMDHEU.

Soiling behaviour of treated and untreated sample

All the samples, 19 treated and four untreated substrates were subjected to a soiling test using natural road
dust (ASTM recommended). The following soiling recipe was used:

Natural road dust : 24g/l

Mineral oil : 1.5 g/l
Water (Total volume) : 1 litre

Fabric samples 4cm x 4 cm square pieces were cut and stirred with the above solution for 30 mins. The
soiled samples were air dried. The extent of soiling was determined by measuring the whiteness/yellowness
index after the soiling treatment. The results are as given in Table 6.

It can be seen from the whiteness and yellowness values in Table 6 that -

i) soiling of resin-treated samples is more than that of untreated samples

ii) chitosan treated samples are less prone to soiling than the resin-treated sample

Conclusion

The present study was carried out to develop low formaldeyde and formaldehyde free finishing formulations
for cellulosic fabrics. Low formaldehyde formulations were developed such that the formaldehyde released
was within the prescribed limits for clothing worn next to the skin. DMDHEU-based formulations are suitable
for this purpose and can be used along with acrylic polymers and other finishing formulations.
The results obtained with DMDHEU based formulations are satisfactory in terms of crease recovery angle,
whiteness retention, tensile strength and formaldehyde released. The formaldehyde released values of
Recipe2, from the unwashed substrate, are within the prescribed limits for outerwear clothing.

There is only a small decrease in the whiteness value of the Recipe 2 treated fabrics as compared to the
untreated substrate. Tensile strength values are not greatly reduced as compared to the untreated
substrate.

Thus, a low formaldehyde finishing formulation based on DMDHEU can be viable both in terms of the
economic aspects as well as the performance of the treated substrate.

Chitosan is a naturally occurring polymer which is also known for its antimicrobial properties. In the present
study, chitosan treated substrates were further divided into two parts and treated with (i) DMDHEU and (ii)
acrylic binder.

The results of crease recovery angle measurement give lower values as compared to the DMDHEU-based
formulations. The feel of the fabrics is also less stiff than the DMDHEU based formulations. The tensile
strength values were reduced but almost equal to the untreated substrate. Whiteness values are even lower
than those of DMDHEU-based formulation. Chitosan has a yellowing effect on the substrate.

The formaldehyde release values of the chitosan + DMDHEU formulation are well within the prescribed
limits for even clothing worn next to the skin. Thus, chitosan-based formulations are comparable to the
DMDHEU finishes with only slightly lower crease recovery angle values.

The soiling behaviour and flammability of all the finished fabrics have also been studied. Among the treated
samples, cotton has a greater tendency for soiling while the viscose and PET N show a lower tendency to
soil. This is concluded from the whiteness/yellowness values of the soiled samples.

The flammability of all the treated samples was determined and here it is seen that the treated samples have
a higher burning time as compared to the untreated samples. Moreover, the chitosan formulations have a
higher burning time, which can be interpreted as better flammability of these samples. Thus, crease-resist
finishing imparts a degree of flame resistance.

From the results of the various tests carried out, it can be said that DMDHEU-based low formaldehyde fin-
ishes are viable economically and performance-wise. If a non-formaldehyde crease-resist finish is desired,
chitosan-based formulations give good results, although with slightly reduced fabric stiffness and whiteness
values.

Literature referred

1) The chemistry of crease-resist cross-linking agents, H. Petersen, Rev. Prog. Coloration, Vol. 17,
1987, p.7-23

2) Self-smoothing fabrics, J.T. Marsh.

3) Chemistry of finishing agents, VA Shenai, Sevak Publications.

4) Formaldehyde-free durable press finishes, Clark M Welch, Rev. Prog. Coloration, Vo1.22, 1992,
p.32-41.

5) An update on formaldehyde release from various resins, B.T. North, Textile Chemist and Colorist,
Vol. 23, No. 4, p. 23-24.

6) Long-term formaldehyde emissions from DMDHEU-finished cotton fabrics, B.A.K. Andrews and B.J.
Trask-Morell, Textile Chemist and Colorist, Vol. 29, No.6, 1997, p.16-19.

7) Chemistry and mechanism of durable press cotton products, John D Turner, JTW Monthly, Nov.
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8) Textiles - Determination of formaldehyde - Part 2: Released formaldehyde, ISO, 1994, ISOIDIS

14184-2.
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13) Performance of formaldehyde Vs. non-formaldehyde cross-linking agents, American Dyestuff Re-
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14) Wrinkle resistant cotton finishing, Textile Asia, Vol. 25, 7, 1994, p.57-60.

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17) Chitosan in textile processing: An update, Colourage, 4717, 2000, p. 33-34.

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About the Authors:

The authors are associated with Man - Made Textiles Research Association (MANTRA), Surat.
 List of Tables

Table 1
Table 2
Table 3
Table 4
Table 5