Solution Solution SBRs SBRs for Silica tirefor Silica tireAsahi Kasei Corporation Asahi Kasei Corporation

Synthetic Rubber DivisionSynthetic Rubber Division

August, 15, 2001

2 page

Rubber business of AsahiRubber business of Asahi•• Kawasaki Plant Kawasaki Plant

(Asahi Chemical)• Capa:150Kton/Y• Tech:Firestone(1964)• Process: Continuous

&Batch• Product:

Low cis BR(PS&Rubber)Sol-SBR (Rubber)

SB-TPE Hydrogenated TPE Transparent Resin

•• Oita PlantOita Plant(Japan Elastomer)

• Capa:60Kton/Y• Tech:Phillips(1968)• Process: Bach

• Product: Low cis BR (PS)

Sol-SBR((PS&Rubber)

SB-TPE Hydrogenated TPE Transparent Resin

August. 2001

OE-SBR(TufdeneTM) for tire

Grade St/Vi ML Oil(phr) Characteristics

1534 18/13 45 37.5 Abrasion resistance 2530 25/13 40 37.5 Good Processability 3330 31/30 65 37.5 RR/Wet grip balance 3335 36/33 55 37.5 High Grip 4350 39/38 42 50 High grip

Green : Conventional type Red : Performance type(Medium Vinyl)

August. 2001 3 page

4 pageGrip

LRR

good　 ↑

→ good

HP Tire(2nd)

～1980

LRR Tire(2nd)

LRR Tire

(3rd)

HP Tire(3nd)

HP Tire

(1st)

LRR Tire(1st)

～2000

～1995

2000

Market trend of PC-Tire

MarketDemand

ConventionalRadial Tire

Silica

CB Age

Silica Age

Demands for LRR/Grip balance are increasing year by year and will continue forever.

Drastic change after "Green Tire " with Silica. (in EU and Japan after)

Uninterrupted Improvement of Materails is requireing from Market

August. 2001

5 page

Material Improvement for PC/Tire tread

C/B Age Silica Age1975 1985 1995 2000

DryS-SBR

OES-SBR

Em-SBR

Sn-Coupled HiVinyl SBR(Ba.) Sn +N-mod.HiVinyl SBR(Ba.)

E-10(Ba.)[Modified-SBRAsahi]

T-3330,3335,4350(cont.)[Asahi- MV-SBR]

VSL5025,5525(cont.)[Bayer-HV-SBR]

Goodyear SIBR

E-50&60(Cont.)[Modified-SBR,Asahi]

Hi-Styrene Em-SBRNote: (Ba.)= Batch Polymzn.process (Cont.)=Continous 〃

August. 2001

August 2001. By Asahi-KASEI

Table A. Asahi's Solution SBR Line-up for Silica Tire Compound

2nd stage 3rd stageConventionalGrade

Now Developing Characteristics

Type (Application)Smallmodification

Supermodification

Dry LRR (low filer & low oil) -25 to -35°C - E-10 Super Wet-RRbalance

( 39 / 31 ) High strength

OEWinterHi-performance Tire

-35 to -45°C Tufdene 3330

( 31 / 30 ) E-50 Good Wet-RR-

SummerHi-performance Tire

-25 to -35°C Tufdene 3335 ( 35.5 / 33 ) winter balance

( 35.5 / 33 )

E-60UltraHi-performance Tire

-15 to -25°C Tufdene 4350 ( 33/ 53 )Super Dry and Wet grip

( 39 / 38 )

( styrene / vinyl )

6 pageAugust. 2001

Tg vs RR of Asahi's OE-SSBR Line-up in Silica tire conpound

0.10

0.15

0.20

0.25-60 -50 -40 -30 -20 -10

[Good ← Low temp. Prop] Tg of SBR(℃, DSC mid) [Grip → Good]

Tan

δ@

50℃

, S

ilic

a O

E c

om

po

un

d R

R →

Go

od

E-50Asahi Super modifid SBR

Good

T4350

T3335

T3330

Asahi MV-SBR (Conventional for silica）

EmulsionS B R

CommercalHV-SBR

E-60

CompoundSBR/ A-oil/ VN-3/N339=100/ 37.5/ 63 / 7

August. 2001 7 page

Characteristics of E-50 & E-60

A. Characteristics of Polymer structure

1.Specified Chemical modifications on Solution SBR for silica compound to improve silica/ rubber interaction

2. High Tg SBR by well balanced Random Styrene and Vinyl content

3. High molecular weight with medium Mw/Mn

B. Characteristics in silica compounds

1. Good hysteresis loss properties, a. lower Tanδ in high temperature, higher Tanδ in low temperature. → Good RR-Grip balance, good Low temp. prop(Softness)-Grip balance. b. Payne effects(strain dependence of G' and Tanδ) reduced → Good dispersion of fillers or good interaction of silica/rubber.

　 　 Asahi thinks improvement of above hysteresis loss properties are caused by increase of silica / rubber interaction and increase of bound rubber content.

3. Possibilities to reduce of Silane coupling agent(Si69 ) content.

8 pageAugust. 2001

August 2001Asahi-Kasei Corporation

Table . List of SSBR grade of Asahi for Silica compound

Gra d eAroma.oil ( ph r )

ML1+4,100℃,(Dry)

ML1+4,100℃,(OE)

Styrene(wt%)

Vinyl (%in BD)

Tg (℃,mid point,byDSC）

Mw/ Mn(typica l )

Modifica t ion Remark

OE E-50 37.5 - 72 35.5 33 -30 2.3 Super

E-60 37.5 - 70 33 52 -19 2.3 Super

Tuf de n e3330 37.5 - 65 31 30 -40 2.4 Small

OE Tuf de n e 3335 37.5 - 55 35.5 33 -30 2.4 Small Many

custome r s

Tuf de n e4350 50 - 42 39 38 -22 2.4 Small

in J apa n , EU & Asia

Dry E-10 0 72 - 39 31 -28 1.4 Super New p r o du c t

( All data are typical value and not the specification)

9 page

New product

August. 2001

Fig. Grade Map of S-SBR Line-up of Asahi (styrene and vinyl)

0

5

10

15

20

25

30

35

40

45

50

0 10 20 30 40 50 60 70 80 90

Vinyl (% in BD) (not % in total polymer)

Sty

ren

e (w

t%)

Asahi/ LV-SBR

Asahi/MV-SBR

TufdeneE (modified)

AsapreneE (modified)

Commercial

Commercial

Commercial

E-SBR

E-50

T3330

T4350

E-60

T2530

T3335

T1534

A531

Tg value : Mid point of DSC

Tg=-7 C00000000000000 0 Tg=-5 C00000000000000 0Tg=-3 C00000000000000 0 Tg=-1 C00000000000000 0

A1204

E-10

August. 200110 page

Model scheme of Modification and Coupling reaction by Mulifunctional regent

BuLi+Butadiene+Styrene → (Polymerization)

Asahi's n(SBR-Li) + X(-R-C-C)4 → X-(R-C-C-SBR)4 (+SBR-Li)Case ∨ |

O O-Li (impurity part)Couplend/Modified part

Case 1. Referenece (SnCl4 or Si Cl4 coupl in g )

4(SBR-Li) + SnCl4 → Sn-SBR4 +LiCl4 + SBR-Li

Sn-Couplend /Sn-Modified (impurity part)

Case 2. Referenece (SnCl4 coupling + mono-functional reagent)

4(SBR-Li) + SnCl4 + Z(-R'=Y) → Sn-SBR4 +LiCl4 + SBR-R'-YlLi +SBR-Li Z (impurity part)

Sn-Couplend /Sn-Modified

Function-Modified

11 pageAugust. 2001

Advatages of Asahi's modification

50

100

150

200Com

p M

L(10

0℃)

Bou

nd R

ubbe

r

M30

0% Tb Eb

Reb

@70

℃

G' 0

℃,0

.1%

Tan

δ0℃

,0.1

%

Tan

δ0℃

,3%

Tan

δ50

℃,3

%

Inde

x(La

rge

valu

e is

pre

fera

ble)

Asahi- typeSiCl4

Compound recipe：SBR/ A-oil/ Silica/ N339/ Si69/ S=100/ 37.5/ 63/ 7/ 6.3/ 1.1

Effect of Asahi's Modification

1) Increse of bound rubber. → Improvement of filler dispersion

2) Improvement of hysterisis loss → Better LRR/Grip balance

12 page

August. 2001

Fig Change of Payne effect by Asahi's Functional Group

Comparison of Modification-Silica compound / Tanδ @50℃ strain dependence

VN3/N339=63/7)（

0.05

0.10

0.15

0.20

0.25

0.1 1.0 10.0

Strain (%)

@50

℃-t

anδ

Asahi-Type

SiCl4

Comparison of Modification-Silica compound / G' @50℃ strain dependenced /

VN3/N339=63/7 )（

1.0

10.0

0.10 1.00 10.00

Strain(%)

50℃

-G'

(MPa) Asahi-Type

SiCl4

Comparison of Modification-Silica compound /Tanδ @0℃ strain dependence

VN3/N339=63/7)（

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

0.1 1.0 10.0

strain(%)

0℃-t

anδ

Asahi-Type

SiCl4

Comparison of Modification-Silica compound / G' @0℃ strain dependence /

VN3/N339=63/7 )（

1.0

10.0

100.0

0.10 1.00 10.00

strain(%)

0℃-G

' (M

Pa)

Asahi-TypeSiCl4

August. 2001

Page 13

At 50 C゚

Δ G' SiCl4 cup. > Asahi Coup

Δ Tanδ SiCl4 cup. > Asahi coup.

→ Asahi' type coupling makes better filer dispersiom and lower RR.

At 0 C゚

ΔG' SiCl4 cup. < Asahi Coup

ΔTanδ SiCl4 cup.<< Asahi coup. Same Tg range but Tanδ are grate differenec. asahi coupling makes better

wet grip and loe temperature

hardness.

0

0. 2

0. 4

0. 6

13 15 17 19 21 23 25 27 29Ti me (mi n)

T3330

E-50

E-60

SBR1712

GPC-Curve of Asahi's S-SBR

August. 2001

Page 14

Asahi modified SBR vs. Commercial HV-SBR

50

100

150

200B

ou

nd

Ru

bb

er

Co

mp

d.

M.

Vis

.

M3

00

%

M3

00

/M1

00

Te

ns

ile

str

en

gth

Elo

ng

ati

on

(%

)

Re

b.

@5

0°C

G'@

0°C

0.1

%

Ta

nδ

@0

°C

0.1

%

Ta

nδ

@0

°C,

3%

Ta

nδ

@5

0°C

, 3

%

ΔG

' @5

0°C

Ind

ex

(L

arg

e i

s p

refe

rab

le)

T-3330E-50E-60HV-SBR

August. 2001

Index= 287

Index= 256

Index= 200

Advantages of Asahi Modified SBR

1) Increased bound rubber and good silica dispersion

2) Good mechanical properties

3) Low hysteresis loss at higher temperature

4) Good LRR/Grip balance

5) Soft around C00000000000000 0

Page 15

Tanδ @ 0°C 0.1% strain vs Tanδ @ 50°C 3% strain

0.12

0.14

0.16

0.18

0.20

0.22

0.24

0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Tanδ @ 0°C 0.1% strain Grip → Good

Tan

δ

@ 5

0°C

3%

str

ain

LR

R →

Go

od

August 2001

E50

E60

HV-SBR/Ger

T3330

T3335

Compd recipeSBR=100 A-oil=37.5

Silica-VN3=63 N339=7Si69=6.3

Good

Note:

LRR/ Wet grip balance・ (= Tanδ 5 C/ Tanδ C）0 0000000000000000000000000000 0

E-50 & E-60 > T-3330 & T-3335 >=HV-SBR/Ger

LRR properties of E-50 is very attractive

Page 16

Tanδ @ 0°C 0.1% strain vs G'@ 0°C 0.1% strain

10

15

20

25

30

35

0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Tanδ @ 0°C 0.1% strain

G'

@ 0

°C

0.1%

str

ain

(P

a)

August 2001

E50

E60

HV-SBR/Ger

T3330

T3335

Good

Compd recipeSBR=100 A-oil=37.5

Silica-VN3=63 N339=7Si69=6.3

Note:

Low temp hardness/・ Wet grip balance (= G' at C/ Tanδ C）0 0000000000000000000000000000 0

E-50 & E-60 > T-3330 & T-3335 > HV-SBR/Ger

G' at low temperaure of・ Asahi SSBR are lower than commecial HV-SBR because of good filler disper si o n

Page 17

Visco-Elasitic cure of E-50, E60,T3335,T3330 & HV-SBR

0.0

0.2

0.4

0.6

0.8

1.0

1.2

-50 -40 -30 -20 -10 0 10 20 30 40 50 60 70Temp(℃）

tanδ

,(-)

[Measured　by　reometrix　Ares,10Hz,strain=1.0%]

HV-SBR

T3335

E-60

T-3330

E-50

5 CTanδ00000000000000 0

HV-SBR 0.149T-3335 0.130E-60 0.124E-50 0.115T-3330 0.114

Note:

Tanδ curve of E-50 &・ E-60 are sharp High Tanδ peak（ ） → suggest good filler dispersion

Above room temp,・ Tanδ of E-50 & E-60 and T3330, 3335 lower than commercial HV-SBR. → good LRR properties expected.

Page 18

Asahi-SBR/BR blends vs #1712(same Tg) in silica

40

60

80

100

120

140

160

Bo

un

d r

ub

ber

Co

mp

d.

Mo

on

ey10

0°C

Hs(

Sh

oe-

A)

M30

0%

M30

0/M

100

Ten

sile

str

eng

th

Elo

gat

ion

Reb

ou

nd

50 ℃

G' 0

°C

0.1%

Tan

δ0°

C

0.1%

Tan

δ0°

C

3%

Tan

δ50

°C

3%

ΔT

anδ

50

°C

Ind

ex (

Lar

ge

valu

e p

refe

rab

le)

3330/U150=75/25

E-50/U150=65/35

SBR1712

August. 2001

Index=196

Advantages of Tufdene/BR blend in silica 1) Increased bound rubber and good filler dispersion (small Δ G') 2) Increased bound rubber

2) Higher M300%

3) Soft in lower temp

4) Goog low rolling resistance

Page 19

Wet grip(Tanδ @ C) vs RR(Tanδ @5 C) of0 0000 00 00 00 00 00 00 00 00 00 00 00 0 0 0E-50/BR blend in silica Compound

0.12

0.14

0.16

0.18

0.200.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8

Tanδ @ C(0.1% strain)00000000000000 0

Tan

δ5

C,3

% st

rain

00000000000000

0

T3330/BR

SBR1712

T3335/ BR

E-50/BR

65/35

85/15

65/35

75/25

100/0

100/0

100/0

Good

Compound recipeSBR+BR 100A-oil 37.5Silica 63N234 7Si69 5

August. 2001

Note :

LRR/wet grip balance・

E-50/BR blend

> T-3330/BR blend

> T-3335/BR blend

>= SBR 1712 Modefication and・ high Mol. wt make good effects on LRR in SBR/BR blend

Page 20

Wet grip(Tanδ @ C) vs Low temp Hardness(G'@ C) of0 0000 00 00 00 00 00 00 00 00 00 00 00 0 0 0E-50/BR blend in silica Compound

4

6

8

10

12

14

16

180.1 0.2 0.3 0.4 0.5 0.6 0.7

Tanδ @ C(0.1% strain)00000000000000 0

G' @

C,3

% st

rain

(MPa)

00000000000000

0

T3330/BR

SBR1712T3335/ BR

E-50/BR

65/35

85/15

65/35

75/25

100/0

100/0

100/0

Good

Compound recipeSBR+BR 100A-oil 37.5Silica 63N234 7Si69 5

August. 2001

Note :

Low temp hardness・ /wet grip balance

E-50/BR blend

> T-3330/BR blend >= T-3335/BR blend

> SBR 1712 Modefication and・

make good effects on Low temp. prop. in SBR/BR blend

Page 21

A u g u s t . 2 0 0 1 , A s a h i - K A S E I C o r p o r a t i o n

I n t r o d u c t i o n o f E - 1 0 , M o d i f i e d S B R f o r s i l i c a c o m p o u n d s

1 . O b j e c t o f d e v e l o p m e n t

D r y S B R ( N o n O E ) f o r S i l i c a c o m p o u n d w i t h s u p e r b a l a n c e d R R a n d G r i p p r o p e r t i e s

2 . C h a r a c t e r i s t i c s o f P o l y m e r s t r u c t u r e

a . N a r r o w M w / M n b y S o l u t i o n S B R t e c h n o l o g y b . T h e r e t y p e s o f C h e m i c a l m o d i f i c a t i o n s u i t a b l e f o r S i l i c a f i l e r c . H i g h T g ( - 2 8 ° C ) w i t h r a t h e r h i g h s t y r e n e c o n t e n t ( 3 9 w t % ) a n d m e d i u m v i n y l c o n t e n t ( 3 1 % i n B D )

3 . P e r f o r m a n c e i n s i l i c a c o m p o u n d s

a . A s a h i ' s c h e m i c a l m o d i f i c a t i o n f o r s i l i c a e x h i b i t s v e r y l o w T a n δ v a l u e a t a r o u n d 5 0 ° C . T a n δ a t 5 0 ° C o f E - 1 0 i n l o w o i l s i l i c a r e c i p e i s b e t t e r t h a n t h a t o f c o m m e r c i a l m o d i f i e d S - S B R .

b . H i g h T a n δ v a l u e a t l o w t e m p e r a t u r e ( a r o u n d 0 ° C ) i s a c h i e v e d b y h i g h T g s t r u c t u r e , b u t G ' v a l u e i s n o t s o l a r g e c o m p a r e d w i t h c o m m e r c i a l S - S B R w i t h m o d i f i c a t i o n .

c . S t r a i n d e p e n d e n c e o f T a n δ a n d G ' a r e v e r y s m a l l a n d P a y n e e f f e c t i s v e r y l o w i n t h e s i l i c a c o m p o u n d o f t h i s S B R b y i m p r o v e d s i l i c a d i s p e r s i o n .

4 . A p p l i c a t i o n

A s a h i t h i n k s t h i s S B R w o u l d m a k e s u p e r s i l i c a c o m p o u n d w i t h g o o d R R - G r i p b a l a n c e , a n d w o u l d b e s u i t a b l e f o r t i r e t r e a d c o m p o u n d w i t h l o w o i l r e c i p e o r e n v i r o n m e n t a l s a f e t y o i l r e c i p e .

P a g e 2 2

Table 1 Basic polymer structures of E-10

E-10 Modified SBR

Production scale Plant Plant

Oil content (phr) 0 0

Polymer Mooney Vis.(ML 1+4, 100°C) 72 45

Styrene content (wt%) 39 22

Vinyl content (% in BD) 31 65

Tg (°C, DSC mid) -28 -26

Remark Newly developed

Page 23

August. 2001

Fig . E-10 vs Commercila modified S-SBR

60

70

80

90

100

110

120

130

140

150

160B

ou

nd

Ru

bb

er

Co

mp

d.

M.

Vis

.

M3

00

%

M3

00

/M1

00

Te

ns

ile

str

en

gth

Elo

ng

ati

on

(%

)

Re

b.

@7

0°C

G'@

0°C

0.1

%

Ta

nδ

@0

°C

0.1

%

Ta

nδ

@0

°C,

3%

Ta

nδ

@5

0°C

, 3

%

ΔG

' @5

0°C

Ind

ex

(L

arg

e i

s p

refe

rab

le)

E-10

Commercail SSBR

August. 2001

Advatages of E-10

1)Higher Styrene MV-SBR with Fuctinal Group. 2) Good mechanical Properties(M300,Tb)

3) High hysterisis loss at low temp. → High grip

4) Low hysterisis loss at high temp. → Lower RR

5) Small Payne effect & large bound rubber → Good fiiler dispersion

Page 24

Fig. E-10 in Silica compound-Tanδ temperature dependence cureve

0.00

0.50

1.00

1.50

-40 -30 -20 -10 0 10 20 30 40 50 60 70

Temp.(℃)

tanδ

1

10

100

1000

G'(

MP

a)

E-10

Commercailmodified SBR

August. 2001

Commercailmodified SBR

E-10

Note : 1) High Tanδ peak 2) Lower Tanδ at high temperature 3) Lo wer G ' v al u e above C00000000000000 0

Page 25

Possibility to redudce Si69 content using E-50

60

80

100

120

140

160

180 B

ound

rub

ber

Com

pd. M

L (1

00℃

）

T-9

0%

M30

0%

Ten

sile

Str

engt

h

Elon

gation

G'

@ 0℃

0.1

%

δ @

0℃ 0

.1%

ｔａｎ

δ @

0℃ 3

%ｔａ

ｎ

Reb

ound

5

C00000000000000

0

δ @

50℃

3%

ｔａｎ

ΔG

' @5

C00000000000000

0

Inde

x(La

rge

valu

e is

pre

fera

ble)

14 C/Si69=6.3phr22222222222222 216 C/Si69=6.3phr00000000000000 0

16 C/Si69=3.15phr00000000000000 0

16 C/Si69=2.1phr00000000000000 0

August 2001

Possibilities to reduce Si69 content

1) Highe Mixing temp. improves LRR and wet grip properties. using E-50

2) Reduced Si69 content (Sulfur compensate) impreves silica disperdion

3) In both cases, increase of compound viscosity and danger to scorch are uneasy matter.

4) There would be a possibility to mix at higher temp. and reduced silane using stable coupling agent Si75.

Page 26

Good Copy

SummarySummary• Asahi’s MV-SBR : TT--3330 & T33353330 & T3335 (OE-SBR)

with good St/Vi balance , & Small modification→ Good results in EU & JP for silica tire.(LRR/Grip balance, Low temp. property, Wear Resistance.)

• New Grade EE--50 and E50 and E--6060 (OE-SBR) with Super Modification and Higher MwSuper Modification and Higher Mw

→ Improved LRR/Grip & Low temp/Grip balanceImproved LRR/Grip & Low temp/Grip balancewould be expected for silica tire in next stage

→ Possibility to reduce silanePossibility to reduce silane coupling agent

• New Grade EE--1010 (Dry-SBR)with Super ModificationSuper Modification

→ Application for low oil formulation & environmental safelow oil formulation & environmental safeoil formulationoil formulation would be expected.

Page 27August 2001