New Way to Improve Rubber for Cord Adhesion

2009 Cytec Industries Inc. All rights reserved.

Johnny Zhang
Asia Pacific TS&D Manager for Liquid Coating Resins
Cytec Surface Specialties



Ralph Schaefer, Cytec Austria
Pioneering Sustainable Change
CYREZ Crosslinker and adhesion promoter
ALNOVOL PN 759 / PN 760 Functionalized
phenolic resins
Content
phenolic resins
Adhesion promoter - CYREZ Curing reaction
+
-
-
N
C H
2
N N
N N
N
O
CH
3
N
C H
2
N N
N N
N
OH
N
N N
N N
N
C H
3
OH
H
O H
2
C H
2
O
HMMM
+ -
Resorc.
+
+
OH
OH
C H
2
O
OH
OH
CH
2
OH O H
2
OH
OH
CH
2
OH
OH
C H
2
O
Resorcinol
Adhesion promoter - CYREZ Curing reaction
N
H
C H
2
N N
N N
N
OH
- C H
2
O
N
H
H
N N
N N
N
2
-
N
H
C H
2
N N
N N
N
OH
N
C H
2
N N
NH N
N
N
N N
N NH
N
O
CH
2
O H
2
Adhesion promoter - CYREZ Curing reaction
N
C H
2
N N
OH
OH
CH
2
R1
O H
R1
N
C H
2
NH N
O
CH
2
-
+
N
H
N N
N N
N
OH
CH
2
OH
R1
O H
2
O H
N
N N
NH N
N
HMT - Curing reaction
OH
OH
N
N
N
N
OH
OH
OH
OH
6
NH
3
4
+
12
OH
OH
OH
OH
NH N
OH
OH
OH
OH
ALNOVOL PN 759 / PN 760
Environmental friendly and almost odor free
Replaces resorcinol or resorcinol based resins
Improves aging properties Improves aging properties
Good adhesion properties (N-structure in matrix)
Increase hardness and stress values
Cost advantages
ALNOVOL PN 760 vs. Resorcinol
Thermal Behaviour
60
80
100
L
o
s
s

i
n

w
e
i
g
h
t

(
%
)
Resorcinol
ALNOVOL PN 760
0
20
40
0 50 100 150 200 250
L
o
s
s

i
n

w
e
i
g
h
t

(
%
)
Temperature (C)
Heating rate: 2C/min
Vulcanisation curve
After recipe adjustment
Green = PN 760
Red = Resorcinol
Formulation - For brass plated steel cord
Resorcinol PN 760
Ingredients [phr] [phr]
Natural rubber 100 100
Carbon black (N 326) 55 55
Stearic acid 2 2
Silica 15 15
Zinc oxid 6 6
Antioxidant 1 1 Antioxidant 1 1
Oil 4 4
Cobalt salt (10% Co) 0.75 0.75
Resorcinol 3
ALNOVOL PN 760 2.5
CYREZ 963E 2.5 2.7
Sulphur 4 4
DCBS 0.9 0.6
TBBS 0.7
Results Dynamic and adhesion properties

ALNOVOL PN 760 Resorcinol
Heat build up (rotation test)
- after 20.000 cycles (C) 85 90
G (Pa) 2.4 E+07 2.2 E+07
Tan delta 70C 0.105 0.114
Pull-out-force (N/cm)/cord coverage (1 = 10%; 10 = 100%)
- after 1 d 23C 50% rel. F. 379 / 8 352 / 8 - after 1 d 23C 50% rel. F. 379 / 8 352 / 8
- after 7 d 90C 100% rel. F. 352 / 4 314 / 4
Tensile strength (MPa) 17.6 17.2
Elongation at break (%) 333 331
Modulus 25% elong. MPa) 2.3 2.2
Hardness 23C (Sh A) 85 82
Repound 23C (%)
- 70C (%)
35
48
35
46

Water absorption
0,25
0,3
0,35
0,4
W
e
i
g
h
t

g
a
i
n

[

%

]
23C - 100% rel. hum.
Vulcanized rubber compound
0
0,05
0,1
0,15
0,2
0 1 2 3 4 5 6 7 8 9 10 11 12 13
W
e
i
g
h
t

g
a
i
n

[

%

]
Time [Days]
PN 759
B 20 S
Resorcinol
PN 760
Resorcinol based
resin
Resorcinol
Corrosion on steel cord
Steel cord corrosion
Ingredients: 100.0 phr Natural rubber
55.0 phr Carbon black (N 326)
2.0 phr Stearic acid
15.0 phr Silica
6.0 phr Zinc oxide
1.0 phr Antioxidants
4.0 phr Oil

Adhesion promoter High Cobalt/High Sulphur

Variations: Com I Com II Com III* Com IV
Co-naphthenate 4 phr 4 phr 4 phr 0.75 phr
ALNOVOL PN 759 2.5 phr
CYREZ 963 2.5 phr
Sulphur 4 phr 6 phr 6 phr 4 phr
TBBS 0.6 phr
DCBS 0.9 phr 0.9 phr 0.9 phr 0.6 phr
* 15 phr carbon black instead of silica
Compound
I II III IV
Mooney ML 1 + 4 120C 25 23 21 23
Vulcanization (Rheometer)
- t 5 min 4.5 4.5 4.3 5.0
- t 90 min 13.3 15.1 16.1 19.8
- torque (max - min) dNm 38.6 47.6 60.4 57.2
Tensile strength MPa 20.2 17.8 13.5 18.0
Elongation at break % 412 291 167 283
Adhesion promoter - Physical properties
Elongation at break % 412 291 167 283
Modulus
- 10% Elongation MPa 1.5 1.9 2.7 2.4
- 50% Elongation MPa 2.4 3.5 5.2 3.7
Resilience 70C % 46 45 44 43
tan delta 70C 0.148 0.133 0.150 0.101
Hardness Shore A 23C () 74 80 85 86
Pull-out force / cord
coverage N/cm / %
- 1 d 23C - 50% r.H. 362 / 80 373 / 90 345 / 90 352 / 80
- 3 d 90C - 100% r.H. 263 / 60 324 / 80 102 / 30 326 / 70
- 7 d 90C - 100% r.H. 192 / 50 150 / 30 85 / 20 316 / 70
Summary
ALNOVOL PN ALNOVOL PN ALNOVOL PN ALNOVOL PN 760 760 760 760 an alternative to Resorcinol
CYREZ CYREZ CYREZ CYREZ is the better alternative to HMT
No big change in compounding necessary
Significant improvement in ageing properties
Usable for steel and textile cord compounds
Less environmental impact
Reduce costs
Replacement of high cobalt high sulphur
Thank you
Contacts: Ralph Schaefer Contacts: Ralph Schaefer Jianmin Li Jianmin Li Kishor Patil Kishor Patil
Tel: Tel: +43 50 399 1222 +43 50 399 1222 +86 21 6422 8920 ex221 +91 226 148 7004 +86 21 6422 8920 ex221 +91 226 148 7004
Mobile: Mobile: +43 664 8115195 +43 664 8115195 ++86 13 601 842 621 86 13 601 842 621 +91 98 2038 1665 +91 98 2038 1665
E E- -mail: mail: ralph.schaefer@cytec.com ralph.schaefer@cytec.com jianmin.li@cytec.com jianmin.li@cytec.com kishor.patil@cytec.com kishor.patil@cytec.com
www.cytec.com www.cytec.com
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