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章志源章志源章志源章志源

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氰特表面技术氰特表面技术氰特表面技术氰特表面技术

Ralph Schaefer, Cytec Austria

Pioneering Sustainable Change

• CYREZ™ – Crosslinker and adhesion promoter

• ALNOVOL™ PN 759 / PN 760 – Functionalizedphenolic resins

Content

phenolic resins

Adhesion promoter - CYREZ Curing reaction

+

--

N

CH2

NN

NN

N

OCH

3

N

CH2

NN

NN

N

OH

N

NN

NN

N

CH3

OH

H

OH2 CH

2O

HMMM

+ -Resorc.+

+

OH

OH

CH2

O

OH

OH

CH2

OH OH2

OH

OH

CH2

OH

OH

CH2

O

Resorcinol

Adhesion promoter - CYREZ Curing reaction

NH

CH2

NN

NN

N

OH

- CH2

O

NH

H

NN

NN

N

2-

NH

CH2

NN

NN

N

OH

N

CH2

NN

NHN

N

N

NN

NNH

N

OCH

2

OH2

Adhesion promoter - CYREZ Curing reaction

N

CH2

NN

OHOH

CH2

R1

OH

R1

N

CH2

NHN

O

CH2

-+

NH

NN

NN

N

OH

CH2

OHR1

OH2

OHN

NN

NHN

N

HMT - Curing reaction

OH

OHN

N N

N

OH

OH

OH

OH

6NH

34

+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

Lo

ss

in

we

igh

t (%

) Resorcinol

ALNOVOL PN 760

0

20

40

0 50 100 150 200 250

Lo

ss

in

we

igh

t (%

)

Temperature (°C)

Heating rate: 2°C/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 1Antioxidant 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 70°C 0.105 0.114

Pull-out-force (N/cm)/cord coverage (1 = 10%; 10 = 100%)

- after 1 d 23°C – 50% rel. F. 379 / 8 352 / 8 - after 1 d 23°C – 50% rel. F. 379 / 8 352 / 8

- after 7 d 90°C – 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 23°C (Sh A°) 85 82

Repound 23°C (%)

- 70°C (%)

35

48

35

46

Water absorption

0,25

0,3

0,35

0,4

Weight gain [ %

]

23°C - 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

Weight gain [ %

]

Time [Days]

PN 759

B 20 S

Resorcinol

PN 760

Resorcinol basedresin

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 + 4 120°C 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 70°C % 46 45 44 43

tan delta 70°C 0.148 0.133 0.150 0.101

Hardness Shore A 23°C (°) 74 80 85 86

Pull-out force / cord coverage N/cm / %

- 1 d 23°C - 50% r.H. 362 / 80 373 / 90 345 / 90 352 / 80

- 3 d 90°C - 100% r.H. 263 / 60 324 / 80 102 / 30 326 / 70

- 7 d 90°C - 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

� CYREZCYREZCYREZCYREZ 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 SchaeferContacts: Ralph Schaefer Jianmin LiJianmin Li Kishor PatilKishor PatilTel: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 7004Mobile:Mobile: +43 664 8115195+43 664 8115195 ++86 13 601 842 621 86 13 601 842 621 +91 98 2038 1665+91 98 2038 1665EE--mail: mail: ralph.schaefer@cytec.comralph.schaefer@cytec.com jianmin.li@cytec.comjianmin.li@cytec.com kishor.patil@cytec.comkishor.patil@cytec.comwww.cytec.comwww.cytec.com

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