FLUORINE-CONTAINING ELASTOMER AND ITS MOLDINGS

J E u r o p a i s c h e s

Patentamt

European Patent Office © Publication number: 0 3 1 4 7 8 6

Office europeen des brevets A 1

© EUROPEAN PATENT APPLICATION published in accordance with Art. 158(3) EPC

© Application number: 87902769.6 © Int. CI.3: C 08 F 2 1 4 / 2 2

^ C 08 F 214/28, C 08 L 27 /16 (22) Date of filing: 08.05.87 C 08 L 27/20, C 08 K 5 /13

Data of the international application taken as a basis:

(ss) International application number: PCT/JP87/00285

@ International publication number: WO88/08857 (17.11.88 88/25)

@ Dateof publication of application: 10.05.89 Bulletin 89/19

© Designated Contracting States: DE FR GB IT NL

© Applicant: Asahi Kasei Kogyo Kabushiki Kaisha 2-6, Dojimahama 1-chome Kita-ku Osaka-shi Osaka 530(JP)

© Inventor: HAYASHI, Kenichi 442 Hamayama Apartment 4-1, Midorigaoka 2-chome Nobeoka-shi Miyazaki-ken 882(JP)

© Inventor: MATSUOKA, Yoshito 5-jo-6, Hamanaka Shataku 4-1, Midorigaoka 1-chome Nobeoka-shi Miyazaki-ken 882(JP)

© Inventor: KASAHARA, Michio 751,Shinmarukocho Nakahara-ku, Kawasaki-shi Kanagawa-ken 21 1(JP)

© Inventor: MORITA, Naoki 181, Kamiodanaka Nakahara-ku, Kawasaki-shi Kanagawa-ken 21 1 (JP)

© Representative : Strehl, Schiibel-Hopf , Groening, Schulz Maximilianstrasse 54 Postfach 22 14 55 D-8000Miinchen22(DE)

ID 00

r - M

O

Q. UJ

© FLUORINE-CONTAINING ELASTOMER AND ITS MOLDINGS. @ A novel fluorine-containing elastomer which has viny- lidene fluoride units, hexafluoropropylene units and, option- ally, tetrafluoroethylene units, and which has a fluorine content of 63.5 to 71 wt %, a content of a fraction of not more than 50,000 in molecular weight (Ms) of up to 5 wt %, a fraction of not less than 1,000,000 in molecular weight of 10 to 35 wt %, and has an intrinsic viscosity (ml/g) of 100 to less than 250. This elastomer has extremely excellent compression set resistance and mechanical strength, and satisfactory work- ability in addition to excellent heat resistance and chemical resistance, and can provide excellent moldings such as rings, gaskets, seals, diaphragms, etc. by vulcanization.

-roydon Printing Company Ltd.

s p e c i f i c a t i o n T I T L E M O D I F I E D

s e e f r o n t p a g e

@n j . m u i j . n e - c o n L a i n i n g e l a s t o m e r and a s h a p e d

a r t i c l e t h e r e o f

The p r e s e n t i n v e n t i o n r e l a t e s to a n o v e l

E l u o r i n e - c o n t a i n i n g e l a s t o m e r h a v i n g a s p e c i f i c

n o l e c u l a r w e i g h t d i s t r i b u t i o n and a s h a p e d a r t i c l e

; h e r e o f . More p a r t i c u l a r l y , t h e p r e s e n t i n v e n t i o n

Ls c o n c e r n e d w i t h a f l u o r i n e - c o n t a i n i n g e l a s t o m e r

f h i c h has a r e l a t i v e l y l a r g e l i m i t i n g v i s c o s i t y

l u m b e r , an e x t r e m e l y low c o n t e n t of low m o l e c u l a r

w e i g h t c o m p o n e n t s and a s p e c i f i c c o n t e n t of h i g h

l o l e c u l a r w e i g h t c o m p o n e n t s and w h i c h i s no t o n l y

: x t r e m e l y e x c e l l e n t in c o m p r e s s i o n s e t r e s i s t a n t

• r o p e r t i e s and m e c h a n i c a l p r o p e r t i e s b u t a l s o has a

' o r k a b i l i t y s u p e r i o r to or c o m p a r a b l e w i t h c o n v e n -

i o n a l f l u o r i n e - c o n t a i n i n g e l a s t o m e r s , and a s h a p e d

r t i c l e t h e r e o f .

— ~ *̂ h ^-mii Lilt; r n o r A l l .

F l u o r i n e - c o n t a i n i n g e l a s t o m e r s a r e e x c e l l e n t i n

h e i r r e s i s t a n c e s to h e a t and c h e m i c a l s and , t h e r e -

o r e , have been a p p r e c i a t e d as s e a l a n t m a t e r i a l s t o

e m p l o y e d u n u e i o u t - m y <-•@*<- ~~

n g s , o i l s e a l s , p a c k i n g s , g a s k e t s , d i a p h r a g m

i t e r i a l s and t h e l i k e .

W i t h r e s p e c t to s e a l a n t m a t e r i a l s w h i c h

re m a n u f a c t u r e d m a i n l y by c o m p r e s s i o n m o l d i n g , i t

5 i m p o r t a n t f o r t h e s e m a t e r i a l s t o h a v e a s m a l l

D i g r e s s i o n s e t . On t h e o t h e r h a n d , a c c o r d i n g t o

he r e c e n t t e c h n o l o g i c a l i n n o v a t i o n , t h e c o n d i t i o n s

n d e r w h i c h s e a l a n t m a t e r i a l s a r e u s e d a r e i n c r e a s -

n g l y s t r i n g e n t a n d , a c c o r d i n g l y , t h e r e s i s t a n c e o f

e a l a n t m a t e r i a l s to c h e m i c a l s and s o l v e n t s a r e

, e c o m i n g more and more i m p o r t a n t . H o w e v e r , i f t h e

i l u o r i n e c o n t e n t of a f l u o r i n e - c o n t a i n i n g e l a s t o m e r

Ls i n c r e a s e d in o r d e r to i m p r o v e t h e r e s i s t a n c e o f

:he e l a s t o m e r t o c h e m i c a l s and s o l v e n t s , t h e r e i s

r a i s e d a new p r o b l e m t h a t n o t o n l y t h e c o m p r e s s i o n

s e t r e s i s t a n c e of t h e e l a s t o m e r i s i n c r e a s e d b u t

a l s o t h e r o l l w o r k a b i l i t y of t h e e l a s t o m e r i s

l o w e r e d .

H e r e t o f o r e , t h e r e h a v e b e e n p r o p o s e d v a r i o u s

c o m p o s i t i o n s w i t h r e s p e c t to a f l u o r i n e - c o n t a i n i n g

e l a s t o m e r . For e x a m p l e , t h e r e h a v e b e e n p r o p o s e d a

m e t h o d f o r p r o d u c i n g a c o p o l y m e r by p o l y m e r i z i n g 60

to 15 % by w e i g h t of v i n y l i d e n e f l u o r i d e ( h e r e i n -

a f t e r r e f e r r e d to as "VdF") u n i t s w i t h 40 to 85 % b y

u < n 4 7 8 6

w . v t ^ u ^ x c u e l u e i e i n a i c e r r e f e r r e d to as "HFP" ) u n i t s ( s e e J a p a n e s e P a t e n t A p p l i c a t i o n

P u b l i c a t i o n No. 3 3 - 7 3 9 4 ) ; a c o p o l y m e r c o n t a i n i n g 3

to 35 % by w e i g h t of t e t r a f l u o r o e t h y l e n e ( h e r e i n -

a f t e r r e f e r r e d to as "TFE") u n i t s and w h e r e i n t h e

: o t a l a m o u n t of VdF u n i t s and HFP u n i t s i s 97 t o 35 % by w e i g h t and t h e w e i g h t r a t i o of VdF u n i t s t o

IFP u n i t s i s in t h e r a n g e of 2 . 3 3 : 1 t o 0 . 6 6 7 : 1 ( s e e

r a p a n e s e P a t e n t A p p l i c a t i o n P u b l i c a t i o n No. 3 6 -

I495); a c o p o l y m e r c o n t a i n i n g 10 to 30 % by w e i g h t >f TFE u n i t s and w h e r e i n t h e t o t a l a m o u n t of V d F

m i t s a n d HFP u n i t s i s 90 t o 70 % by w e i g h t a n d t h e

' e i g h t r a t i o of VdF u n i t s to HFP u n i t s i s i n t h e

a n g e of 1 . 6 : 1 . 0 t o 4 . 0 : 1 . 0 ( s e e J a p a n e s e P a t e n t

p p l i c a t i o n P u b l i c a t i o n No. 4 8 - 1 8 9 5 7 ) ; and a

o p o l y m e r c o m p r i s i n g 57 to 61 % by w e i g h t of VdF

n i t s , 27 to 31 % by w e i g h t of HFP u n i t s and 10 t o '

4 % by w e i g h t of TFE u n i t s ( s e e J a p a n e s e P a t e n t

p p l i c a t i o n P u b l i c a t i o n No. 5 3 - 1 4 9 2 9 1 ) . On t h e

t h e r h a n d , v a r i o u s p r o p o s a l s have b e e n m a d e

D n c e r n i n g t h e a d j u s t m e n t of t h e m o l e c u l a r w e i g h t

L s t r i b u t i o n of a f l u o r i n e - c o n t a i n i n g e l a s t o m e r .

Dr e x a m p l e , t h e r e h a v e b e e n p r o p o s e d a m e t h o d f o r

r e d u c i n g a c o p o l y m e r h a v i n g a b i m o d a l m o l e c u l a r

s i g h t d i s t r i b u t i o n c o m p r i s i n g a t w o - s t a g e p o l y -

l e r i z a t i o n p r o c e s s ( c o n t i n u o u s p o l y m e r i z a t i o n j ,

r h e r e i n p o l y m e r i z a t i o n i s i n i t i a l l y e f f e c t e d f o r a

t igh m o l e c u l a r w e i g h t c o p o l y m e r and t h e n f o r a l o w

a o l e c u l a r w e i g h t c o p o l y m e r ( s e e J a p a n e s e P a t e n t

a p p l i c a t i o n P u b l i c a t i o n No. 5 1 - 2 5 2 7 9 ) ; a m e t h o d f o r

p r o d u c i n g a c o p o l y m e r or t e r p o l y m e r h a v i n g a l o w

yiooney v i s c o s i t y and e x c e l l e n t w o r k a b i l i t y b y

s u s p e n s i o n p o l y m e r i z a t i o n ( s e e J a p a n e s e P a t e n t

A p p l i c a t i o n P u b l i c a t i o n Nos. 4 9 - 2 9 6 3 0 and 5 1 - 8 4 3 2 ) ;

and a f l u o r i n e - c o n t a i n i n g e l a s t o m e r h a v i n g a

b i m o d a l m o l e c u l a r w e i g h t d i s t r i b u t i o n and a h i g h

m o l e c u l a r w e i g h t ( s e e E u r o p e a n P a t e n t A p p l i c a t i o n

P u b l i c a t i o n No. 0 1 8 6 1 8 0 A 2 ) . H o w e v e r , f r o m t h e

v i e w p o i n t of h a v i n g , in c o m b i n a t i o n , d e s i r e d

p r o p e r t i e s w h i c h i n c l u d e e x c e l l e n t c o m p r e s s i o n s e t

r e s i s t a n t p r o p e r t i e s and e x c e l l e n t w o r k a b i l i t y ,

t h e s e p r o p o s a l s a r e s t i l l i n s u f f i c i e n t .

In g e n e r a l , i f t h e c o n t e n t of low m o l e c u l a r

w e i g h t c o m p o n e n t s in a f l u o r i n e c o n t a i n i n g e l a s t o m e r

i s i n c r e a s e d , t h e w o r k a b i l i t y i s i m p r o v e d b u t t h e

m e c h a n i c a l p r o p e r t i e s i n c l u d i n g c o m p r e s s i o n s e t

r e s i s t a n t p r o p e r t i e s a r e l o w e r e d , w h e r e a s i f t h e

c o n t e n t of h i g h m o l e c u l a r w e i g h t c o m p o n e n t s i s

i n c r e a s e d , t h e m e c h a n i c a l p r o p e r t i e s i n c l u d i n g

c o m p r e s s i o n s e t r e s i s t a n t p r o p e r t i e s a r e i m p r o v e d

0 3 1 4 7 8 6

b u t t h e w o r k a b i l i t y i s l o w e r e d . T h u s , t h e r e h a s

b e e n a t e c h n i c a l d i l e m m a t h a t a f l u o r i n e - c o n t a i n i n g

e l a s t o m e r c a n n o t be s i m u l t a n e o u s l y c h a r a c t e r i z e d b y

an e x c e l l e n t w o r k a b i l i t y and e x c e l l e n t m e c h a n i c a l

p r o p e r t i e s i n c l u d i n g c o m p r e s s i o n s e t r e s i s t a n t

p r o p e r t i e s . T h e r e f o r e , i t h a s b e e n d e s i r e d to s o l v e

t h e d i l e m m a and d e v e l o p a f l u o r i n e - c o n t a i n i n g

e l a s t o m e r h a v i n g b o t h e x c e l l e n t c o m p r e s s i o n s e t

r e s i s t a n t p r o p e r t i e s and an e x c e l l e n t w o r k a b i l i t y .

D i s c l o s u r e of t h e P r e s e n t I n v e n t i o n

An o b j e c t of t h e p r e s e n t i n v e n t i o n i s t o

p r o v i d e a f l u o r i n e - c o n t a i n i n g e l a s t o m e r h a v i n g

e x c e l l e n t p r o p e r t i e s w h i c h can be u s e d u n d e r

s t r i n g e n t c o n d i t i o n s , t h a t i s , a f l u o r i n e - c o n t a i n i n g

e l a s t o m e r w h i c h i s n o t o n l y e x c e l l e n t in c o m p r e s s i o n

s e t r e s i s t a n t p r o p e r t i e s and r e s i s t a n c e to c h e m i c a l s

and s o l v e n t s bu t a l s o h a s a w o r k a b i l i t y s u p e r i o r t o

or c o m p a r a b l e w i t h c o n v e n t i o n a l f l u o r i n e - c o n t a i n i n g

e l a s t o m e r s .

The p r e s e n t i n v e n t o r s h a v e made an e x t e n s i v e

and i n t e n s i v e r e s e a r c h a n d , as a r e s u l t , f o u n d

t h a t a f l u o r i n e - c o n t a i n i n g e l a s t o m e r can b e

i m p r o v e d w i t h r e s p e c t to i t s c o m p r e s s i o n s e t r e s i s -

t a n t p r o p e r t i e s and w o r k a b i l i t y by c o n t r o l l i n g t h e

J 3 1 4 / 8 6

c o n t e n t of low m o l e c u l a r w e i g h t c o m p o n e n t s to a

s p e c i f i c l e v e l and l o w e r i n g t h e c o n t e n t of h i g h

t n o l e c u l a r w e i g h t c o m p o n e n t s t o a l e v e l as low a s

p o s s i b l e . B a s e d on t h e s e f i n d i n g s , t h e p r e s e n t i n -

v e n t i o n h a s b e e n c o m p l e t e d .

A c c o r d i n g to t h e p r e s e n t i n v e n t i o n , t h e r e i s

p r o v i d e d a f l u o r i n e - c o n t a i n i n g e l a s t o m e r c o m p r i s i n g

v i n y l i d e n e f l u o r i d e u n i t s , h e x a f l u o r o p r o p y l e n e

u n i t s and 35 to 0 % by w e i g h t , b a s e d on t h e

e l a s t o m e r , of t e t r a f l u o r o e t h y l e n e u n i t s , t h e t o t a l

of s a i d v i n y l i d e n e f l u o r i d e u n i t s and s a i d h e x a -

f l u o r o p r o p y l e n e u n i t s b e i n g 65 to 100 % by w e i g h t

b a s e d on t h e w e i g h t of t h e e l a s t o m e r , t h e w e i g h t

r a t i o of s a i d v i n y l i d e n e f l u o r i d e u n i t s to s a i d

h e x a f l u o r o p r o p y l e n e u n i t s b e i n g in t h e r a n g e o f

80 :20 to 4 0 : 6 0 , and w h e r e i n :

(a) t h e f l u o r i n e c o n t e n t of t h e e l a s t o m e r i s

6 3 . 5 to 71 % by w e i g h t ,

(b) t h e l i m i t i n g v i s c o s i t y n u m b e r ( m l / g ) o f

t h e e l a s t o m e r i s i n t h e r a n g e of f r o m 100 t o

l e s s t h a n 2 5 0 ,

(c) t h e c o n t e n t of f r a c t i o n s h a v i n g m o l e c u l a r

w e i g h t s of 5 0 , 0 0 0 o r l e s s i n t h e e l a s t o m e r i s

5 % by w e i g h t or l e s s , a n d

(d) t h e c o n t e n t of f r a c t i o n s h a v i n g m o l e c u l a r

0 3 1 4 7 8 6

w e i g h t s of 1 , 0 0 0 , 0 0 0 or more in t h e e l a s t o m e r

i s 10 to 35 % by w e i g h t .

The f l u o r i n e - c o n t a i n i n g e l a s t o m e r of t h e

p r e s e n t i n v e n t i o n i n c l u d e s a c o p o l y m e r c o m p r i s i n g

VdF u n i t s and HFP u n i t s and a t e r p o l y m e r f u r t h e r

c o m p r i s i n g TFE u n i t s .

The m o s t p r o m i n e n t c h a r a c t e r i s t i c f e a t u r e o f

t h e f l u o r i n e - c o n t a i n i n g e l a s t o m e r of t h e p r e s e n t

i n v e n t i o n r e s i d e s in t h a t i t h a s a s p e c i f i c

m o l e c u l a r w e i g h t d i s t r i b u t i o n . As e x p l a i n e d a b o v e ,

in g e n e r a l , i f t h e c o n t e n t of low m o l e c u l a r w e i g h t

c o m p o n e n t s in a f l u o r i n e - c o n t a i n i n g e l a s t o m e r i s

i n c r e a s e d , t he w o r k a b i l i t y b e c o m e s i m p r o v e d b u t t h e


r e s i s t a n t p r o p e r t i e s a r e l o w e r e d , w h e r e a s i f t h e

c o n t e n t of h i g h m o l e c u l a r w e i g h t c o m p o n e n t s i s

i n c r e a s e d , t h e m e c h a n i c a l p r o p e r t i e s i n c l u d i n g

c o m p r e s s i o n s e t r e s i s t a n t p r o p e r t i e s a r e i m p r o v e d

b u t t h e w o r k a b i l i t y i s l o w e r e d . Thus t h e r e h a s b e e n

a t e c h n i c a l d i l e m m a t h a t a f l u o r i n e - c o n t a i n i n g

e l a s t o m e r c a n n o t be s i m u l t a n e o u s l y c h a r a c t e r i z e d b y

an e x c e l l e n t w o r k a b i l i t y and e x c e l l e n t m e c h a n i c a l

p r o p e r t i e s i n c l u d i n g c o m p r e s s i o n s e t r e s i s t a n t

p r o p e r t i e s . H o w e v e r , a c c o r d i n g to t h e p r e s e n t

i n v e n t i o n , i t has u n e x p e c t e d l y b e e n f o u n d t h a t b y

: o n t r o l l i n g p a r t i c u l a r l y t h e a m o u n t or t r a c t i o n s

l a v i n g m o l e c u l a r w e i g h t s of 5 0 , 0 0 0 or l e s s ( h e r e -

i n a f t e r o f t e n r e f e r r e d to as "M5n) and t h e a m o u n t o f

f r a c t i o n s h a v i n g m o l e c u l a r w e i g h t s of 1 , 0 0 0 , 0 0 0 o r

nore ( h e r e i n a f t e r o f t e n r e f e r r e d t o as "M100") t o

s p e c i f i c r a n g e s , a f l u o r i n e - c o n t a i n i n g e l a s t o m e r c a n

De i m p r o v e d w i t h r e s p e c t to i t s w o r k a b i l i t y a n d


r e s i s t a n t p r o p e r t i e s . T h u s , t h e l o n g - s t a n d i n g d i f f i -

c u l t i e s due t o t h e a b o v e - m e n t i o n e d t e c h n i c a l d i l e m m a

have b e e n c o m p l e t e l y o b v i a t e d .

In t h e p r e s e n t i n v e n t i o n , M5 i s 5 % by w e i g h t

or l e s s a n d M10Q i s 10 t o 35 % by w e i g h t b a s e d o n

t h e e l a s t o m e r . The s m a l l e r t h e M5, t h e m o r e

e x c e l l e n t t h e c o m p r e s s i o n s e t r e s i s t a n t p r o p e r t i e s

and , h e n c e , t h e r e i s no p a r t i c u l a r l o w e r l i m i t w i t h

r e s p e c t t o M5. H o w e v e r , f r o m t h e v i e w p o i n t of e a s e

in m a n u f a c t u r i n g , t h e l o w e r l i m i t i s p r e f e r a b l y

0 .4 % by w e i g h t . T h e r e f o r e , f r o m t h e v i e w p o i n t s o f

t h e d e s i r e d p r o p e r t i e s of t h e e l a s t o m e r and e a s e i n

m a n u f a c t u r i n g , M5 is in t h e r a n g e of 0.4 to 5 % b y

w e i g h t , p r e f e r a b l y in t h e r a n g e of 0.8 to 3 % b y

w e i g h t b a s e d on t h e w e i g h t of t h e e l a s t o m e r .

In t h e p r e s e n t i n v e n t i o n , M1 00 i s 10 to 35 % b y

w e i g h t , p r e f e r a b l y 1 0 t o 30 % by w e i g h t b a s e d on t h e

0 3 1 4 7 8 6

c idSLo i i i e i . . m100 e x c e e d i n g Jb % by w e i g h t i s n o t

d e s i r a b l e b e c a u s e t h e r o l l w o r k a b i l i t y of t h e

e l a s t o m e r i s l o w e r e d . M10Q l e s s t h a n 1 0 % by w e i g h t

i s a l s o no t d e s i r a b l e b e c a u s e t h e r e c a n n o t b e

o b t a i n e d a w e l l - b a l a n c e d c o m b i n a t i o n of w o r k a b i l i t y

and m e c h a n i c a l p r o p e r t i e s i n c l u d i n g c o m p r e s s i o n s e t

r e s i s t a n t p r o p e r t i e s of t h e e l a s t o m e r .

The f l u o r i n e c o n t e n t of t h e f l u o r i n e - c o n t a i n i n g

e l a s t o m e r of t h e p r e s e n t i n v e n t i o n i s 63.5 to 71 %

by w e i g h t . As i s d e s c r i b e d a b o v e , t h e f l u o r i n e -

c o n t a i n i n g e l a s t o m e r of t h e p r e s e n t i n v e n t i o n

i n c l u d e s a c o p o l y m e r c o m p r i s i n g VdF u n i t s and HFP

u n i t s and a t e r p o l y m e r f u r t h e r c o m p r i s i n g TFE u n i t s .

The f l u o r i n e c o n t e n t d e p e n d s s o l e l y on t h e VdF u n i t

c o n t e n t among t h e s e t h r e e t y p e s of m o n o m e r i c c o m p o -

n e n t s . T h a t i s , i f t h e VdF u n i t c o n t e n t i s

i n c r e a s e d , t h e f l u o r i n e c o n t e n t i s d e c r e a s e d , w h i l e

i f t h e VdF u n i t s c o n t e n t i s d e c r e a s e d , t h e f l u o r i n e

c o n t e n t i s i n c r e a s e d . The f l u o r i n e c o n t e n t o f

53.5 % by w e i g h t c o r r e s p o n d s to 75 % by w e i g h t ,

b a s e d on t h e w e i g h t of t h e e l a s t o m e r , of VdF u n i t s .

Ef t h e VdF u n i t c o n t e n t i s m o r e t h a n 75 % by w e i g h t ,

bhe c h e m i c a l r e s i s t a n c e of t he e l a s t o m e r i s l o w e r e d .

Dn t he o t h e r h a n d , t h e f l u o r i n e c o n t e n t of 71 % b y

w e i g h t c o r r e s p o n d s to 30 % by w e i g h t , b a s e d on t h e

) < n 4 7 8 6

r e i g h t of t h e e l a s t o m e r , of VdF u n i t s . I t t n e v a t

i n i t c o n t e n t i s l e s s t h a n 30 % by w e i g h t , t h e

f l u o r i n e - c o n t a i n i n g e l a s t o m e r b e c o m e s r e s i n o u s w h e n

Lt c o m p r i s e s a c o m p o s i t i o n i n w h i c h t h e TFE u n i t

c o n t e n t i s l a r g e , w h i l e when t h e HFP u n i t c o n t e n t i s

L a r g e , t h e r a t e of p o l y m e r i z a t i o n in p r o d u c i n g t h e

s l a s t o m e r i s l o w e r e d a n d , t h e r e f o r e , t h e d e s i r e d

E l u o r i n e - c o n t a i n i n g e l a s t o m e r c a n n o t be o b t a i n e d ,

rhe f l u o r i n e c o n t e n t w h i c h p r o v i d e s f o r an e l a s t o m e r

h a v i n g a d e s i r a b l e e l a s t i c i t y i s 64.5 to 69.5 % b y

w e i g h t .

S t a t e d w i t h r e s p e c t t o t h e p r o p o r t i o n s of t h e

m o n o m e r u n i t s c o n s t i t u t i n g t h e f l u o r i n e - c o n t a i n i n g

e l a s t o m e r of t h e p r e s e n t i n v e n t i o n , t h e e l a s t o m e r

c o m p r i s e s v i n y l i d e n e f l u o r i d e u n i t s , h e x a f l u o r o p r o -

p y l e n e u n i t s and 35 to 0 % by w e i g h t , b a s e d on t h e

e l a s t o m e r , o f t e t r a f l u o r o e t h y l e n e u n i t s , w h e r e i n t h e

t o t a l of t h e v i n y l i d e n e f l u o r i d e u n i t s and t h e h e x a -

f l u o r o p r o p y l e n e u n i t s i s 65 to 100 % by w e i g h t b a s e d

on t h e e l a s t o m e r , and t h e w e i g h t r a t i o of t h e

v i n y l i d e n e f l u o r i d e u n i t s t o t h e h e x a f l u o r o p r o p y l e n e

u n i t s i s in t h e r a n g e of 8 0 : 2 0 t o 4 0 : 6 0 .

W i t h r e s p e c t to t h e c o p o l y m e r c o m p r i s i n g VdF

u n i t s and HFP u n i t s , t h e p r e f e r a b l e r a n g e of t h e

w e i g h t r a t i o of t h e VdF u n i t s t o t h e HFP u n i t s i s

0 3 1 4 7 8 €

75 :25 to 4 0 : 6 0 . I f t h e VdF u n i t s c o n t e n t is m o r e

t h a n 75 % by w e i g h t , t h e e l a s t o m e r b e c o m e s r e s i n o u s ,

w h i l e i f t h e VdF u n i t s c o n t e n t i s l o w e r t h a n 40 % b y

w e i g h t , p o l y m e r i z a t i o n b e c o m e s d i f f i c u l t . In e i t h e r

c a s e t h e d e s i r e d f l u o r i n e - c o n t a i n i n g e l a s t o m e r

c a n n o t be o b t a i n e d . More p r e f e r a b l y , t h e VdF u n i t

c o n t e n t i s 70 to 50 % by w e i g h t . A c c o r d i n g l y , t h e

HFP u n i t c o n t e n t i s p r e f e r a b l y 25 to 60 % by w e i g h t

and more p r e f e r a b l y 30 to 50 % by w e i g h t .

W i t h r e s p e c t to t h e t e r p o l y m e r , when t h e f l u o -

r i n e c o n t e n t i s in t h e r a n g e of 63.5 to 71 % b y

w e i g h t , t h e t o t a l w e i g h t of t h e VdF u n i t s and t h e

HFP u n i t s i s 65 % by w e i g h t o r m o r e b a s e d on t h e

e l a s t o m e r , t h e TFE u n i t c o n t e n t i s 35 % by w e i g h t o r

l e s s and t h e w e i g h t r a t i o of t h e VdF u n i t s t o t h e

HFP u n i t s i s i n t h e r a n g e of 8 0 : 2 0 t o 5 0 : 5 0 . I f t h e

TFE u n i t c o n t e n t i s m o r e t h a n 35 % by w e i g h t , t h e

f l u o r i n e - c o n t a i n i n g e l a s t o m e r b e c o m e s r e s i n o u s ,

w h i c h i s n o t d e s i r a b l e . The p r e f e r a b l e r a n g e of t h e

TFE u n i t c o n t e n t i s 5 to 35 % by w e i g h t . Wi th a TFE

u n i t c o n t e n t of 5 % by w e i g h t o r m o r e , t h e p o l y -

m e r i z a t i o n r e a c t i o n p r o c e e d s s m o o t h l y , w h i c h f a c i l i -

t a t e s to i m p a r t t h e d e s i r e d v a l u e of t h e l i m i t i n g

v i s c o s i t y n u m b e r to t h e r e s u l t i n g e l a s t o m e r .

In t e r m s of a l i m i t i n g v i s c o s i t y n u m b e r ( m l / g )

s m e a s u r e s of t h e m o l e c u l a r w e i g h t of a f l u o r i n e -

g a i n i n g e l a s t o m e r , t h e f l u o r i n e - c o n t a i n i n g

. s t o m e r of t h e p r e s e n t i n v e n t i o n h a s a v a l u e o f

] in t h e r a n g e of f r o m 100 t o l e s s t h a n 2 5 0 ,

e f e r a b l y 120 to l e s s t h a n 2 5 0 .

i n t h e f l u o r i n e - c o n t a i n i n g e l a s t o m e r of t h e

e s e n t i n v e n t i o n , f r o m t h e v i e w p o i n t of w o r k -

d l i t y , i t i s p r e f e r r e d t h a t when [n ] i s 100 t o

iSs t h a n 160, M1 oo be 10 t o l e s s t h a n 20 % b y

s i g h t , w h e n [n ] i s 1 60 t o l e s s t h a n 2 2 0 , M100 be 2 0

o l e s s t h a n 30 % by w e i g h t , a n d w h e n [r, ] i s 220 t o

s s s t h a n 250, M100 be 30 t o 35 % by w e i g h t .

The a b o v e - m e n t i o n e d t e r p o l y m e r i s e s p e c i a l l y

x c e l l e n t w i t h r e s p e c t to t h e b a l a n c e of c o m p r e s s i o n

e t r e s i s t a n t p r o p e r t i e s , r e s i s t a n c e to c h e m i c a l s

.nd s o l v e n t s , and w o r k a b i l i t y . In t h e t e r p o l y m e r o f

:he p r e s e n t i n v e n t i o n , i t i s more p r e f e r r e d t h a t

:he TFE u n i t c o n t e n t be 25 to 5 % by w e i g h t . W i t h

r e s p e c t t o t h e w e i g h t r a t i o of VdF u n i t s a n d H F P

. n i t s , i t i s more p r e f e r a b l y 60 :40 to 5 0 : 5 0 w h e n

[n] i s 100 t o l e s s t h a n 160 a n d M100 i s 1 0 t o l e s s

t h a n 20 % by w e i g h t b a s e d on t h e w e i g h t of t h e

e l a s t o m e r , 7 0 : 3 0 t o 6 0 : 4 0 when [n] i s 160 to l e s s

t h a n 220 and M100 i s 20 t o l e s s t h a n 30 % b y

0 3 1 4 7 8 6

wexyrvc, ana o u : z u to / u : J 0 when Lnj i s 220 to l e s s

t h a n 250 and 0Q is 30 to 35 % by w e i g h t .

As d e s c r i b e d t h e r e i n b e f o r e , in t h e p r e s e n t

i n v e n t i o n i t i s e s s e n t i a l f o r M5 t o be 5 % by w e i g h t

or l e s s . Even t h e f l u o r i n e - c o n t a i n i n g e l a s t o m e r

h a v i n g a r e l a t i v e l y s m a l l v a l u e of [n] w i t h i n t h e

r a n g e of [n ] d e s c r i b e d a b o v e and h a v i n g a h i g h

f l u o r i n e c o n t e n t , i s c a u s e d t o have an u n e x p e c t e d l y

s m a l l c o m p r e s s i o n s e t , when t h e M5 c o n t e n t i s 5 % b y

w e i g h t or l e s s .

M o r e o v e r , in t h e f l u o r i n e - c o n t a i n i n g e l a s t o m e r

of t h e p r e s e n t i n v e n t i o n i t i s more p r e f e r r e d t h a t

t h e r a t i o of t h e w e i g h t a v e r a g e m o l e c u l a r w e i g h t

(Mw) to t h e n u m b e r a v e r a g e m o l e c u l a r w e i g h t ( i n ) ,

t h a t i s , Mw/Mn be in t h e r a n g e of 2 to 4. By

c o n t r o l l i n g t h e Mw/Mn a t t h i s r a n g e , t h e m o l e c u l a r

w e i g h t d i s t r i b u t i o n can be g r e a t l y n a r r o w e d , l e a d i n g

to f u r t h e r i m p r o v e m e n t of t h e d e s i r e d p r o p e r t i e s .

C o n v e n t i o n a l f l u o r i n e - c o n t a i n i n g e l a s t o m e r s a r e

g e n e r a l l y p r o d u c e d by e m u l s i o n p o l y m e r i z a t i o n e x c e p t

in s p e c i a l c a s e s s u s p e n s i o n p o l y m e r i z a t i o n or s o l u -

t i o n p o l y m e r i z a t i o n i s e m p l o y e d . H o w e v e r , t h e t y p e

of p o l y m e r i z a t i o n w h i c h i s s u i t e d f o r p r o d u c i n g t h e

f l u o r i n e - c o n t a i n i n g e l a s t o m e r of t h e p r e s e n t i n v e n -

t i o n i s s u s p e n s i o n p o l y m e r i z a t i o n . W i t h r e s p e c t t o

e a c t i o n c o n d i t i o n s t o r p r o d u c i n g une u u o i i u b -

: o n t a i n i n g e l a s t o m e r of t h e p r e s e n t i n v e n t i o n , t h e

' o l l o w i n g can be m e n t i o n e d . The p o l y m e r i z a t i o n

; e m p e r a t u r e i s 50 °C or h i g h e r . As a c a t a l y s t , a

l y d r o c a r b o n p e r o x y d i c a r b o n a t e s u c h as d i i s o p r o p y l

j e r o x y d i c a r b o n a t e i s e m p l o y e d , and t h e t o t a l a m o u n t

3f t h e c a t a l y s t i s a d d e d a t o n c e . The p o l y m e r i -

s a t i o n r e a c t i o n i s c o n d u c t e d f o r a p e r i o d of 7 to 1 8

l o u r s . I f t h e p o l y m e r i z a t i o n p r e s s u r e i s r a i s e d , t h e

p o l y m e r i z a t i o n t i m e can be s h o r t e n e d .

H e r e i n b e l o w , t h e s u s p e n s i o n p o l y m e r i z a t i o n f o r

p r o d u c i n g t h e f l u o r i n e - c o n t a i n i n g e l a s t o m e r of t h e

p r e s e n t i n v e n t i o n w i l l be i l l u s t r a t i v e l y d e s c r i b e d .

I n t o an a q u e o u s m e d i u m i s d i s p e r s e d an i n e r t

o r g a n i c s o l v e n t , in w h i c h a p r e s c r i b e d m o n o m e r

m i x t u r e ( s t a r t i n g m o n o m e r m i x t u r e ) i s d i s s o l v e d . A

s u s p e n s i o n s t a b i l i z e r and an o i l - s o l u b l e c a t a l y s t

a r e a d d e d t h e r e t o , f o l l o w e d by a m e c h a n i c a l

s t i r r i n g w h i l e m a i n t a i n i n g t h e t e m p e r a t u r e a t 50 t o

60 °C. S u b s e q u e n t l y , a d d e d t h e r e t o i s a f r e s h

m o n o m e r m i x t u r e ( a d d i t i o n a l m o n o m e r m i x t u r e ) t o

m a i n t a i n t h e p o l y m e r i z a t i o n p r e s s u r e a t a

p r e d e t e r m i n e d l e v e l w i t h i n t h e r a n g e of 10 t o

17 k g / c m 2 - G , and t h e r e b y a d v a n c i n g t h e r e a c t i o n .

The p r o p o r t i o n s of t h e m o n o m e r u n i t s in t h e

0 3 1 4 7 8 6

r e s u l t a n t i i u o r i n e - c o n t a m i n g e l a s t o m e r d e p e n d s o n

t h e r e l a t i o n s h i p b e t w e e n t h e p r o p o r t i o n s of t h e

s t a r t i n g m o n o m e r s and t h o s e of t h e a d d i t i o n a l

m o n o m e r s .

The p r o p o r t i o n s of t h e s t a r t i n g m o n o m e r s a n d

t h o s e of t h e a d d i t i o n a l m o n o m e r s can be d e t e r m i n e d

by gas c h r o m a t o g r a p h y (G.C.) , and t h e p r o p o r t i o n s

of t h e m o n o m e r u n i t s in t h e f l u o r i n e - c o n t a i n i n g

e l a s t o m e r can be d e t e r m i n e d by d i s s o l v i n g t h e e l a s -

t o m e r in a c e t o n e and s u b j e c t i n g t h e r e s u l t a n t s o l u -

t i o n to 19FNMR.

As t h e i n e r t o r g a n i c s o l v e n t u s e d in t h e s u s -

p e n s i o n p o l y m e r i z a t i o n , t h e r e may be e m p l o y e d a n

o r g a n i c s o l v e n t w h i c h d o e s n o t h a v e a c a r b o n -

h y d r o g e n l i n k a g e , s u c h a l i n k a g e b e i n g p r o n e t o

c a u s e r a d i c a l c h a i n t r a n s f e r . Of s u c h s o l v e n t s ,

1 ,1 , 2 - t r i c h l o r o - 1 , 2 , 2 - t r i f l u o r o e t h a n e i s p r e f e r r e d

f r o m t h e v i e w p o i n t of p e r f o r m a n c e and c o s t . As a

s u s p e n s i o n s t a b i l i z e r , m e t h y l c e l l u l o s e i s p r e -

f e r r e d . As an o i l - s o l u b l e c a t a l y s t , a d i a l k y l

p e r o x y d i c a r b o n a t e s u c h as d i i s o p r o p y l p e r o x y -

c a r b o n a t e i s p r e f e r r e d b e c a u s e of i t s h i g h d e c o m -

p o s i t i o n t e m p e r a t u r e .

F u r t h e r , i t s h o u l d be n o t e d t h a t a c c o r d i n g t o

t h e p r e s e n t i n v e n t i o n , t h e f l u o r i n e - c o n t a i n i n g

0 3 1 4 7 8 6

e l a s t o m e r of t h e p r e s e n t i n v e n t i o n h a v i n g t h e

d e s i r e d [n] can be o b t a i n e d by p r o d u c i n g a f l u o r i n e -

c o n t a i n i n g e l a s t o m e r h a v i n g a v a l u e of [ n] w h i c h i s

10 to 100 l a r g e r t h a n t h e d e s i r e d v a l u e of [n] a n d

t h e n s u b j e c t i n g i t t o e x t r u s i o n . The t y p e s o f

e x t r u d e r s a r e n o t l i m i t e d , and any c u s t o m a r y

e x t r u d e r may be e m p l o y e d f o r t h e p u r p o s e i n s o f a r a s

i t i s of a h e a t e d t y p e and i s c a p a b l e of e x e r t i n g

s h e a r i n g s t r e s s . T h i s m e t h o d w i l l be d e s c r i b e d

h e r e i n u n d e r by t a k i n g as an e x a m p l e t h e c a s e w h e r e a

t w i n e x t r u d e r i s u s e d . When t h e p r e s e n t f l u o r i n e -

c o n t a i n i n g e l a s t o m e r i s e x t r u d e d by m e a n s of a t w i n

e x t r u d e r h a v i n g 1 to 2 s e a l r i n g s a t a b a r r e l

t e m p e r a t u r e of 140 to 280 °C, a r e v o l u t i o n n u m b e r o f

s c r e w s of 120 t o 400 rpm a n d an e x t r u s i o n r a t e of 2 0

to 50 k g / H r , t h e t e m p e r a t u r e of t h e f l u o r i n e -

c o n t a i n i n g e l a s t o m e r b e c o m e s 280 to 350 °C. [n] o f

t h e f l u o r i n e - c o n t a i n i n g e l a s t o m e r t h u s e x t r u d e d

d e c r e a s e s , and M-jqo d e c r e a s e s b u t s u b s t a n t i a l l y n o

i n c r e a s e i s o b s e r v e d w i t h r e s p e c t to M^. As a

r e s u l t , s u r p r i s i n g l y , t h e w o r k a b i l i t y of t h e

e l a s t o m e r i s i m p r o v e d b u t t h e p r o p e r t i e s of a v u l c a -

n i z a t e made f r o m t h e e l a s t o m e r u n d e r g o s u b s t a n t i a l l y

no c h a n g e . In o r d e r to c o n t r o l M5 to 5 % by w e i g h t

or l e s s , i t i s p r e f e r r e d to e x t r u d e a f l u o r i n e -

0 3 1 4 7 8 6

c o n t a i n i n g e l a s t o m e r h a v i n g a v a l u e of [n] w h i c h i s

10 to 100 l a r g e r t h a n t h e d e s i r e d [n ] by m e a n s of a n

e x t r u d e r . I f [n] of t h e e l a s t o m e r to be e x t r u d e d i s

more t h a n 100 [n ] l a r g e r t h a n t h e d e s i r e d [n ] , t h e

5 e l a s t o m e r w i l l d i s a d v a n t a g e o u s l y be d i s c o l o r e d . S o m e

r e s u l t s of e x t r u s i o n s a r e s h o w n in T a b l e 1 .

1 / -

(F c o n t e n t (F c o n t e n t 6 8 . 7 wt%) 6 7 . 3 w t % )

b e f o r e a f t e r b e f o r e a f t e r e x t r u - e x t r u - e x t r u - e x t r u - s i o n s i o n s i o n s i o n

L ri J 111 ' - "

M5 1.1 1 . 5 0 .8 1 . 2

r o p e r t i e s of M100 3 6 . 0 2 2 . 2 44 .1 3 0 . 0

n v u l c a n i z e d _ _ _ l a s t o m e r Mw/Mn 3 .0 2 . 4 2 . 7 Z . i

r o l l - k n i t t i n g 204 17 322 1 8 n u m b e r 3 )

n a r a n e s s { J I S - A )

t e n s i l e s t r e s s a t 100% e l o n g - g a t i o n

> r o p e r t i e s ( k g f / c m ) )f v u l c a n i z e d e l a s t o m e r

t e n s i l e s t r e n g t h ( k g f / c m ^ )

e l o n g a t i o n (%)

c o m p r e s s i o n s e t (%) ( 2 0 0 ° C / 7 2 H r )

48 46 61 56

I77 170 199 1 8 5

300 300 255 2 5 5

20 20 17 1 6

N o t e :

1 ) c o m p o s i t i o n of s a m p l e A: V d F / H F P / T F E =

0 3 1 4 7 8 6 '

@ • j . u / j j . i / ^ j . i r = b a . / wt%

2) c o m p o s i t i o n of s a m p l e B: VdF /HFP /TFE =

5 2 . 4 / 2 7 . 8 / 1 8 . 8 F = 67.3 wt%

3) The r o l l - k n i t t i n g n u m b e r was d e t e r m i n e d a s

f o l l o w s . 6 - I n c h r o l l s w e r e e m p l o y e d { t h e

s p e e d r a t i o of t h e f r o n t r o l l to t h e b a c k

r o l l = 1 : 1 . 1 4 ) , t h e r o l l t e m p e r a t u r e w a s

m a i n t a i n e d a t 30 + 2 °C, and t h e r o l l

n i p was a d j u s t e d a t 0.8 mm. The f l u o r i n e -

c o n t a i n i n g e l a s t o m e r was s u b j e c t e d to t a i l i n g

by i n t r o d u c i n g i t b e t w e e n t h e r o l l s , 50 g a t a

t i m e a t 5 - s e c o n d i n t e r v a l s . The t o t a l n u m b e r

of r e v o l u t i o n of t h e r o l l a t w h i c h t h e

i n t r o d u c e d f l u o r i n e - c o n t a i n i n g e l a s t o m e r b e g a n

to s t i c k t o t h e r o l l i n a u n i f o r m s e m i t r a n s -

p a r e n t s h e e t f o r m was t a k e n as t h e " r o l l -

k n i t t i n g n u m b e r " .


> r e s e n t i n v e n t i o n can be v u l c a n i z e d by m e a n s of a

> o l y a m i n e c o m p o u n d , p o l y o l c o m p o u n d or t h e l i k e , a n d

v u l c a n i z a t i o n t h e r e o f by means of a p o l y o l c o m p o u n d

> a r t i c u l a r l y a l l o w s t h e f l u o r i n e - c o n t a i n i n g

i l a s t o m e r to r e m a r k a b l y e x e r t i t s i m p r o v e d p r o p e r -

: i e s . H e r e i n b e l o w , t h e v u l c a n i z a t i o n m e t h o d u s i n g a

>olyol c o m p o u n d i s d e s c r i b e d .

To t h e f l u o r i n e - c o n t a i n i n g e l a s t o m e r a r e a d d e d

in a c i d b i n d e r , a p o l y o l c o m p o u n d , a v u l c a n i z a t i o n

i c c e l e r a t o r a n d , a c c o r d i n g to n e e d , a f i l l e r ,

f o l l o w e d by k n e a d i n g . S u b s e q u e n t l y , t h e k e a d e d

a i x t u r e i s h e a t e d to e f f e c t v u l c a n i z a t i o n .

As an a c i d b i n d e r , t h e r e may be m e n t i o n e d a n

o x i d e o r h y d r o x i d e of a b i v a l e n t m e t a l s u c h as a n

o x i d e or h y d r o x i d e of m a g n e s i u m , c a l c i u m , z i n c o r

l e a d . The a m o u n t of t h e b i n d e r to be u s e d i s i n

t h e r a n g e of 1 t o 30 p a r t s by w e i g h t , p r e f e r a b l y 2

t o 20 p a r t s by w e i g h t p e r 100 p a r t s by w e i g h t o f

t h e e l a s t o m e r .

As a p o l y o l c o m p o u n d , t h e r e may be m e n t i o n e d

t i y d r o q u i n o n e , 2 , 2 - b i s ( 4 - h y d r o x y p h e n y l ) p r o p a n e - .

( b i s p h e n o l A), 2 , 2 - b i s ( 4 - h y d r o x y p h e n y l ) p e r f l u o r o -

p r o p a n e ( b i s p h e n o l AF), 4 , 4 ' - d i h y d r o x y d i p h e n y l -

m e t h a n e , and 2 , 2 - b i s ( 4 - h y d r o x y p h e n y l ) b u t a n e . T h e

a m o u n t of t h e p o l y o l c o m p o u n d t o be u s e d i s 0.1 t o

10 p a r t s by w e i g h t , p r e f e r a b l y 0.6 to 5 p a r t s b y

w e i g h t p e r 1 00 p a r t s by w e i g h t of t h e e l a s t o m e r .

As a v u l c a n i z a t i o n a c c e l e r a t o r , t h e r e may b e

m e n t i o n e d a q u a t e r n a r y o n i u m s a l t , a q u a t e r n a r y

p h o s p h o n i u m s a l t , a q u a t e r n a r y a m m o n i u m s a l t a n d

i m i n i u m s a l t , s u c h as t e t r c r m e t h y l a m m o n i u m c h l o r i d e ,

0 3 1 4 7

t e t r a e t h y l a m m o n i u m c h l o r i d e , t e t r a p r o p y l a m m o n i u m

c h l o r i d e , t e t r a b u t y l a m m o n i u m c h l o r i d e , t e t r a b u t y l -

a m m o n i u m b r o m i d e , b i s ( b e n z y l d i p h e n y l p h o s p h i n e )

i m i n i u m c h l o r i d e , t e t r a b u t y l p h o s p h o n i u m c h l o r i d e ,

b e n z y l t r i p h e n y l p h o s p h o n i u m c h l o r i d e and b e n z y l -

t r i o c t y l p h o s p h o n i u m c h l o r i d e . The a m o u n t of t h e

v u l c a n i z a t i o n a c c e l e r a t o r i s 0.05 to 2 p a r t s b y

w e i g h t , p r e f e r a b l y 0.1 to 1 p a r t by w e i g h t p e r 1 0 0

p a r t s by w e i g h t of t h e e l a s t o m e r . As a f i l l e r o r

r e i n f o r c i n g a g e n t , c a r b o n b l a c k , s i l i c a , c l a y , t a l c

or t h e l i k e may be e m p l o y e d d e p e n d i n g on t h e u s e .

A m i x t u r e of t h e f l u o r i n e - c o n t a i n i n g e l a s t o m e r t

a p l o y o l c o m p o u n d , a v u l c a n i z a t i o n a c c e l e r a t o r and e

f i l l e r i s k n e a d e d by m e a n s of r o l l s o r a B a n b u r y

m i x e r , and s u b j e c t e d to a p r i m a r y v u l c a n i z a t i o n in c

m e t a l mold u n d e r p r e s s u r e and t h e n to a s e c o n d a r y

v u l c a n i z a t i o n . G e n e r a l l y , t h e p r i m a r y v u l c a n i z a t i o n

i s e f f e c t e d a t 100 t o 2 0 0 ° C f o r 10 t o 180 m i n u n d e r

20 t o 100 k g / c m -G and t h e s e c o n d a r y v u l c a n i z a t i o n

i s e f f e c t e d a t 150 t o 3 0 0 ° C f o r s e v e r a l m i n u t e s t o

30 h o u r s . O p t i o n a l l y , t h e s e c o n d a r y v u l c a n i z a t i o n

may be o m i t t e d .

T h r o u g h t h e v u l c a n i z a t i o n , t h e r e can be o b -

t a i n e d a h e a t - f i x i n g r o l l , a c o n t r o l v a l v e , a d i a -

p h r a g m , s h a p e d p a c k i n g s s u c h as 0 - r i n g , V - p a c k i n g ,

3 3 1 4 7 8 b

J - p a c k i n g , Y - p a c k i n g , D - r i n g , t r i a n g u l a r r i n g , T -

rring and X - r i n g , a g a s k e t , a r u b b e r v a l v e s e a t t y p e

b u t t e r f l y v a l v e , a s t e m v a l v e , an o i l s e a l , a

s h a p e d a r t i c l e f o r u s e w i t h SF c l a s s e n g i n e o i l , a

f u e l h o s e , a h e a t - s h r i n k a b l e t u b i n g , a w e t f r i c t i o n

m a t e r i a l , a w i r e c o a t i n g , a p i e z o e l e c t r i c m a t e r i a l ,

b e l l o w s f o r s m o k e d u c t j o i n t .

In t h e u s e of t h e e l a s t o m e r as a d i a p h r a g m , a n

e l o n g a t i o n i s r e q u i r e d r a t h e r t h a n a c o m p r e s s i o n s e t

r e s i s t a n c e a n d , t h e r e f o r e , v u l c a n i z a t i o n by m e a n s o f

a p o l y a m i n e c o m p o u n d i s a l s o e f f e c t i v e in m o l d i n g

t he f l u o r i n e - c o n t a i n i n g e l a s t o m e r of t h e p r e s e n t

i n v e n t i o n . The a b o v e - m e n t i o n e d c o n d i t i o n s f o r

v u l c a n i z a t i o n by m e a n s of a p o l y o l c o m p o u n d m a y

a p p l y t o t h i s v u l c a n i z a t i o n by m e a n s of a p o l y a m i n e

c o m p o u n d . In e f f e c t i n g t h e v u l c a n i z a t i o n by m e a n s

of a p o l y a m i n e c o m p o u n d , t h e f o l l o w i n g f o r m u l a t i o n

may be e m p l o y e d . .

The f o r m u l a t i o n may c o m p r i s e 100 p a r t s b y

w e i g h t of t h e e l a s t o m e r , 0.3 to 5 p a r t s by w e i g h t ,

p r e f e r a b l y 0.5 to 4 p a r t s by w e i g h t of a p o l y a m i n e

c o m p o u n d s u c h as h e x a m e t h y l e n e d i a m i n e c a r b a m a t e a n d

1 to 30 p a r t s by w e i g h t , p r e f e r a b l y 5 to 20 p a r t s b y

w e i g h t of an o x i d e of a b i v a l e n t m e t a l .

W i t h r e s p e c t t o t h e f l u o r i n e - c o n t a i n i n g

- 22 -

0 3 1 4 7 8 6

e l a s t o m e r of t h e p r e s e n t i n v e n t i o n , t h e m e a s u r i n g

c o n d i t i o n s f o r t h e l i m i t i n g v i s c o s i t y n u m b e r and t h e

m o l e c u l a r w e i g h t d i s t r i b u t i o n (M5 and M-jgg), and t h e

s t a n d a r d c o n d i t i o n s f o r t h e v u l c a n i z a t i o n by m e a n s

of a p o l y o l c o m p o u n d a r e as f o l l o w s .

(1) L i m i t i n g v i s c o s i t y n u m b e r

A 0.1 g / 1 0 0 ml s o l u t i o n of t h e e l a s t o m e r i n

m e t h y l e t h y l k e t o n e i s s u b j e c t e d to v i s c o s i t y

m e a s u r e m e n t u s i n g a c a p i l l a r y v i s c o m e t e r a t 3 5 ° C .

(2) M o l e c u l a r w e i g h t d i s t r i b u t i o n

L i q u i d c h r o m a t o g r a p h y : LC-3A ( m a n u f a c t u r e d b y

S h i m a d z u C o r p . , J a p a n )

C o l u m n s : KF-80M ( t w o ) + K F - 8 0 0 P ( p r e c o l u m n ) ( m a n u -

f a c t u r e d by Showa Denko K.K., J a p a n )

D e t e c t o r : E R C - 7 5 1 0 S ( m a n u f a c t u r e d by EL MA O p t i c a l

Works , L t d . , J a p a n )

I n t e g r a t o r : 700 OA ( m a n u f a c t u r e d by S y s t e m

I n s t r u m e n t s Co., L t d . , J a p a n )

D e v e l o p e r : t e t r a h y d r o f u r a n e

C o n c e n t r a t i o n : 0.1 % by w e i g h t

T e m p e r a t u r e : 35 °C

S t a n d a r d p o l y m e r f o r m o l e c u l a r w e i g h t c a l i b r a t i o n :

v a r i o u s m o n o d i s p e r s e p o l y s t y r e n e s ( m a n u f a c t u r e d b y

Toyo Soda Mfg Co., L t d . , J a p a n ) (Mw/Mn=1 .2 (max) )

n o t e : t h e M5 a n d M-, 0Q c o n t e n t s a r e

O I 4 / O D

c a l c u l a t e d t r o m t n e r e s u l t s uj. l uc a u u v c

m e a s u r e m e n t s .

(3) S t a n d a r d c o n d i t i o n s f o r t h e v u l c a n i z a t i o n

y m e a n s of a p o l y o l c o m p o u n d

' l u o r i n e - c o n t a i n i n g e l a s t o m e r : 100 p a r t s by w e i g h t

t i g h l y a c t i v a t e d m a g n e s i u m o x i d e : 3 p a r t s by w e i g h t

l a l c i u m h y d r o x i d e : 6 p a r t s by w e i g h t

J i s p h e n o l AF: 2 p a r t s by w e i g h t

J i s ( b e n z y l d i p h e n y l p h o s p h i n e ) i m i n i u m c h l o r i d e : 0 . 3

p a r t s by w e i g h t

Medium t h e r m a l c a r b o n : 30 p a r t s by w e i g h t

Means f o r k n e a d i n g : r o l l s

P r i m a r y h e a t p r e s s v u l c a n i z a t i o n : 177 °C, 10 m i n

S e c o n d a r y o v e n v u l c a n i z a t i o n : 232 °C, 24 h o u r s

W i t h r e s p e c t to t h e m e a s u r e m e n t of t h e

m e c h a n i c a l p r o p e r t i e s of .-the p o l y o l - v u l c a n i z e d

e l a s t o m e r , No. 3 d u m b b e l l s p e c i m e n s b l a n k e d o u t f r o m

a 2 m m - t h i c k s h e e t of v u l c a n i z e d e l a s t o m e r w e r e

s u b j e c t e d t o m e a s u r e m e n t u s i n g a t e n s i l e m a c h i n e

( m a n u f a c t u r e d by Toyo S e i k i Co., L t d . , J a p a n ) a t a

p u l l i n g r a t e of 50 c m / m i n a c c o r d i n g t o t h e m e t h o d o f

J I S - K 6 3 0 1 . @

On t h e o t h e r h a n d , w i t h r e s p e c t t o t h e m e a s u r e -

m e n t of t h e c o m p r e s s i o n s e t , s u b s t a n t i a l l y in a c c o r -

d a n c e w i t h t h e m e t h o d of J I S - K 6 3 0 1 , p o l y o l - v u l c a n -

to I 4 / o o

zed P -24 t y p e O - r i n g s w e r e c o m p r e s s e a so t n a u t n e

h i c k n e s s t h e r e o f d e c r e a s e s by 25 % and k e p t a t

!Q0 °C f o r 72 h o u r s a n d t h e n a l l o w e d t o c o o l a t r o o m

: e m p e r a t u r e f o r 30 m i n , f o l l o w e d by m e a s u r e m e n t

i s i n g a t h i c k n e s s m e t e r ( m a n u f a c t u r e d by K o b u n s h i

C e i k i Co . , L t d . , J a p a n h

F u r t h e r , t h e c o n d i t i o n s f o r t h e a b r a s i o n

r e s i s t a n c e m e a s u r e m e n t was as f o l l o w s .

C o n d i t i o n s f o r a b r a s i o n r e s i s t a n c e m e a s u r e m e n t

T a b e r a b r a s i o n (ASTM D1 0 4 4 - 5 6 ) was m e a s u r e d

u n d e r t h e f o l l o w i n g c o n d i t i o n s .

M a c h i n e : T a b e r m a c h i n e

( m a n u f a c t u r e d by Toyo T e s t e r C o r p o r a t i o n ,

J a p a n )

T r u c k w h e e l : H - 2 2

U n i t of w e a r : w e i g h t l o s s ( m g ) / 1 0 0 0

t i m e s ( room t e m p e r a t u r e )


p r e s e n t i n v e n t i o n has a low Mooney v i s c o s i t y ( M o o n e y

S c o r c h ) and an e x c e l l e n t w o r k a b i l i t y , and i t h a s

a l s o good mold r e l e a s e c h a r a c t e r i s t i c s so t h a t t h e

mold h a r d l y t a k e s g r i m e . The v u l c a n i z e d e l a s t o m e r

h a s a low t e n s i l e s t r e s s a t 1 00 % e l o n g a t i o n a n d a

low h a r d n e s s and , in a d d i t i o n to t h e s e s o - c a l l e d

e l a s t o m e r i c p r o p e r t i e s , i t has s u c h an e x c e l l e n t

- 25 -

0 3 1 4 7 8 6

p r o p e r t y t h a t i t i s low in c o m p r e s s i o n s e t . T h e

v u l c a n i z e d e l a s t o m e r h a s a c o m p r e s s i o n s e t a s

r e m a r k a b l y l o w as 20 o r l e s s as t e s t e d a t 200 ° C

f o r 72 h o u r s , and a l s o has a l a r g e t e n s i l e s t r e n g t h

and d o e s n o t b e c o m e b r i t t l e e v e n a t low t e m p e r a t u r e .

F u r t h e r , t h e e l a s t o m e r e x h i b i t s a l m o s t no m i l l

s h r i n k a g e . F u r t h e r m o r e , s i n c e i t s Mooney v i s c o s i t y

t ML-j + 1Q (121 ° C ) ] i s i n t h e r a n g e of 90 t o 1 4 5 ,

e v e n i f [n] i s i n c r e a s e d , t h e e x c e l l e n t w o r k a b i l i t y

of t h e e l a s t o m e r i s m a i n t a i n e d . H e n c e , i n c o m p r e s -

s i o n m o l d i n g , t h e f l u i d i t y of t h e e l a s t o m e r i s

p r o p e r l y c o n t r o l l e d , t h e r e b y e x h i b i t i n g l e s s a i r

e n t r a p m e n t and l e s s b u r r .

P r e f e r r e d E m b o d i m e n t of t h e I n v e n t i o n

The p r e s e n t i n v e n t i o n w i l l be d e s c r i b e d in m o r e

d e t a i l w i t h r e f e r e n c e t o t h e E x a m p l e s , w h i c h s h o u l d

n o t be c o n s t r u e d t o be l i m i t i n g t h e s c o p e of t h e

p r e s e n t i n v e n t i o n .

E x a m p l e 1

The a i r in an a u t o c l a v e h a v i n g a c a p a c i t y o f

a b o u t 15 l i t e r s w h i c h i s p r o v i d e d w i t h an e l e c t r o -

m a g n e t i c s t i r r e r was f u l l y r e p l a c e d by n i t r o g e n g a s ,

and an e v a c u a t i o n - N 2 f i l l i n g c y c l e was r e p e a t e d 3

t i m e s . A f t e r t h e n i t r o g e n r e p l a c e m e n t , u n d e r

3 3 1 4 7 8 6

r e d u c e d p r e s s u r e , t h e a u t o c l a v e was c h a r g e d w i t h

5800 g of d e g a s s e d p u r i f i e d w a t e r , 2670 g of 1 , 1 , 2 -

t r i c h l o r o - 1 , 2 , 2 - t r i f l u o r o e t h a n e ( h e r e i n a f t e r

r e f e r r e d to as " F r e o n - 1 1 3") and 2.9 g of m e t h y l -

c e l l u l o s e ( v i s c o s i t y 5 0 c p ) , f o l l o w e d by s t i r r i n g a t

500 rpm w h i l e m a i n t a i n i n g t h e t e m p e r a t u r e a t 50 ° C .

S u b s e q u e n t l y , t h e r e was c h a r g e d a m o n o m e r m i x t u r e a s

a c h a r g e g a s w h i c h c o n s i s t e d of 26 .4 % by w e i g h t o f

VdF, 68.1 % by w e i g h t of HFP, and 5.5 % by w e i g h t o f

TFE u n t i l a p r e s s u r e of 1 3 k g / c m 2 - G was a t t a i n e d .

T h e n , 51 g of a F r e o n - 1 13 s o l u t i o n c o n t a i n i n g 10.5 %

by w e i g h t of d i i s o p r o p y l p e r o x y d i c a r b o n a t e as a

c a t a l y s t was i n t r o d u c e d to s t a r t t h e p o l y m e r i z a t i o n .

As t h e p o l y m e r i z a t i o n p r o c e e d e d , t h e p r e s s u r e

d e c r e a s e d to 1 2.5 k g / c m 2 - G . T h e n , t h e r e was a d d e d a

m o n o m e r m i x t u r e c o n s i s t i n g of 55 .3 % by w e i g h t o f

VdF, 28.3 % by w e i g h t of HFP and 16 .4 % by w e i g h t o f

TFE as an a d d i t i o n a l g a s , t h e r e b y t o b r i n g t h e

p r e s s u r e b a c k to 13 k g / c m 2 - G . R e p e a t i n g t h i s o p e r a -

t i o n , t h e p o l y m e r i z a t i o n r e a c t i o n was p e r f o r m e d f o r

9 h o u r s . A f t e r c o m p l e t i o n of t h e p o l y m e r i z a t i o n

r e a c t i o n , t h e r e m a i n i n g m o n o m e r m i x t u r e was d i s -

c h a r g e d . The o b t a i n e d s u s p e n s i o n was s u b j e c t e d t o

c e n t r i f u g a t i o n to r e m o v e w a t e r a n d , a f t e r t h o r o u g h l y

w a s h e d w i t h w a t e r , s u b j e c t e d to v a c u u m d r y i n g a t

- 27 -

O I 4 I O w

00 °C t o o b t a i n a b o u t a Kg 01 t n « u e a . L i . c u

l a s t o m e r . The o b t a i n e d f l u o r i n e - c o n t a i n i n g

l a s t o m e r was s u b j e c t e d to 1 9FNMR a n a l y s i s to f i n d

h a t t h e e l a s t o m e r c o n s i s t e d of 55.1 % by w e i g h t o f

dF u n i t s , 29.1 % by w e i g h t of HFP u n i t s and 15.8 %

iy w e i g h t of TFE u n i t s and t h a t [n] was 2 2 8 .

The t h u s o b t a i n e d f l u o r i n e - c o n t a i n i n g e l a s t o m e r

las s u b j e c t e d t o e x t r u s i o n u n d e r t h e b e l o w - d e s c r i b e d

i x t r u s i o n c o n d i t i o n s u s i n g t h e b e l o w - d e s c r i b e d

i x t r u d e r . A f t e r c u t t i n g by a h o t c u t t e r , t h e

s l a s t o m e r was l e f t t o c o o l , t h e r e b y o b t a i n i n g

p e l l e t s of t h e e l a s t o m e r .

[ E x t r u d e r ]

m a n u f a c t u r e d by t h e J a p a n S t e e l W o r k s , L t d . , J a p a n

Mode l : T E X 4 4 P S - 3 0 A W - 2 V ( t w i n - s c r e w )

[ E x t r u s i o n C o n d i t i o n s ]

T e m p e r a t u r e 170 ° C

R e v o l u t i o n n u m b e r of s c r e w s 300 r p m

S a m p l e s u p p l y r a t e -• 30 k g / h r

W i t h r e s p e c t t o t h e p e l l e t i z e d f l u o r i n e -

c o n t a i n i n g e l a s t o m e r , [n ] was 169 , Mn was 23.9 x

104, Mw/Mn was 2 .2 , M5 c o n t e n t was 2.0 % by w e i g h t ,

M100 c o n t e n t was 13.3 % by w e i g h t , and t h e M o o n e y

v i s c o s i t y [ML-, + 10 (121 °C)] was 1 0 2 .

As a r e s u l t of t h e p o l y o l v u l c a n i z a t i o n of t h e

- to -

0 3 1 4 7 8 6

p e n e t i z e a r l u o r i n e - c o n t a i n m g e l a s t o m e r u n d e r t h e

s t a n d a r d c o n d i t i o n s , t h e r e was o b t a i n e d a v u l -

c a n i z e d p r o d u c t h a v i n g e x t r e m e l y e x c e l l e n t m e c h a n -

i c a l p r o p e r t i e s . The m e c h a n i c a l p r o p e r t i e s of t h i s

v u l c a n i z e d r u b b e r a r e shown in T a b l e 2 .

T a b l e 2

H a r d - T e n s i l e T e n s i l e E l o n - Com- n e s s s t r e s s s t r e n g t h g a t i o n p r e s s i o n

( J I S - A ) a t 100 % ( K g f / c m 2 ) (%) s e t (%) e l o n - g a t i o n ( K g f / c m 2 )

10 5* 183 240 16

i x a m p i e /.

The p o l y m e r i z a t i o n was e f f e c t e d in s u b s t a n -

: i a l l y t h e same m a n n e r as in E x a m p l e 1 e x c e p t t h a t

:he p o l y m e r i z a t i o n c o n d i t i o n s w e r e as i n d i c a t e d i n

Cable 5 a t i t s c o l u m n e n t i t l e d " p o l y m e r i z a t i o n

r o n d i t i o n s " , and t h e e x t r u s i o n was c o n d u c t e d u n d e r

:he same c o n d i t i o n s as in E x a m p l e 1. B e f o r e t h e

s x t r u s i o n , [ri] was 143. In T a b l e 5 a r e s h o w n t h e

r e s u l t s of t h e p o l y m e r i z a t i o n and t h e p r o p e r t i e s o f

bhe p e l l e t i z e d e l a s t o m e r and t h e v u l c a n i z e d r u b b e r .

2y -

3 3 1 4 7 8 6

Example 3

In s u b s t a n t i a l l y t h e s ame m a n n e r as in E x a m p l e

1 , p u r i f i e d F r e o n - 1 1 3 and a s u s p e n s i o n s t a b i l i z e r

w e r e c h a r g e d i n t o an a u t o c l a v e , f o l l o w e d by s t i r r i n g

a t 500 rpm w h i l e k e e p i n g t h e t e m p e r a t u r e a t 50 ° C .

S u b s e q u e n t l y , t h e r e w e r e i n t r o d u c e d a m o n o m e r

m i x t u r e c o n s i s t i n g of 16.9 % by w e i g h t of VdF a n d

83.1 % by w e i g h t o f HFP u n t i l t h e p r e s s u r e b e c a m e

1 5 . 0 k g / c m 2 - G and t h e n 51 g of a F r e o n - 1 1 3 s o l u t i o n

c o n t a i n i n g 10.5 % by w e i g h t of d i i s o p r o p y l

p e r o x y d i c a r b o n a t e as a c a t a l y s t was i n t r o d u c e d t o

s t a r t t h e p o l y m e r i z a t i o n . As t h e p o l y m e r i z a t i o n

p r o c e e d e d , t h e p r e s s u r e d e c r e a s e d to 14.5 k g / c m - G .

T h e n , t h e r e w a s a d d e d a m i x e d g a s c o n s i s t i n g o f

5 1 . 7 % by w e i g h t of VdF and 48.3 % by w e i g h t of HFP

as an a d d i t i o n a l m o n o m e r , t h e r e b y to b r i n g t h e

p r e s s u r e b a c k t o 1 5 k g / c m 2 - G . R e p e a t i n g t h i s o p e r a -

t i o n , t h e p o l y m e r i z a t i o n r e a c t i o n was p e r f o r m e d f o r

15 h o u r s to o b t a i n a b o u t 5 kg of t h e d e s i r e d

e l a s t o m e r . The e l a s t o m e r c o n s i s t e d of 52.0 % b y

w e i g h t of VdF u n i t s and 48.0 % by w e i g h t of HFP

u n i t s , a n d [ n ] w a s 1 5 1 , I n was 17 .9 x 1 04 , Mw/Mn w a s

3 .2 , M5 was 4.3 %, M100 was 19.6 %, and M o o n e y

v i s c o s i t y [ML1 + 1Q (121 °C)] was 1 3 3 .

0 3 1 4 7 8 6

The t h u s o b t a i n e d f l u o r i n e - c o n t a i n i n g e l a s t o m e r

was s u b j e c t e d to p o l y o l v u l c a n i z a t i o n u n d e r t h e

s t a n d a r d c o n d i t i o n s . The p r o p e r t i e s of t h e o b t a i n e d

v u l c a n i z e d r u b b e r a r e s h o w n in T a b l e 3 .

T a b l e 3 -

H a t d - T e n s i l e T e n s i l e E l o n - C o m - n e s s s t r e s s s t r e n g t h g a t i o r i p r e s s i o n

( J I S - A ) a t 100 % * ( K g f / c m 2 ) (%) s e t (%) e l o n - g a t i o n ( K g f / c m 2 )

78 47 154 265 16

E x a m p l e s 4 and 5

S u b s t a n t i a l l y t h e s ame p r o c e d u r e s as in E x a m p l e

1 w e r e r e p e a t e d e x c e p t t h a t t h e p o l y m e r i z a t i o n

c o n d i t i o n s w e r e as i n d i c a t e d i n T a b l e 5 a t i t s

c o l u m n e n t i t l e d " p o l y m e r i z a t i o n c o n d i t i o n s " , and t h e

e x t r u s i o n was c o n d u c t e d u n d e r t h e same c o n d i t i o n s a s

in E x a m p l e 1. Wi th r e s p e c t to E x a m p l e s 4 and 5, t h e

v a l u e s of [n] b e f o r e e x t r u s i o n w e r e r e s p e c t i v e l y 2 3 0

and 1 67. The r e s u l t s of t h e p o l y m e r i z a t i o n , t h e

p r o p e r t i e s of t h e p e l l e t i z e d e l a s t o m e r , and t h e

p r o p e r t i e s of t h e v u l c a n i z e d r u b b e r a r e s h o w n i n

T a o i e d •

E x a m p l e 6

The p o l y m e r i z a t i o n was p e r f o r m e d in s u b s t a n -

t i a l l y t h e same m a n n e r as in E x a m p l e 3 e x c e p t t h a t

t h e p o l y m e r i z a t i o n c o n d i t i o n s w e r e as i n d i c a t e d i n

T a b l e 4 a t i t s c o l u m n e n t i t l e d " p o l y m e r i z a t i o n

c o n d i t i o n s " . The r e s u l t s of t h e p o l y m e r i z a t i o n , t h e

p r o p e r t i e s of t h e e l a s t o m e r , and t h e p r o p e r t i e s o f

t h e v u l c a n i z e d r u b b e r a r e s h o w n in T a b l e 4 .

— o Cr-i »-> E CM

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3 3 1 4 7 8 6

C o m p a r a t i v e E x a m p l e 1

The a i r in an a u t o c l a v e h a y i n g a c a p a c i t y of 1 5

L i t e r s w h i c h i s p r o v i d e d w i t h an e l e c t r o m a g n e t i c

s t i r r e r was f u l l y r e p l a c e d by n i t r o g e n g a s , and a n

e v a c u a t i o n - N 2 f i l l i n g c y c l e was r e p e a t e d 3 t i m e s ,

f o l l o w e d by r e d u c i n g t h e p r e s s u r e t o a l e v e l as l o w

as p o s s i b l e . S u b s e q u e n t l y , t h e a u t o c l a v e w a s

c h a r g e d w i t h 7500 g of d e g a s s e d p u r i f i e d w a t e r , 15 g

of a m m o n i u m p e r s u l f a t e a n d , as an e m u l s i f i e r , 22 .5 g

of a m m o n i u m p e r f l u o r o o c t a n o i c a c i d , and m a i n t a i n e d

a t 85 °C. T h e n , t h e r e was c h a r g e d a m o n o m e r m i x t u r e

c o n s i s t i n g of 34.9 % by w e i g h t of VdF, 44.9 % b y

w e i g h t of HFP and 20.2 % by w e i g h t of TFE u n t i l a

p r e s s u r e of 8 k g / c m 2 - G was a t t a i n e d . As t h e

p o l y m e r i z a t i o n p r o c e e d e d , t h e p r e s s u r e d e c r e a s e d t o

7 k g / c m 2 - G . T h e n , t h e r e was a d d e d an a d d i t i o n a l

m o n o m e r m i x t u r e c o n s i s t i n g of 45.1 % by w e i g h t o f

VdG, 3 1 . 4 % by w e i g h t of HFP and 23.5 % by w e i g h t o f

TFE, t h e r e b y to b r i n g t h e p r e s s u r e b a c k to 8 k g / c m -

G. R e p e a t i n g t h i s o p e r a t i o n , t h e p o l y m e r i z a t i o n

r e a c t i o n was p e r f o r m e d f o r 1.5 h o u r and , t h e n , t h e

r e m a i n i n g m o n o m e r m i x t u r e was d i s c h a r g e d to t e r m i -

n a t e t h e p o l y m e r i z a t i o n .

To t h e o b t a i n e d e m u l s i o n was a d d e d a m a g n e s i u m

c h l o r i d e s o l u t i o n to s a l t o u t t h e p o l y m e r . T h e

- 37 -

3 3 1 4 7 8 6

p o l y m e r was t h o r o u g h l y w a s h e d w i t h w a t e r and , t h e n ,

s u b j e c t e d t o v a c u u m d r y i n g a t 100 °C to o b t a i n a b o u t

1 .5 kg of a f l u o r i n e - c o n t a i n i n g e l a s t o m e r . T h e

19FNMR m e a s u r e m e n t s h o w e d t h a t t h e f l u o r i n e -

c o n t a i n i n g e l a s t o m e r c o n s i s t e d of 46.7 % by w e i g h t

of VdF u n i t s , 34 .0 % by w e i g h t of HFP u n i t s a n d

1 9 . 3 % by w e i g h t o f TFE u n i t s , [n ] was 106 m l / g , Mn

was 10.3 x 104 , Mw/Mn was 1 0 . 5 , M5 was 9.5 %, a n d

M100 was 27 .4 %.

T h i s f l u o r i n e - c o n t a i n i n g e l a s t o m e r w a s

s u b j e c t e d t o p o l y o l v u l c a n i z a t i o n u n d e r t h e s t a n d a r d

c o n d i t i o n s . The Mooney v i s c o s i t y of t h e v u l c a n i z a t e

was 91. The p r o p e r t i e s of t h e v u l c a n i z e d r u b b e r a r e

shown in T a b l e 6 .

T a b l e 6

H a r d - T e n s i l e T e n s i l e E l o n g a - C o m p r e s - n e s s s t r e s s s t r e n g t h t i o n s i o n s e t

( J I S - A ) a t 100 % ( k g f / c m 2 ) (%) (%) e l o n g a - t i o n ( k g f / c m 2 )

83 6 6 169 2 4 4 44

0 3 1 4 7 8 6

E x a m p l e 6

H e a t - f i x i n g r o l l

U s i n g t h e f l u o r i n e - c o n t a i n i n g e l a s t o m e r p o l y -

m e r i z e d i n E x a m p l e 2, a c o m p o s i t i o n was p r e p a r e d

a c c o r d i n g to t h e f o l l o w i n g f o r m u l a t i o n .

C o m p o n e n t s ( p a r t s by w e i g h t )

F l u o r i n e - c o n t a i n i n g e l a s t o m e r 1 0 0

Medium t h e r m a l c a r b o n 1 0

C a l c i u m h y d r o x i d e 4

Lead o x i d e 10

B i s p h e n o l . AF 2

b e n z y l t r i p h e n y p h o s p h o n i u m 0 . 6 c h l o r i d e

The c o m p o s i t i o n t h u s p r e p a r e d was k n e a d e d w e l l

a n d f o r m e d i n t o a t h i n s h e e t u s i n g a 6 - i n c h m i x i n g

r o l l . T h i s s h e e t was s u b j e c t e d to p r e s s m o l d i n g a t

177 °C u s i n g an e l e c t r i c h e a t p r e s s to p r o d u c e a

s a m p l e h a v i n g a s i z e of 200 mm x 100 mm x 0.5 mm

( t h i c k n e s s ) , f o l l o w e d by o v e n v u l c a n i z a t i o n a t

232 °C f o r 24 h o u r s . T h i s s a m p l e was r o l l e d u p

a r o u n d t h e u p p e r r o l l of a l a m i n a t o r ( m a n u f a c t u r e d

by M i t s u b i s h i C o r p o r a t i o n , J a p a n ) and t h e t e m p e r a -

t u r e of t h e s a m p l e s u r f a c e was r a i s e d to 180 ° C .

S u b s e q u e n t l y , a t o n e r i m a g e was f i x e d by a p p l y i n g

l i q u i d p o l y o r g a n o s i l o x a n e h a v i n g m e r c a p t o g r o u p s a s

13 1 4 / O D

u n c t i o n a l g r o u p s o n t o t h e s u r t a c e oi cne s a m p x e .

lo o f f s e t o c c u r r e d .

F u r t h e r , t h e f l u o r o r u b b e r was s u b j e c t e d t o

f a b e r a b r a s i o n m e a s u r e m e n t s u b s t a n t i a l l y i n

i c c o r d a n c e w i t h ASTM D1 0 4 4 - 5 6 t o f i n d t h a t t h e

/ o l u m e l o s s was 170 m g / 1 0 0 0 r e v o l u t i o n s .

C u r r e n t l y in t h e f i e l d of a f i x i n g r o l l , a

E l u o r o r e s i n , s i l i c o n e r u b b e r or t h e l i k e i s u s e d a s

a m a t e r i a l b u t e a c h of t h e s e m a t e r i a l s h a s p r o b l e m s

w i t h r e s p e c t t o t o n e r - f i x i n g a b i l i t y , d u r a b i l i t y ,

e t c . H o w e v e r , by u s i n g t h e f l u o r i n e - c o n t a i n i n g

e l a s t o m e r of t h e p r e s e n t i n v e n t i o n , a f i x i n g r o l l

h a v i n g an e x c e l l e n t f i x i n g a b i l i t y and an e x c e l l e n t

d u r a b i l i t y i s o b t a i n e d .

E x a m p l e 7

C o n t r o l v a l v e

I n t o t h e f l u o r i n e - c o n t a i n i n g e l a s t o m e r o b t a i n e d

in E x a m p l e 1 w e r e i n c o r p o r a t e d 2.0 p h r o f b i s p h e n o l

AF, 0.6 p h r of b e n z y l t r i p h e n y l p h o s p h o n i u m c h l o r i d e ,

30 ph r of m e d i u m t h e r m a l (MT) c a r b o n b l a c k , 6 p h r o f

c a l c i u m h y d r o x i d e and 3 p h r of h i g h l y a c t i v a t e d

m a g n e s i u m o x i d e , and t h e n v u l c a n i z a t i o n m o l d e d t o

o b t a i n a r u b b e r s h e e t . W i t h r e s p e c t to t h e

o b t a i n e d r u b b e r s h e e t , a s u r f a c e a d h e s i o n w a s

m e a s u r e d as d e s c r i b e d b e l o w .

- 40 -

0 3 1 4 7 8

A r u b b e r s h e e t [2 .0 m m ( t h i c k n e s s ) x 35 mm x

35 mm] was a t t a c h e d o n t o t h e u p p e r s u r f a c e of a f l a t

s t a n d u s i n g a h e a t r e s i s t a n t d o u b l e s i d e a d h e s i v e

t a p e and t h e r e o n was p l a c e d a h a l f - s t e e l ( J I S S - 4 5 C )

r i n g h a v i n g a f l a t b o t t o m w h i c h r i n g was p r o v i d e d

w i t h a w e i g h t - r e c e i v i n g p o r t i o n and a h a n g i n g m e a n s

so t h a t t h e f l a t b o t t o m c o n t a c t e d t h e r u b b e r s h e e t

( t h e r i n g was 25 mm in o u t e r d i a m e t e r and 19 mm i n

i n n e r d i a m e t e r , and t h e f l a t b o t t o m t h e r e o f i n

c o n t a c t w i t h t h e r u b b e r s h e e t had p r e v i o u s l y b e e n

a b r a d e d w i t h # 1 0 0 0 a b r a s i v e p a p e r ) . S u b s e q u e n t l y , a

w e i g h t was p l a c e d on t h e w e i g h t - r e c e i v i n g p o r t i o n o f

t h e r i n g so t h a t t h e t o t a l l o a d on t h e r u b b e r s h e e t

became 609 mm/cm2. The w h o l e was h e a t e d in an o v e n

a t 120 °C f o r 20 h o u r s , and t h e n t a k e n ou t a n d

a l l o w e d to s t a n d to c o o l f o r a b o u t 4 h o u r s . W h e n

t h e t e m p e r a t u r e d e s c e n d e d t o 23 °C, t h e w e i g h t w a s

r e m o v e d . Then , t h e r i n g a d h e r i n g t o t h e r u b b e r

s h e e t was c o n n e c t e d , by t h e h a n g i n g m e a n s , to a

t e n s i l e m a c h i n e h a v i n g a l o a d c e l l , and p u l l e d a t a

p u l l i n g r a t e of 50 m m / m i n to m e a s u r e t h e a d h e s i o n

s t r e n g t h . The r e s u l t i s shown in T a b l e 7 .

In v a r i o u s k i n d s of v a l v e s u s e d in a u t o m o b i l e s

e t c . , a d h e s i o n o f t e n o c c u r s b e t w e e n a v u l c a n i z e d

r u b b e r and an a d j a c e n t m e t a l p a r t a t t h e c o n t a c t

)15 1 4 / I J D

l o i n t t h e r e o f , w h i c h l e a d s to a s e r i o u s p r o m e m

s n d a n g e r i n g h u m a n l i f e . To o b v i a t e t h e a b o v e -

l e n t i o n e d p r o b l e m , a m e t h o d h a s b e e n d e v e l o p e d f o r

i m p a r t i n g an a n t i - a d h e s i v e p r o p e r t y to t h e s u r f a c e

jf a v u l c a n i z e d r u b b e r . In s u c h a c o n v e n t i o n a l

n e t h o d , r u b b e r m a t e r i a l s a r e i m p a r t e d w i t h an a n t i -

a d h e s i v e p r o p e r t y by i n c o r p o r a t i n g t h e r e i n t o a n

a d d i t i v e s u c h as t a l c , z e o l i t e , g r a p h i t e , T e f l o n o r

the l i k e . F u r t h e r , t h e r e h a v e b e e n p r o p o s e d a n o t h e r

m e t h o d in w h i c h o n l y t h e s u r f a c e p o r t i o n of a r u b b e r

m a t e r i a l i s c h e m i c a l l y or p h y s i c a l l y t r e a t e d t o

i m p a r t a n t i - a d h e s i v e n e s s t h e r e t o . H o w e v e r , e a c h o f

t h e s e m e t h o d s h a s a d r a w b a c k , t h a t i s , t h e f o r m e r

i m p a i r s t h e e s s e n t i a l p r o p e r t i e s of a r u b b e r

m a t e r i a l and t h e l a t t e r s o m e t i m e s b r i n g s a b o u t

s a f e t y and h e a l t h p r o b l e m s in a d d i t i o n to p r o b l e m s

a b o u t d u r a b i l i t y and r e l i a b i l i t y . By u s i n g t h e

f l u o r i n e - c o n t a i n i n g e l a s t o m e r of t h e p r e s e n t i n v e n -

t i o n h a v i n g a s p e c i f i c s t r u c t u r e , t h e p r o b l e m s

i n e v i t a b l y a c c o m p a n y i n g t h e c o n v e n t i o n a l m e t h o d s c a n

be c o m p l e t e l y s o l v e d .

E x a m p l e 8

W i t h r e s p e c t t o t h e p o l y m e r o b t a i n e d in E x a m p l e

5, a d h e s i o n was m e a s u r e d in t h e s a m e m a n n e r as i n

E x a m p l e 7. The r e s u l t i s s h o w n in T a b l e 7 .

0 3 1 4 7 8 6

C o m p a r a t i v e E x a m p l e s 2 and 3

U s i n g V i t o n E - 6 0 and V i t o n B w h i c h a r e

f l u o r i n e - c o n t a i n i n g e l a s t o m e r s p r o d u c e d by I .E. d u

Pon de N e m o u r s and C o m p a n y , a d h e s i o n was m e a s u r e d

in t n e s a m e m a n n e r as m E x a m p l e 8. The r e s u l t s

a r e shown in T a b l e 7 .

T a b l e 7

To h a l f s t e e l ( S - 4 5 C ) w i t h i t s s u r f a c e a b r a d e d w i t h # 1 0 0 0 a b r a s i v e p a p e r

a d h e s i o n a d h e s i o n ( k g f ) ( k g / c m 2 )

E x a m p l e 7 2 0 . 0 9 . 7

Example 8 21 .5 1 0 . 4

C o m p a r a t i v e E x a m p l e 2 2 8 . 7 1 3 . 8

C o m p a r a t i v e E x a m p l e 3 3 4 . 5 1 6 . 7

sxampie 9

S h a p e d p a c k i n g s s u c h as 0 - r i n g , V - p a c k i n g , U -

j a c k i n g , Y - p a c k i n g , D - r i n g , t r i a n g u l a r r i n g , T - r i n g

- 43 -

3 3 1 4 7 8 6

and X - r i n g

U s i n g t h e v u l c a n i z e d c o m p o s i t i o n o b t a i n e d i n

E x a m p l e 1 , t h e f o l l o w i n g t e s t was c o n d u c t e d . W i t h

r e s p e c t to a c o m p r e s s i o n s e t r e s i s t a n c e , an O - r i n g

( i n n e r d i a m e t e r 23.7 mm, t h i c k n e s s 3.5 mm) w a s

c o m p r e s s e d so t h a t t h e t h i c k n e s s d e c r e a s e d by 25 %,

and p u t in an o v e n and h e a t e d a t 200 °C f o r 1 7 0 0

h o u r s , f o l l o w e d by m e a s u r e m e n t a c c o r d i n g to J I S

K6301. An a b r a s i o n r e s i s t a n c e was e x a m i n e d by a

T a b e r a b r a s i o n t e s t s u b s t a n t i a l l y in a c c o r d a n c e w i t h

ASTM D1 0 4 4 - 5 6 . The T a b e r a b r a s i o n t e s t was c o n -

d u c t e d u s i n g a t r u c k w h e e l H-22 u n d e r s u c h c o n d i -

t i o n s t h a t t h e t o t a l n u m b e r of r e v o l u t i o n was 1 0 0 0

and a l o a d of 1 kg was a p p l i e d . The r e s u l t s a r e

s h o w n in T a b l e 8 .

B e s i d e ,.a c o m p r e s s i o n s e t r e s i s t a n c e , t h e s h a p e d

p a c k i n g s a r e r e q u i r e d to h a v e an a b r a s i o n r e s i s t a n c e

when t h e y a r e u s e d t o s e a l a m o v i n g p a r t . H o w e v e r ,

t h e c o n v e n t i o n a l f l u o r i n e - c o n t a i n i n g e l a s t o m e r s

w h i c h a r e u s e d in t h e f i e l d s r e q u i r i n g r e s i s t a n c e s

to h e a t , an o i l , a s o l v e n t or c h e m i c a l s h a v e n o t

n e c e s s a r i l y s u f f i c i e n t c o m p r e s s i o n s e t r e s i s t a n c e

and a b r a s i o n r e s i s t a n c e . In c o n t r a s t , t h e

v u l c a n i z e d c o m p o s i t i o n c o n t a i n i n g t h e f l u o r i n e -

c o n t a i n i n g e l a s t o m e r of t h e p r e s e n t i n v e n t i o n has a

3 3 1 4 7 8 6

L a r g e l y i m p r o v e d c o m p r e s s i o n s e t r e s i s t a n c e a n d

a b r a s i o n r e s i s t a n c e .

Example 1 0


E x a m p l e 2, t h e same t e s t s as in E x a m p l e 9 w e r e

c o n d u c t e d . The r e s u l t s a r e s h o w n in T a b l e 8 .

Example 1 1





U s i n g a v u l c a n i z e d c o m p o s i t i o n p r o d u c e d i n

s u b s t a n t i a l l y t h e same m a n n e r as in E x a m p l e 1

e x c e p t t h a t V i t o n E-60 m a n u f a c t u r e d by E . I . du P o n t

de N e m o u r s and C o m p a n y was u s e d i n p l a c e of t h e

f l u o r i n e - c o n t a i n i n g e l a s t o m e r of E x a m p l e 1 and t h a t

p r e s s v u l c a n i z a t i o n was e f f e c t e d f o r 20 m i n , t h e

same t e s t s as in E x a m p l e 9 w e r e c o n d u c t e d . T h e

r e s u l t s a r e s h o w n in T a b l e 8 .

- 45 -

0 3 1 4 7 8 6

T a b l e 8

E x a m p l e E x a m p l e E x a m p l e C o m p a r a t i v e 9 10 11 E x a m p l e 4

Com- p r e s s i o n 63 65 59 8 0 s e t ( % )

W e a r ( m g ) 265 340 280 4 0 0

E x a m p l e 1 2

O i l s e a l s



r e s p e c t t o a c o m p r e s s i o n s e t r e s i s t a n c e , an 0 - r i n g



and p u t in an o v e n and h e a t e d a t 200 °C f o r 1 7 0 0



T a b e r a b r a s i o n t e s t s u b s t a n t i a l l y i n a c c o r d a n c e w i t h





- 46 -

3 3 1 4 7 8 6

shown in T a b l e 9 .

B e s i d e a c o m p r e s s i o n s e t r e s i s t a n c e , o i l s e a l s

are r e q u i r e d to h a v e an a b r a s i o n r e s i s t a n c e w h e n

t hey a r e u s e d to s e a l a m o v i n g p a r t . H o w e v e r , t h e

c o n v e n t i o n a l f l u o r i n e - c o n t a i n i n g e l a s t o m e r s w h i c h

a r e u s e d in t h e f i e l d s r e q u i r i n g r e s i s t a n c e s t o

h e a t , an o i l , a s o l v e n t or c h e m i c a l s h a v e n o t

n e c e s s a r i l y s u f f i c i e n t c o m p r e s s i o n s e t r e s i s t a n c e

and a b r a s i o n r e s i s t a n c e . In c o n t r a s t , t h e


c o n t a i n i n g e l a s t o m e r of t h e p r e s e n t i n v e n t i o n h a s a

l a r g e l y i m p r o v e d c o m p r e s s i o n s e t r e s i s t a n c e a r i d

a b r a s i o n r e s i s t a n c e .

E x a m p l e 1 3




E x a m p l e 1 4


E x a m p l e 5, t h e same t e s t s as i n E x a m p l e 12 w e r e




s u b s t a n t i a l l y t h e same m a n n e r as in E x a m p l e 1 e x c e p t

t h a t V i t o n E-60 m a n u f a c t u r e d by E . I . du P o n t d e

- 47 -

'O I 4 / D O

[emour s and Company was u s e d m p x a c e ot m e

: l u o r i n e - c o n t a i n i n g e l a s t o m e r of E x a m p l e 1 and t h a t

i r e s s v u l c a n i z a t i o n was e f f e c t e d f o r 20 min , t h e

;ame t e s t s as in E x a m p l e 12 w e r e c o n d u c t e d . T h e

r e s u l t s a r e s h o w n in T a b l e 9 .

: a D i e y


Zom- D r e s s i o n 63 65 59 8 0 s e t ( % )

Wear (mg) 265 340 280 4 0 0

3 x a m p l e 1 5

D i a p h r a g m


E x a m p l e 1 , a f l e x c r a c k i n g t e s t was c o n d u c t e d a t

25 °C, a n d t h e n u m b e r of f l e x i n g s a t c r a c k w a s

m e a s u r e d u s i n g a de M a t t i a m a c h i n e a c c o r d i n g t o J I S

K6301. The r e s u l t i s s h o w n in T a b l e 1 0 .

D i a p h r a g m s a r e m a n u f a c t u r e d f r o m an e l a s t o m e r

a l o n e or a c o m p o s i t e m a t e r i a l c o n t a i n i n g e l a s t o m e r

and a c l o t h , and in e i t h e r c a s e a f l e x c r a c k i n g

r e s i s t a n c e i s r e q u i r e d . H o w e v e r , t h e c o n v e n t i o n a l

- 48 -

0 3 1 4 7 8 8

f l u o r i n e - c o n t a i n i n g e l a s t o m e r s w h i c h a r e u s e d in t h e

f i e l d s r e q u i r i n g r e s i s t a n c e s to h e a t , an o i l , a

s o l v e n t or c h e m i c a l s h a v e n o t n e c e s s a r i l y s u f f i c i e n t

f l e x i n g r e s i s t a n c e . In c o n t r a s t , t h e v u l c a n i z e d

c o m p o s i t i o n c o n t a i n i n g t h e f l u o r i n e - c o n t a i n i n g

e l a s t o m e r of t h e p r e s e n t i n v e n t i o n h a s a l a r g e l y

i m p r o v e d f l e x c r a c k i n g r e s i s t a n c e .

E x a m p l e 1 6


E x a m p l e 2, t h e same t e s t as in E x a m p l e 15 w a s

c o n d u c t e d , t h e r e s u l t i s s h o w n in T a b l e 1 0 .

E x a m p l e 17


E x a m p l e 5, t he same t e s t as in E x a m p l e 15 w a s

c o n d u c t e d . The r e s u l t i s s h o w n in T a b l e 1 0 .




t h a t V i t o n E-60 m a n u f a c t u r e d by E. I. du P o n t d e

N e m o u r s and Company was u s e d in p l a c e of t h e

f l u o r i n e - c o n t a i n i n g e l a s t o m e r of E x a m p l e 1 and t h a t

p r e s s v u l c a n i z a t i o n was e f f e c t e d f o r 20 min , t h e

s a m e t e s t as in E x a m p l e 1 5 was c o n d u c t e d .

0 3 1 4 7 8 6

T a b l e 10

Number of f l e x i n g s t o c r a c k i n i t i a t i o n

E x a m p l e 15 4 0 0 0

E x a m p l e 16 more t h a n 5 0 0 0 0

E x a m p l e 17 6 0 0 0

C o m p a r a t i v e E x a m p l e 6 8 0 0

E x a m p l e 1 8

G a s k e t


E x a m p l e 1 , a c o m p r e s s i o n s e t r e s i s t a n c e t e s t w a s

c o n d u c t e d as f o l l o w s . An O- r i n g ( i n n e r d i a m e t e r

2 3 . 7 mm, t h i c k n e s s 3.5 mm) was c o m p r e s s e d so t h a t

t h e t h i c k n e s s d e c r e a s e s by 25 %, and p u t in an o v e n

and h e a t e d a t 200 °C f o r 1700 h o u r s , f o l l o w e d b y

m e a s u r e m e n t a c c o r d i n g to J I S K6301. The r e s u l t i s

s h o w n in T a b l e 1 1 .

G a s k e t s a r e r e q u i r e d to h a v e a c o m p r e s s i o n s e t

r e s i s t a n c e . H o w e v e r , t h e c o n v e n t i o n a l f l u o r i n e -

c o n t a i n i n g e l a s t o m e r s w h i c h a r e u s e d in t h e f i e l d s

- 50 -

0 3 1 4 7 8

r e q u i r i n g r e s i s t a n c e s to h e a t , an o i l , a s o l v e n t o r

c h e m i c a l s h a v e no t n e c e s s a r i l y s u f f i c i e n t l o n g - t e r m

c o m p r e s s i o n s e t r e s i s t a n c e . In c o n t r a s t , t h e v u l -

c a n i z e d c o m p o s i t i o n c o n t a i n i n g t h e f l u o r i n e -

c o n t a i n i n g e l a s t o m e r of t h e p r e s e n t i n v e n t i o n h a s a

l a r g e l y i m p r o v e d l o n g - t e r m c o m p r e s s i o n s e t r e s i s -

t a n c e .

E x a m p l e 1 9




E x a m p l e 20







t h a t V i t o n E-60 p r o d u c e d by E . I . du P o n t de N e m o u r s

and Company was u s e d in p l a c e of t h e f l u o r i n e -

c o n t a i n i n g e l a s t o m e r of E x a m p l e 1 and t h a t p r e s s

v u l c a n i z a t i o n was e f f e c t e d f o r 20 min , t h e s ame t e s t

as in E x a m p l e 18 was c o n d u c t e d . The r e s u l t i s s h o w n

in T a b l e 1 1 .

0 3 1 4 7 8 6

T a b l e 11


C o m - p r e s s i o n 63 65 59 80 s e t ( % )

E x a m p l e 21

R u b b e r v a l v e s e a t t y p e b u t t e r f l y v a l v e





c o m p r e s s e d so t h a t t h e t h i c k n e s s d e c r e a s e d by 25 %

and p u t i n an o v e n and h e a t e d a t 200 °C f o r 1 7 0 0



T a b e r a b r a s i o n t e s t s u b s t a n t i a l l y in a c c o r d a n c e w i t h





s h o w n in T a b l e 1 2 .

The r u b b e r v a l v e s e a t of an e n c l o s e d b u t t e r f l y

v a l v e i s r e q u i r e d to h a v e a c o m p r e s s i o n s e t r e s i s -

- 52 -

0 3 1 4 7 8 6

t a n c e ana a D r a s i o n r e s i s t a n c e . H o w e v e r , t h e c o n v e n -

t i o n a l f l u o r i n e - c o n t a i n i n g e l a s t o m e r s w h i c h a r e u s e d

in t h e f i e l d s r e q u i r i n g r e s i s t a n c e s t o h e a t , o i l ,

s o l v e n t s and c h e m i c a l s do n o t n e c e s s a r i l y h a v e

s u f f i c i e n t c o m p r e s s i o n s e t r e s i s t a n c e and a b r a s i o n

r e s i s t a n c e . In c o n t r a s t , t h e v u l c a n i z e d c o m p o s i t i o n

c o n t a i n i n g t h e f l u o r i n e - c o n t a i n i n g e l a s t o m e r of t h e

p r e s e n t i n v e n t i o n h a s a s i g n i f i c a n t l y i m p r o v e d

c o m p r e s s i o n s e t r e s i s t a n c e and a b r a s i o n r e s i s t a n c e .

E x a m p l e 22



c o n d u c t e d . The r e s u l t s a r e s h o w n in T a b l e 1 2 .

E x a m p l e 23



c o n d u c t e d . t h e r e s u l t s a r e s h o w n in T a b l e 1 2 .


U s i n g t h e v u l c a n i z e d c o m p o s i t i o n p r o d u c e d i n



and c o m p a n y was u s e d in p l a c e of t h e f l u o r i n e -

c o n t a i n i n g e l a s t o r m e r of E x a m p l e 1 and t h a t p r e s s

v u l c a n i z a t i o n was e f f e c t e d f o r 20 m i n , t h e s a m e

t e s t s as in E x a m p l e 21 w e r e c o n d u c t e d . The r e s u l t s

- 53 -

0 3 1 4 7 8 8

a r e s n o w n m T a b l e 1 2 .

T a b l e 1 2


Com- p r e s s i o n 63 65 59 8 0 s e t ( % )

W e a r ( m g ) 265 340 280 4 0 0

E x a m p l e 2 4

b t em v a l v e


S x a m p l e 1 , t h e f o l l o w i n g t e s t was c o n d u c t e d . W i t h


[ i n n e r d i a m e t e r 23.7 mm, t h i c k n e s s 3.5 mm) w a s


ind p u t i n an o v e n and h e a t e d a t 200 °C f o r 1 7 0 0

l o u r s , f o l l o w e d by m e a s u r e m e n t a c c o r d i n g to J I S

C6301. An a b r a s i o n r e s i s t a n c e was e x a m i n e d by a

[@aber a b r a s i o n t e s t s u b s t a n t i a l l y in a c c o r d a n c e w i t h

iSTM D1 0 4 4 - 5 6 . The T a b e r a b r a s i o n t e s t was c o n -

0 3 1 4 7




shown in T a b l e 1 3 .

A s t e m v a l v e i s r e q u i r e d t o h a v e a c o m p r e s s i o n

s e t r e s i s t a n c e and a b r a s i o n r e s i s t a n c e . H o w e v e r ,

t h e c o n v e n t i o n a l f l u o r i n e - c o n t a i n i n g e l a s t o m e r s

w h i c h a r e u s e d in t h e f i e l d s r e q u i r i n g r e s i s t a n c e s

to h e a t , o i l , s o l v e n t s or c h e m i c a l s do n o t

n e c e s s a r i l y h a v e s u f f i c i e n t c o m p r e s s i o n s e t r e s i s -

t a n c e and a b r a s i o n r e s i s t a n c e . In c o n t r a s t , t h e


c o n t a i n i n g e l a s t o m e r of t h e p r e s e n t i n v e n t i o n has a

s i g n i f i c a n t l y i m p r o v e d c o m p r e s s i o n s e t r e s i s t a n c e

and a b r a s i o n r e s i s t a n c e .

E x a m p l e 25


E x a m p l e 2, t h e same t e s t s as i n E x a m p l e 24 w e r e

c o n d u c t e d . The r e s u l t s a r e s h o w n in T a b l e 1 3 .

E x a m p l e 26



c o n d u c t e d . The r e s u l t s a r e s h o w n i n T a b l e 1 3 .


U s i n g t h e v u l c a n i z e d c o m p o s i t i o n p r o d u c e d i n

- 55 -

0 3 1 4 7 8 6



and c o m p a n y was u s e d in p l a c e of t h e f l u o r i n e -

c o n t a i n i n g e l a s t o r m e r of E x a m p l e 1 and t h a t p r e s s

v u l c a n i z a t i o n was e f f e c t e d f o r 20 m i n , t h e s a m e

t e s t s as in E x a m p l e 24 w e r e c o n d u c t e d . The r e s u l t s

a r e s h o w n in T a b l e 1 3 .

T a b l e 13


C o m - p r e s s i o n 63 65 59 80 s e t ( % )

W e a r ( m g ) 265 340 280 4 0 0

E x a m p l e 27

S h a p e d a r t i c l e f o r u s e w i t h SF c l a s s e n g i n e

o i l


E x a m p l e 2, t h e f o l l o w i n g t e s t s w e r e c o n d u c t e d . An

i m m e r s i o n t e s t was c o n d u c t e d s u b s t a n t i a l l y i n

a c c o r d a n c e w i t h J I S K6301 , i n w h i c h t e s t a t e s t

s a m p l e was i m m e r s e d in Honda G e n u i n e U l t r a M o t o r O i l

0 3 1 4 7 8 6

SF a t 150 °C f o r 500 h o u r s . Wi th r e s p e c t t o

c o m p r e s s i o n s e t r e s i s t a n c e , an 0- r i n g ( i n n e r

d i a m e t e r 23.7 mm, t h i c k n e s s 3.5 mm) was c o m p r e s s e d

so t h a t t h e t h i c k n e s s d e c r e a s e s by 25 % and i m m e r s e d

in H o n d a G e n u i n e U l t r a M o t o r O i l a t 150 °C f o r 5 0 0


K6301. The r e s u l t s a r e s h o w n in T a b l e 1 4 .

In r e c e n t y e a r s , in a c c o r d a n c e w i t h t h e t r e n d

t h a t a u t o m o b i l e s a r e b e c o m i n g f u e l - s a v i n g and m a i n -

t e n a n c e - f r e e , e n g i n e o i l s h a v e b e e n s h i f t i n g f r o m

t h e SD and SE c l a s s e s to t h e SF c l a s s . In u s i n g a n

SF c l a s s e n g i n e o i l , t h e c o n t e n t s of a d d i t i v e s s u c h

as a d e t e r g e n t - d i s p e r s a n t and w e a r r e s i s t a n t a g e n t

a r e i n c r e a s e d a n d / o r t h e t y p e s of a d d i t i v e s h a v e

b e e n c h a n g e d , and a r e n o t t h e same as t h o s e u s e d i n

c o n v e n t i o n a l e n g i n e o i l s .

Due t o t h e a b o v e m e n t i o n e d c h a n g e s in- t h e

a d d i t i v e s of SF c l a s s e n g i n e o i l s , t h e p r o p e r t i e s o f

c o n v e n t i o n a l p o l y o l - v u l c a n i z e d f l u o r i n e - c o n t a i n i n g

e l a s t o m e r c o m p o s i t i o n s a r e l a r g e l y d e t e r i o r a t e d

u n d e r t h e a t t a c k of t h e s e e n g i n e o i l a d d i t i v e s . A

p o l y m i n e - v u l c a n i z e d f l u o r i n e - c o n t a i n i n g e l a s t o m e r

c o m p o s i t i o n i s r e s i s t a n t to e n g i n e o i l a d d i t i v e s a s

c o m p a r e d w i t h a p o l y o l - v u l c a n i z e d f l u o r i n e -

c o n t a i n i n g e l a s t o m e r c o m p o s i t i o n b u t i s e x t r e m e l y

n f e r i o r to t h e p o l y o l - v u l c a n i z e a compofc.j-i_j.uu x n

o m p r e s s i o n s e t r e s i s t a n c e . On t h e o t h e r h a n d , a

l e r o x i d e - v u l c a n i z e d f l u o r i n e - c o n t a i n i n g e l a s t o m e r

: o m p o s i t i o n i s e x c e l l e n t in r e s i s t a n c e to an SF

: l a s s e n g i n e o i l , b u t i s n o t o n l y i n f e r i o r t o a

) o l y o l - v u l c a n i z e d c o m p o s i t i o n in c o m p r e s s i o n s e t

r e s i s t a n c e , b u t a l s o has p r o b l e m s i n w o r k a b i l i t y ,

such as h a v i n g an a d h e s i o n p r o b l e m w i t h t h e g r e a t

a m o u n t of b u r r f o r m e d i n a m e t a l m o l d i n p r e s s

H o l d i n g and h a v i n g d i f f i c u l t i e s in b o n d i n g w i t h a

m e t a l l i c m a t e r i a l .

The p o l y o l - v u l c a n i z e d c o m p o s i t i o n c o n t a i n i n g

t he f l u o r i n e - c o n t a i n i n g e l a s t o m e r of t h e p r e s e n t

i n v e n t i o n i s e x c e l l e n t in c o m p r e s s i o n s e t r e s i s t a n c e

and a l s o i n m a i n t a i n i n g i t s p r o p e r t i e s e v e n i n an S F

c l a s s e n g i n e o i l a n d , t h e r e f o r e , i s s u i t a b l e f o r u s e

as s h a p e d p a c k i n g s w h i c h may c o n t a c t w i t h an SF

c l a s s e n g i n e o i l , s u c h as O - r i n g , V - p a c k i n g , U -

p a c k i n g , Y - p a c k i n g , D - r i n g , t r i a n g u l a r r i n g , T - r i n g

and X - r i n g , and f o r u s e as an o i l s e a l , d i a p h r a g m ,

g a s k e t , r u b b e r v a l v e s e a t t y p e b u t t e r f l y v a l v e a n d

s t e m v a l v e .

C o m p a r a t i v e E x a m p l e 1 0

U s i n g a c o m p o s i t i o n p r o d u c e d in s u b s t a n t i a l l y

t h e same m a n n e r as in E x a m p l e 1 e x c e p t t h a t D a i - e l

- 58 -

0 3 1 4 7 8 6

G-901 p r o d u c e d by D a i k i n I n d u s t r i e s , L t d . , J a p a n w a s

u s e d in p l a c e of t h e f l u o r i n e - c o n t a i n i n g e l a s t o m e r

of E x a m p l e 1 and t h a t 1 .5 p a r t s by w e i g h t of P e r h e x a

2 .5B ( p r o d u c e d by NIPPON OIL & FATS CO., LTD.) and 4

p a r t s by w e i g h t of t r i a l l y l i s o c y a n u r a t e w e r e u s e d i n

p l a c e of c a l c i u m h y d r o x i d e , h i g h l y a c t i v a t e d

m a g n e s i u m o x i d e , b i s p h e n o l AF and b i s ( b e n z y l d i -

p h e n y l p h o s p h i n e ) i m i n i u m c h l o r i d e , p r e s s v u l c a n i z a -

t i o n was e f f e c t e d a t 1 60 °C f o r 1 0 m i n a n d t h e n

v u l c a n i z a t i o n was e f f e c t e d in an o v e n a t 180 °C f o r

4 h o u r s to c o m p l e t e a p e r o x i d e - v u l c a n i z a t i o n . T h e

t h e same t e s t s as in E x a m p l e 27 w e r e c o n d u c t e d . T h e

r e s u l t s a r e s h o w n in T a b l e 1 4 .

T a b l e 14

E x a m p l e 27 C o m p a r a t i v e ' E x a m p l e 1 0

C o m p r e s s i o n 43 56 s e t (%)

Change i n T e n s i l e -17 - 3 7 s t r e n g t h ( % )

Change i n e l o n g a t i o n -10 - 2 4

(%)

0 3 1 4 7 8 6

P r o b a b i l i t y of U t i l i z a t i o n in I n d u s t r y


p r e s e n t i n v e n t i o n i s e x c e l l e n t in r e s i s t a n c e s t o h e a t

and c h e m i c a l s and i s n o t o n l y e x t r e m e l y e x c e l l e n t i n

5 c o m p r e s s i o n s e t r e s i s t a n t p r o p e r t i e s and m e c h a n i c a l

p r o p e r t i e s b u t a l s o h a s a w o r k a b i l i t y s u p e r i o r to o r

c o m p a r a b l e w i t h c o n v e n t i o n a l f l u o r i n e - c o n t a i n i n g

e l a s t o m e r s . M o r e o v e r , by v u l c a n i z a t i o n of t h e

f l u o r i n e - c o n t a i n i n g e l a s t o m e r by means of a v u l c a n -

10 i z i n g a g e n t s u c h as a p o l y a m i n e c o m p o u n d or a p o l y o l

c o m p o u n d , t h e r e c a n be o b t a i n e d e x c e l l e n t e l a s t i c

s h a p e d a r t i c l e s s u c h as h e a t - f i x i n g r o l l s , v a l v e s ,

r i n g s , s e a l s , p a c k i n g s , g a s k e t s and t h e l i k e .

- 60 -

) 3 1 4 7 8 ©

What i s c l a i m e d i s :

i. A f l u o r i n e - c o n t a i n i n g e l a s t o m e r c o m p r i s i n g v i n y l i d e n e

f l u o r i d e u n i t s , h e x a f l u o r o p r o p y l e n e u n i t s and 35 to 0 % b y

w e i g h t , b a s e d on t h e w e i g h t of t h e e l a s t o m e r , of h e x a -

E l u o r o e t h y l e n e u n i t s , t h e t o t a l of s a i d v i n y l i d e n e

f l u o r i d e u n i t s and s a i d h e x a f l u o r o p r o p y l e n e u n i t s b e i n g 65

to 100 % by w e i g h t b a s e d on t h e w e i g h t o f t h e e l a s t o m e r ,

t he w e i g h t r a t i o of s a i d v i n y l i d e n e f l u o r i d e u n i t s to s a i d

h e x a f l u o r o p r o p y l e n e u n i t s b e i n g in t h e r a n g e of 80 :20 t o

4 0 : 6 0 , and w h e r e i n :

(a) t h e f l u o r i n e c o n t e n t of t h e e l a s t o m e r i s 63.5 t o

71 % by w e i g h t ,

(b) t h e l i m i t i n g v i s c o s i t y n u m b e r ( m l / g ) of t h e

e l a s t o m e r i s i n t h e r a n g e of f r o m 1 00 t o l e s s t h a n

2 5 0 ,

(c) t h e c o n t e n t of f r a c t i o n s h a v i n g m o l e c u l a r w e i g h t s

of 5 0 , 0 0 0 or l e s s i n t h e e l a s t o m e r i s 5 % by w e i g h t o r

l e s s , a n d

(d) t h e c o n t e n t of f r a c t i o n s h a v i n g m o l e c u l a r w e i g h t s

of 1 , 0 0 0 , 0 0 0 or more in t h e e l a s t o m e r i s 10 to 35 % b y

w e i g h t .

2. The f l u o r i n e - c o n t a i n i n g e l a s t o m e r a c c o r d i n g to c l a i m 1 ,

w h e r e i n s a i d l i m i t i n g v i s c o s i t y n u m b e r ( m l / g ) i s in t h e

r a n g e of f rom 120 to l e s s t n a n ^ s u .


w h e r e i n t h e w e i g h t r a t i o of s a i d v i n y l i d e n e f l u o r i d e u n i t s

t o s a i d h e x a f l u o r o p r o p y l e n e u n i t s i s in t h e r a n g e of 7 5 : 2 5

5 t o 4 0 : 6 0 .

4. The f l u o r i n e - c o n t a i n i n g e l a s t o m e r a c c o r d i n g t o c l a i m 1 ,

w h e r e i n t h e t o t a l of s a i d v i n y l i d e n e f l u o r i d e u n i t s a n d

s a i d h e x a f l u o r o p r o p y l e n e u n i t s i s 65 to 95 % by w e i g h t

b a s e d on t h e w e i g h t o f t h e e l a s t o m e r , t h e c o n t e n t of s a i d

L0 t e t r a f l u o r o e t h y l e n e u n i t s in t h e e l a s t o m e r i s 35 to 5 % b y

w e i g h t , and t h e w e i g h t r a t i o of s a i d v i n y l i d e n e f l u o r i d e

u n i t s t o s a i d h e x a f l u o r o p r o p y l e n e u n i t s i s in t h e r a n g e o f

8 0 : 2 0 t o 5 0 : 5 0 .

5. The f l u o r i n e - c o n t a i n i n g e l a s t o m e r a c c o r d i n g to c l a i m 3

15 or 4, w h e r e i n s a i d l i m i t i n g v i s c o s i t y n u m b e r ( m l / g ) i s i n

t h e r a n g e of f r o m 100 t o l e s s t h a n 160 a n d t h e c o n t e n t o f

f r a c t i o n s h a v i n g m o l e c u l a r w e i g h t of 1 , 0 0 0 , 0 0 0 or more i n

t h e e l a s t o m e r i s 10 t o l e s s t h a n 20 % by w e i g h t .

6. The f l u o r i n e - c o n t a i n i n g e l a s t o m e r a c c o r d i n g t o c l a i m 3

20 or 4, w h e r e i n s a i d l i m i t i n g v i s c o s i t y n u m b e r ( m l / g ) i s i n

t h e r a n g e of f r o m 160 t o l e s s t h a n 220 a n d t h e c o n t e n t o f

f r a c t i o n s h a v i n g m o l e c u l a r w e i g h t of 1 , 0 0 0 , 0 0 0 o r more i n

t h e e l a s t o m e r i s 20 to 30 % by w e i g h t .

7. The f l u o r i n e - c o n t a i n i n g e l a s t o m e r a c c o r d i n g to c l a i m 3

25 to 4, w h e r e i n s a i d l i m i t i n g v i s c o s i t y n u m b e r ( m l / g ) of t h e

- bz -

0 3 1 4 "

e l a s t o m e r i s m t h e r a n g e of f r o m 220 t o l e s s t h a n 250 a n d

t h e c o n t e n t of f r a c t i o n s h a v i n g m o l e c u l a r w e i g h t o f

1 , 0 0 0 , 0 0 0 or more in t h e e l a s t o m e r i s 30 to 35 % by w e i g h t .




b a s e d on t h e w e i g h t of t h e e l a s t o m e r , t h e c o n t e n t of s a i d

t e t r a f l u o r o e t h y l e n e u n i t s in t h e e l a s t o m e r i s 25 to 5 % b y


u n i t s to s a i d h e x a f l u o r o p r o p y l e n e u n i t s i s in t h e r a n g e o f

6 0 : 4 0 to 5 0 : 5 0 .




b a s e d on t h e w e i g h t of t h e e l a s t o m e r , t h e c o n t e n t o f s a i d

t e t r a f l u o r o e t h y l e n e u n i t s in t h e e l a s t o m e r i s 25 t o 5 % b y


4 H i i t s ^ d f e o ^ ^ a d ^ f e e x a f l u o r o p r o p y l e n e u n i t s i s in t h e r a n g e o f

7 0 : 3 0 to 6 0 : 4 0 .

1 0. The f l u o r i n e - c o n t a i n i n g e l a s t o m e r a c c o r d i n g to c l a i m

7, w h e r e i n t he t o t a l of s a i d v i n y l i d e n e f l u o r i d e u n i t s a n d


b a s e d on t h e w e i g h t of t h e e l a s t o m e r , t h e c o n t e n t o f s a i d

t e t r a f l u o r o e t h y l e n e u n i t s in t h e e l a s t o m e r i s 25 to 5 % b y


)3 1 4 I B O

i n i t s to s a i d h e x a f l u o r o p r o p y l e n e u n i t s i s in t n e r a n g e 0 1

10:20 t o 7 0 : 3 0 .

1. An e x t r u d e d p r o d u c t of a f l u o r i n e - c o n t a i n i n g e l a s t o m e r

is d e s c r i b e d in c l a i m 1 , in w h i c h t h e l i m i t i n g v i s c o s i t y

l u m b e r i s 10 t o 100 l a r g e r t h a n t h o s e i n t h e r a n g e o f f r o m

1 00 to l e s s t h a n 250, s a i d f l u o r i n e - c o n t a i n i n g e l a s t o m e r

n a v i n g b e e n s u b j e c t e d to e x t r u s i o n u s i n g a h e a t e d e x t r u d e r ,

to f o r m t h e e x t r u d e d p r o d u c t .

12. A s h a p e d a r t i c l e w h i c h i s p r o d u c e d by v u l c a n i z i n g a

m i x t u r e of a p o l y o l c o m p o u n d and a f l u o r i n e - c o n t a i n i n g

e l a s t o m e r c o m p r i s i n g v i n y l i d e n e f l u o r i d e u n i t s and h e x a -

f l u o r o p r o p y l e n e u n i t s , o p t i o n a l l y w i t h t e t r a f l u o r o e t h y l e n e

u n i t s , and w h e r e i n :

(a) t h e f l u o r i n e c o n t e n t of t h e e l a s t o m e r i s 63 .5 t o

71 % by w e i g h t ,



2 5 0 ,

(c) t h e c o n t e n t of f r a c t i o n s h a v i n g m o l e c u l a r w e i g h t s

of 5 0 , 0 0 0 o r l e s s i n t h e e l a s t o m e r i s 5 % by w e i g h t o r

l e s s , a n d


of 1 , 0 0 0 , 0 0 0 or more in t h e e l a s t o m e r i s 1 0 to 35 % b y

w e i g h t .

13. A s h a p e d a r t i c l e a c c o r d i n g to c l a i m 12, w h i c h i s a

3 3 1 4 7 8 6

i e a t - f i x i n g r o l l , a c o n t r o l v a l v e , or a s h a p e d p a c J c m g

s e l e c t e d f r o m t h e g r o u p c o n s i s t i n g of an 0- r i n g , V - p a c k i n g ,

j - p a c k i n g , Y - p a c k i n g , D - r i n g , t r i a n g u l a r r i n g , T - r i n g a n d

X - r i n g , a g a s k e t , a r u b b e r v a l v e s e a t t y p e b u t t e r f l y

v a l v e , a s t e m v a l v e , an o i l s e a l , a s h a p e d a r t i c l e f o r u s e

w i t h SF c l a s s e n g i n e o i l , a f u e l h o s e , h e a t - s h r i n k a b l e

t u b i n g , a we t f r i c t i o n m a t e r i a l , w i r e c o a t i n g , a

p i e z o e l e c t r i c m a t e r i a l or b e l l o w s f o r s m o k e d u c t j o i n t .

14. A d i a p h r a g m w h i c h i s p r o d u c e d by v u l c a n i z i n g a m i x -

t u r e of a p o l y a m i n e c o m p o u n d o r a p o l y o l c o m p o u n d a n d a

f l u o r i n e - c o n t a i n i n g e l a s t o m e r c o m p r i s i n g v i n y l i l d e n e

f l u o r i d e u n i t s and h e x a f l u o r o p r o p y l e n e u n i t s , o p t i o n a l l y

w i t h t e t r a f l u o r o e t h y l e n e u n i t s , and w h e r e i n :

(a) t h e f l u o r i n e c o n t e n t of t h e e l a s t o m e r i s 63.5 t o

71 % by w e i g h t ,



2 5 0 ,

(c) t h e c o n t e n t of f r a c t i o n s h a v i n g , m o l e c u l a r w e i g h t s

of 5 0 , 0 0 0 o r l e s s in t h e e l a s t o m e r i s 5 % by w e i g h t o r

l e s s , a n d


of 1 , 0 0 0 , 0 0 0 or more in t h e e l a s t o m e r i s 10 to 35 % b y

w e i g h t .

INTERNATIONAL bfcAKCH K t r U K I _Q 3 1 4 7 ft < International Application No PCT/ JP 8 7 / OX) 2 c o

CLASSIFICATION OF SUBJECT MATTcK (it several ciassincauon symoois appiy, indicate an; @> According to l n t . m . t , o n « i ^ j ? ^ . ^ I n t . CI4 C 0 8 L 2 7 / 2 0 , C 0 8 K 5 / 1 3

. FIELDS SEARCHED Minimum Documentation Searched *

:iassification System | Classification Symbols

C 0 8 F 2 1 4 / 2 2 , C 0 8 F 2 1 4 / 2 8 , C 0 8 L 2 7 / 1 6 , IPC C 0 8 L 2 7 / 2 0 , C 0 8 K 5 / 1 3

Documentation Searched other than Minimum Documentation 3 the Extent that such Documents are Included in the Fields Searched *

III. DOCUMENTS CONSIDERED TO BE RELEVANT" lategory * \ Citation of Document, is with indication, where appropriate, of the relevant passages n | Relevant to Claim No.

X JP , A, 6 2 - 5 9 6 1 1 ( A s a h i K a s e i Kogyo 1 - 1 4 K a b u s h i k i K a i s h a ) 16 M a r c h 1987 (16 . 03. 87) ( F a m i l y : n o n e ) Co lumn of C l a i m

i JP , B l , 3 3 - 7 3 9 4 ( E . I . Du P o n t de N e m o u r s l - l l and C o m p a n y ) 27 A u g u s t 1958 (27 . 08. 58) ( F a m i l y : n o n e ) i Co lumn of C l a i m

X

X

X

JP , B l , 5 2 - 4 6 9 9 8 ( D a i k m 29 N o v e m b e r 1977 (29 . 1 1 . Co lumn of C l a i m

JP, B l , 4 8 - 1 8 9 5 7 ( D a i k i n 9 J u n e 1973 (09 . 06. 7 3 ) Co lumn of C l a i m

I n d u s t r i e s , 77) ( F a m i l y

b t a . ) : n o n e ) !

I n d u s t r i e s , i t a . ) ( F a m i l y : n o n e )

JP Bl , 4 9 - 2 9 3 1 0 ( D a i k i n I n d u s t r i e s , L t d . 2 A u g u s t 1974 (02 . 08. 7 4 ) & US, A, 3 8 0 1 5 5 2 & JP , Bl , 4 9 - 2 9 6 3 0 & JP , B l , 4 9 - 2 9 6 3 1 & GB, A, 1 3 8 4 3 9 8

1 - 1 4

1 - 1 4

1 - 1 4

* Special categories of cited documents: " "A" document defining the general state of the art which is not

considered to be of particular relevance "E" earlier document but published on or after the international

filing date "L" document which may throw doubts on priority claim (s) or

which is cited to establish the publication date of another citation or other special reason (as specified)

"0" document referring to an oral disclosure, use. exhibition or other means

"P" document published prior to the international filing date but later than the priority date claimed

1 later uOCUmeni puuu&neu tmei inc inicmiohwikii mtny uok priority date and not in conflict with the application but cited to understand the principle or theory underlying the invention

'X" document of oarticj:ar relevance: the claimed invention cannot be considerea novel or cannot be considered to involve an inventive step

•Y" document of particular relevance: the claimed invention cannot be considered to i-volve an inventive step when the document is combined with one or more other such documents, such combination being obvious to a person skilled in the art

'&" document member of the same patent family

IV. CERTIFICATION Date of the Actual Completion ot the International searcn '

J u l y 15, 1987 (15 . 07. 87 )

Date 01 Mailing 01 ltlls ««ci(!<uiuit<H otsarcn nefjuti -

J u l y 27, 1987 (27 . 07. 8 7 )

International Searching Authority 1

J a p a n e s e P a t e n t O f f i c e Signature 01 AUincriiea unnci --

Form PCT ISA 2l0 'second sheet) (October 19(71

ii.catior. :o. Jt" . X / J F b / / L w 0 w

:URTHER INFORMATION CSUVINUbff WKKS iff:- - - w ™

1 7 3 * 51/

JS, A, 2 9 6 8 6 4 9 ( E . I . du P o n t de N e m o u r s and C o m p a n y ) L7 J a n u a r y 1961 (17 . 01. 61) ( F a m i l y : n o n e )

TP, A, 5 3 - 1 4 9 2 9 1 ( E . I . Du P o n t d e 2 6 D e c e m b e r 197 8 & US, A, 4 1 2 3 6 0 3

( E . I . Du P o n t de N e m o u r s c 26 D e c e m b e r 1978 (26. 1 2 . & US, A, 4 1 2 3 6 0 3 & BE, A ,

_ DK, A, 2 3 7 4 7 8 & SE, A, "

& NL, A, 7 8 0 5 9 2 3 & DE, A ,

_ FR, A, 2 3 9 3 0 1 2 & LU, A , & AU, A, 3 6 6 3 0 7 8 & FR, B ,

ind C o m p a n y ) 7 8 ) 8 6 7 6 1 9

' 8 0 4 1 2 8 2 8 2 3 1 7 9 7 9 7 2 8 2 3 9 3 0 1 2

L - 1 4

L - X l

V.U OBSERVATIONS WHERE CERTAIN CLAIMS WERE FOUND UNSEARCHABLE '°

This international search report has not been established in respect ot certain claims unoer Aracie 1 1 u> tai ior me iciiowina roasuna.

1 .0 Claim numbers , because they relate to subject matter " not required to be searched by this Authority, namely:

2.D Claim numbers because they relate to parts ot the international application that do not comply with the prescribed require- ments to such an extent that no meaningful international search can be carried out 13. specifically:

VI.D OBSERVATIONS WHERE UNITY OF INVENTION IS LACKING "

This Internationa! Searching Authority found multiple inventions in tnis international appiicaiion as ioiiows.

1 .□ As all required additional search fees were timely paid by the applicant, this international search report covers ail searchable claims of the international application

2.D As only some of the required additional search fees were timely paid by the applicant, this international search report covers only those caims of the international application for which fees were paid, specifically claims:

3.D No required additional search fees were timely paid by the applicant. Consequently, this international search report is restricted to the invention first mentioned in the claims: it is covered by claim numbers:

D As all searchable claims could be searched without erfOTTjustirying an aaoitionai ree. me inrernauonai aearcning Muinomy uiu uui mnn payment of any additional fee

Remark on Protest I I The additional search fees were accompanied bv applicant's protest. LJ No protest accompanied the payment of additional search tees

F.vm PC"' 'SA . - «.- isupoiemeniai sheet l-H .Octolie' 'HSU

international Appiicat.O" No

RJiiTHEfi l?!FOPVIAT5?>M COMT-vyO F'.OM THE SECOND SHEET

0 3 1 4 7 8 6

P C T / J P 8 7 / 0 0 2 8 5 ™ ' 1

& CA, A, 1 1 0 3 3 9 8 & SU, A, 8 6 5 1 2 9 & GB, A, 1 6 0 0 9 4 0 & NL, B, 1 7 1 7 1 2 & IE, B, 46834 & DK, B, 1 4 7 4 9 7 & DK, C, 1 4 7 4 9 7

V.D OBSERVATIONS WHERE CERTAIN CLAIMS WERE FOUND UNSEARCHABLE"

This international search report has not been established in respect of certain claims under Article 17(2) (a) for the following reasons: 1 .Lj Claim numbers because they relate to subject matter 12 not required to be searched by this Authority, namely:

2.D Claim numbers , because they relate to parts of the international application that do not comply with the prescribed require- ments to such an extent that no meaningful international search can be carried out 13, specifically:

VI.D OBSERVATIONS WHERE UNITY OF INVENTION IS LACKING 1

This International Searching Authority found multiple inventions in this international application as follows:

1 ,Lj As all required additional search fees were timely paid by the applicant, this international search report covers all searchable claims of the international application.

2.0 As only some of the required additional search fees were timely paid by the applicant, this international search report covers only those claims of the international application for which fees were paid, specifically claims:

3.D No required additional search fees were timely paid by the applicant. Consequently, this international search report is restricted to the invention first mentioned in the claims: it is covered by claim numbers:

As all searchable claims could be searched without effort justifying an additional fee, the International Searching Authority did not invite payment of any additional fee.

Remark on Protest Lj The additional search fees were accompanied by applicant's protest. Lj No protest accompanied the payment of additional search fees

Form PCT ISA 210 (supplemental sheet (2)) lOctober 1'981)

FLUORINE-CONTAINING ELASTOMER AND ITS MOLDINGS

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