Preparation and adhesion properties of

waterborne polyurethane-coated resin for

synthetic leather
Cite as: AIP Conference Proceedings 2083, 030005 (2019); https://doi.org/10.1063/1.5094315
Published Online: 21 March 2019

Eun Ji Kim, In Kyu Paik, and Jae Hyung Park

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© 2019 Author(s).
 Preparation and Adhesion Properties of Waterborne
Polyurethane-coated Resin for Synthetic Leather
Eun Ji Kim1, a), In Kyu Paik1 and Jae Hyung Park1
1
Korea Institute Footwear & Leather Technology (152 DangGamSeo-Ro, Busanjin-Gu, Busan, 471-54, South Korea)
a)
Corresponding author: ejkim@kiflt.re.kr

Abstract. The purpose of this study is to evaluate the adhesive properties of waterborne polyurethane-coated resin for
synthetic leather by omitting the primer and the preparation of waterborne polyurethane-coated resin for synthetic leather
with excellent adhesion by omitting the pre-treatment process. First, after synthesizing flexible polyurethane dispersion
using Poly (tetrahydrofuran)(PTMG, Mw=2,000) and Isophorone diisocyanate(IPDI), coating resins have been created by
adding various silane coupling agents, an additive, and tested of their characteristics. As a result, a polyurethane
dispersion for synthetic leather with fine adherence strength (Ethylene vinyl acetate(EVA, mid-sole) : 2.9 kgf/cm,
rubber(out-sole) : 3.4 kg f /cm) has been developed without use of primer.G

INTRODUCTION
A shoe consists of upper, mid-sole, and out-sole. In process of shoe assembly, harmful substances such as
volatile organic compounds are released from usage of primers containing organic solvents [1]. As a result, posing a
serious threat to atmosphere and work environment, thus, currently regulation on the usage is being imposed
globally [2]. In order to solve these problems, it is necessary to develop an aqueous polyurethane coating resin for
synthetic leather which does not require primer processing, which is an essential part in shoe making.
Synthetic leather consists of epidermis layer, papillary layer, reticular layer and textile layer. It is a structure
similar to that of natural leather consisting of the papillary layer, reticular layer and the flesh layer. This is shown in
Figure 1.

(a) (b)
FIGURE 1. Structure of (a)synthetic leather and (b)natural leather.

The waterborne polyurethane is mainly used in the coating resin constituting the epidermis layer of the synthetic
leather. In order to give a feeling like natural leather, flexibility, shape stability, vulcanization resistance, thermal
stability and interlaminar adhesion are required. However, since the waterborne polyurethane is produced by salt
formation capable of being dispersed in water from the ionomer, the water-resistance is lower than that of the
solvent-type polyurethane resin due to the hydrophilicity of the central ion [1]. Further, there is a disadvantage that
the affinity with the adhering material is poor and the adhesive strength is low, and studies are needed to improve it.
TABLE 1. Composition(mole) of WPU G
G PTMGG IPDIG DMPAG TEAG EDAG

WPU (mole)G 1.5G 3.0G 1.1G 1.1G 0.4G

7th International Conference on Nano and Materials Science (ICNMS 2019)

AIP Conf. Proc. 2083, 030005-1–030005-5; https://doi.org/10.1063/1.5094315
Published by AIP Publishing. 978-0-7354-1813-4/$30.00

030005-1
 EXPERIMENTAL TECHNIQUES
Materials

Poly(tetramethyleneoxideglycol) (PTMG, number-average molecular weight = 2,000g/mol; Aldrich Chemical)

was dried at 85ଇand 1-2mmHg for several hours until no bubbling was observed. Isophorone diisocyanate (IPDI,
Aldrich Chemical), 2,2-bishydroxymethylpropionic acid (DMPA, Aldrich Chemical), N-methyl-2-pyrrolidone(NMP,
Junsei Chemical), Triethylamine (TEA, Junsei Chemical) and Ethylene diamine (EDA, Junsei Chemical) were used
without further purification. Also, 3-Glycidyloxypropyl trimethoxysilane (GPMS, Shin-Etsu: KBM 403), [3-
(Methacryloyloxy) propyl] trimethoxysilane (MAPMS, Shin-Etsu: KBM 503), (3-Mercaptopropyl) trimethoxysilane
Etsu: KBM 803), and Vinyltrimethoxysilane (VTMS, Shin-Etsu: KBM 1003) were used as functional additives.

Synthesis of waterborne polyurethane

The composition of the waterborne polyurethane-coated resin(WPU) used in this study is given in Table 1. The
WPU was synthesized with the pre-polymer mixing process in Figure 2. Polyol was placed in a four-necked
separable flask equipped with a thermometer, a stirrer, a condenser with a drying tube, an inlet of dry nitrogen, and a
heat jacket and was degassed in vacuum at 85ଇ for 30min. DMPA/NMP (1/2 w/w) was added to the flask, stirred at
the same temperature for 30 minutes, IPDI was added dropwise, and the flask was further stirred for 3 hours. The
reaction mixture was allowed to react at 85ଇ until the theoretical NCO content was reached. The change in the
NCO value during the reaction was determined with the standard dibutylamine back titration method (ASTM D
1638). Then, acetone was added to the NCO-terminated pre-polymer mixture to adjust the viscosity of the solution.
The temperature of the reactants was lowered to 65ଇGand TEA was then added to the reaction mixture to neutralize
the carboxyl groups of the NCO-terminated pre-polymer. After 30min of neutralization, distilled water (70wt%) was
added to the reaction mixture with vigorous stirring under about 1000rpm stirring. The neutralized pre-polymer was
chain-extended until the NCO peak (2270cm-1) in the IR spectra had completely disappeared. All the WBPUs were
obtained by the evaporation of acetone and the subsequent addition of an adequate amount of distilled water.

Preparation of waterborne polyurethane-coated resin and their filmsGGG

First, acetic acid (AA) is added to distilled water to prepare an aqueous solution having a pH of 4.5.
Subsequently, 10 g of a silane coupling agent was added to 90 g of the AA aqueous solution at pH 4.5, and the
mixture was stirred for 30 minutes to obtain a 10% aqueous silane coupling agent solution. 10% of a silane coupling
agent aqueous solution was added to the prepared WPU and blended for 2 hours to obtain various aqueous
polyurethane-coated resins. The film (typically about 0.1 mm thick) was poured into a Petri dish and the aqueous
dispersion was allowed to dry for one day at room temperature.
NCO CH3

+ + n HOH2C C CH2OH
OH CH2CH2CH2CH2O H H3C CH3
n
H3C NCO
PTMG COOH
IPDI DMPA

3hr (85oC) NCO

H CH3 O H3C CH3

NCO N C O CH2 C CH2 O C N CH3
O COOH H
CH3 O O H3C CH3
H3C
H3C N C O CH2CH2CH2CH2O C N CH3

H H

1. MEK + TEA
2. Distilled water
3. Chain extender(EDA) NCO

H CH3 H3C CH3

O
NCO N C O CH2 C CH2 O C N CH3
O - +
COO N H(Et)3 H
CH3 O O H3C CH3
H3C
H3C N C O CH2CH2CH2CH2O C N CH3

H H
MEK removal

Waterborne Polyurethane

FIGURE 2. The preparation process of waterborne polyurethane.

030005-2
 TABLE 2. Sample Designation, Composition and Viscosity of the WPU using silane coupling agent G

Sample WPUG 10% Silane coupling agent solution (wt%)G Viscosity

designationG (cps.)G
(wt%)G GPMSG MAMSG MPMSG VTMSG

WPUG 100G -G -G -G -G 2910G

WP-GPG 100G 10G -G -G -G 1840G

WP-MAG 100G -G 10G -G -G 2250G

WP-MPG 100G -G -G 10G -G 1920G

WP-VTG 100G -G -G -G 10G 2050G

RESULTS AND DISCUSSION

FT-IR AnalysisGG

The structure of the resulting WPU was identified with FT-IR spectroscopy. As shown in Figure 3, the typical
IR spectrum of the WPU showed the bands near 3330cm -1(N-H stretching), 1700cm-1(C=O stretching) and 1540cm-
1
(C-N-H bending). The characteristic carbonyl group peak appearing at 1700cm -1 region tells about the change in
intermolecular bonding such as hydrogen bonding and dipole-dipole interaction between carbonyl group [3].
The following is a comparison of the FT-IR spectra according to the type of silane coupling agent added(Figure
3 (b)). In the spectra of all the resins(WP-GP, WP-MA, WP-MP and WP-VT) added with the silane coupling agent
unlike the single spectrum(WPU) of the polyurethane resin, 1020cm-1 and 1106cm-1 (Si-O-Si a stretching) was
found. In addition, the epoxide ring peak of 1225~1280 cm-1 can be identified in the spectrum of WP-GP, and the
peak of -SH(mercapto) group of 2550 cm-1 can be found in the spectrum of WP-MP and the -CH = CH2 group peak
of 980~1000 cm-1 in the spectrum of WP-VT.

60
WPU WPU

50
v(-CH2-) WP-GP

40
Transmittance(%)
Transmittance(%)

v(-CH2-) WP-MA

v(N-H) urethane
30 H-Bonded WP-MP

v(C-N)
+G(N-H)
20 WP-VT

v(C=O) urethane
10 H-Bonded
va(C-H) in CH2
vs(C-H) in CH2

0
4000 3000 2000 1000 4000 3000 2000 1000

Wavenumber(cm-1) Wavenumber(cm-1)

(a) (b)
FIGURE 3. FT-IR spectra of (a) WPU sample and (b) WPU using various silane coupling agents.

SEM

In order to confirm the dispersibility of the silane coupling agent to the polyurethane resin, SEM was measured
and the results are shown in Figure 4. It was found that the addition of silane coupling agent resulted in a whitish
change compared to the existing film, but the film was uniformly dispersed. This is because a homogeneous solution
prepared by hydrolyzing a silane coupling agent in an acidic solution was applied to waterborne polyurethane.
However, in the case of WP-MP, a part of the film was united due to the reaction of some of the additives during the
injection of the additive due to the very high reactivity of the mercapto group in the silane coupling agent added to
the resin. However, in the case of WP-MP, a part of the film was united due to the reaction of some of the additives
during the injection of the additive due to the very high reactivity of the mercapto group in the silane coupling agent
added to the resin.

030005-3
 (a) (b) (c) (d) (e)
FIGURE 4. SEM images of the WPU film samples using various silane coupling agents; (a) WPU, (b)WP-GP, (c)WP-MA,
(d)WP-MP, (e)WP-VT.

Thermogravimetric Analysis

The thermals stability of the WPUs was investigated using thermogravimetric analysis from 30ć to 600ć in
nitrogen. Like the WPU control, the thermal degradation of WPUs in nitrogen is a two-step process [4-5]. These
degradation processes are clearly demonstrated in the thermogram derivative curves illustrated in Figure 5 (a). In
addition, when the decomposition of 5% of the sample occurred, the temperature was improved by 2 ~ 5 ć
compared with the case without addition of the silane coupling agent. As a result of checking the residual amount at
550 ć, and the thermal stability was improved.

16
100 WPU WP-GP
WP-GP 14
WP-MA
80 WP-MP
WP-VT 12

10
Stress(MPa)

60
Weight(%)

40
6
WPU

20 4 WP-MA

2 WP-MP WP-VT
0
0
0 100 200 300 400 500 600 0 200 400 600 800 1000

Temperature(oC) Strain(%)

(a) (b)
FIGURE 5. (a)TGA curves and (b)Stress-Strain curves of the WPU film samples using various silane coupling agents.

Stress-Strain Behavior

Stress-strain curves for the WPU films with different silane coupling agents are provided in Figure 5 (b). All
curves are shown up to the fracture stress point of the sample. The stress, strain, and modulus values are shown in
Table 3. In case of WP-GP compared to pure WPU without addition of silane coupling agent, tensile strength
increased to 15.8 MPa and WP-MA increased elongation. There was no change in tensile strength with the addition
of other silane coupling agents and the elongation was lowered. However, the modulus is similar to or slightly lower
than that of conventional ones, and thus it is considered that it will not be a big problem in use as a coating agent

TABLE 3. Thermal Properties and Mechanical Properties of the WPU film samples using various silane coupling agents.

TGA
Tensile strength 100% Modulus
Sample designation Elongation at break (%)
T5% (MPa) (MPa)
Residue at 550ć

WPU 271.5 0.04 5.9 711 1.3

WP-GP 276.9 0.84 15.8 649 1.3

WP-MA 274.1 1.44 3.4 1046 0.8

WP-MP 274.2 1.55 1.6 635 0.7

WP-VT 273.1 2.28 2.1 721 1.0

030005-4
Adhesive Strength

Figure 6 shows the result of applying WPU resin and WPU resin including various silane coupling agent to EVA
(for mid-sole) and rubber (for out-sole) without using primer. Adhesive strength was evaluated in terms of initial
and state. The initial adhesive strength was indicated by a bar graph, and the degree of increase in the state adhesive
strength is indicated by a line. As a result, there was no significant difference in the initial adhesive strength, but the
state of the adhesive strength of the synthetic leather coated with the resin added with the silane coupling agent was
improved. This is interpreted as the effect of the added silane coupling agent. Trimethoxysilane is represented by the
chemical formula of X-Si (OCH3) 3, where X is an organic functional group such as glycidoxy, methacryl, mercapto,
vinyl, As it imparts wettability to increase the adhesive strength. The highest results were obtained in the samples of
"WP-VT". This appears to be due to the double bond of the functional groups of vinyltrimethoxysilane.

4.0
EVA
3.5 Rubber

3.0
Adhesive strength(kgf/cm)

2.5

2.0

1.5

1.0

0.5

0.0
WPU WP-GP WP-MA WP-MP WP-VT

FIGURE 6. Adhesive strengths of the WPU film samples using various silane coupling agents.

CONCLUSIONS

In this study, we applied the silane coupling agent to the waterborne polyurethane to prepare a skin resin for
synthetic leather with good adhesion without pretreatment. As a result, heat resistance and vulcanization resistance
were improved by adding a silane coupling agent to the aqueous polyurethane, which is suitable for use as a coating
resin for synthetic leather. In the case of adhesive strength, the state adhesive strength was improved in all the
samples to which the silane coupling agent was added without using the pre-treatment agent, and the largest
improvement was observed especially in WP-VT.

ACKNOWLEDGMENTS

This paper is the result of the core technology development project of industry (material number: 10048308)
which was funded by the government (Ministry of Industry and Commerce) in 2018 and supported by the Korea
Industrial Technology Evaluation and Management Service.

REFERENCES

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4. T. Kiyotsukuri, T. Masuda, N. Tsutsumi, W. Sakai and M. Nagata, Polymer, 36, 2629-2635 (1995).
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