EP0080906A2 Patente

Europaisches
Pat ent amt

European
Patent Office
Office
europeen
des brevet s
Publication number.
0 0 8 0 9 0 6
A 2

EUROPEAN PATENT APPLICATION
Application number: 82306413.4
Date of filing: 02.12.82
Int. CI.3: D 01 F 6/ 62
D 01 D 5/ 08
Priority: 02.12.81 JP 194129/81
Date of publication of application:
08.06.83 Bulletin 83/23
Designated Contracting States:
DE FR GB LU
(71) Applicant: TOYOBOPETCORD CO., LTD
2-8 Dojimahama 2-chome
Kita-ku Osaka-shi Osaka-fu(JP)
Inventor: Yabuki, Kazuyuki
1,Katata 2-chome
Otsu-shi Shiga-ken(JP)
^2) Inventor: Kohmura, Yohji
63-7-2, Kanayama
Tsuruga-shi Fukui-ken(JP)
Inventor: twasaki, Mitsuo
8- 2-207, Kureha-cho
Tsuruga-shi Fukui-ken(JP)
^) Inventor: Yasuda, Hiroshi
9- 2Kitaoji 3-chome
Otsu-shi Shiga-ken(JP)
Representative: Lawrence, Peter Robin
Broughton et al.
Gill, Jennings &Every 53-64 Chancery Lane
London WC2A1HN(GB)
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Polyester fibres and their production.
A polyester fibre having excellent thermal dimensional
stability and chemical stability as well as high tenacity, which
is a drawn
yarn produced by melt-spinning a polyester
comprising predominantly polyethylene terephthalate, soli-
difying the
spun yarn
and then drawing the
yarn
The
polyester has specified properties such as intrinsic viscosity,
diethylene glycol content, and carboxyl
group content, and
the
yarn
has specified properties such
as average birefring-
ence, yarn tenacity and difference of
average birefringence
between surface and centre of monofilament, and further
low dry heat shrink and work loss when heat-treated. The
spinning
and drawing is conducted under specified condi-
tions. The resultant polyester fibre is useful
as a reinforce-
ment for rubber goods, specifically as a tyre cord.
The
p r e s e n t
i n v e n t i o n r e l a t e s t o p o l y e s t e r
f i b r e s
h a v i n g e x c e l l e n t
p i o p e r t i e s i n c l u d i n g good
t h e r m a l
d i m e n s i o n a l
s t a b i l i t y , good
c h e mi c a l
s t a b i l i t y and h i g h
t e n a c i t y ,
and
p r o c e s s e s
f or t h e i r p r o d u c t i o n .
P o l y e s t e r
y a r n s
h a v i n g h i g h t e n a c i t y , p a r t i -
c u l a r l y p o l y e s t e r t i r e
y a r n , a r e o r g a n i c f i b r e s h a v i n g w e l l
b a l a n c e d p h y s i c a l p r o p e r t i e s and ha ve b e e n
wi d e l y u s e d i n
v a r i o u s i n d u s t r i e s .
In s p i t e
of r e c e n t s i g n i f i c a n t i n c r e a s e s i n
t he c o s t of t h e
s t a r t i n g
m a t e r i a l s of
many o r g a n i c f i b r e s ,
f o r e x a mp l e n y l o n 6, t he c o s t of t he
s t a r t i n g
m a t e r i a l s
of
p o l y e s t e r s ( p a r t i c u l a r l y p o l y e t h y l e n e t e r e p h t h a l a t e )
has i n c r e a s e d l e s s and i t i s
e x p e c t e d
t h a t t h i s s t a b l e c o s t
of p o l y e s t e r s w i l l be ma i n t a i n e d i n f u t u r e . Th i s f a c t
may p r o mo t e
t h e e n l a r g e d demand of t h e
p o l y e s t e r h i g h
t e n a c i t y y a r n s .
Howe ve r f o r
some p u r p o s e s
t h e c o n v e n t i o n a l
p o l y e s t e r y a r n s
do not have s a t i s f a c t o r y t h e r ma l d i m e n -
s i o n a l s t a b i l i t y ,
c h e mi c a l
s t a b i l i t y
and a d h e s i o n w i t h
m a t e r i a l s t o be r e i n f o r c e d ( e . g . r u b b e r s ) . I t i s t h e r e -
f o r e r e q u i r e d t o i mp r o v e
t h e s e
p r o p e r t i e s .
Me t h o d s have be e n
p r o p o s e d f or
i m p r o v i n g
s uc h
p r o p e r t i e s
of p o l y e s t e r y a r n s .
For i n s t a n c e , f o r
i mp r o v e me n t
of t h e r ma l d i m e n s i o n a l s t a b i l i t y , t h e r e h a v e
be e n p r o p o s e d p o l y e s t e r f i b r e s
h a v i n g a c o m p a r a t i v e l y
l o we r i n t r i n s i c v i s c o s i t y ( c . f .
J a p a n e s e
P a t e n t La i d
Op e n
A p p l i c a t i o n No. 3 1 8 5 2 / 1 9 7 8 ) , p o l y e s t e r
f i b r e s o b t a i n e d
b y
d r a wi n g a h i g h l y o r i e n t a t e d u n d r a wn
y a r n
( s o - c a l l e d "POY"
wh i c h i s an a b b r e v i a t i o n of p a r t i a l l y o r i e n t a t e d y a r n ) ( c f .
US P a t e n t 4 , 1 9 5 , 0 5 2 ) , and
p o l y e s t e r f i b r e s i r r a d i a t e d b y
e l e c t r o n
r a y s
( c f .
J a p a n e s e P a t e n t La i d
Open A p p l i c a t i o n
No. 5 7 0 7 0 / 1 9 8 0 ) . For i mp r o v e me n t
of c h e mi c a l
s t a b i l i t y ,
t h e r e ha s b e e n
p r o p o s e d a me t h o d of l o we r i n g t h e c o n t e n t
of c a r b o x y l end
g r o u p
( h e r e i n a f t e r r e f e r r e d t o as " c a r b o x y l
g r o u p " ) i n t h e
p o l y e s t e r ( c f . J a p a n e s e
P a t e n t La i d
Op e n
A p p l i c a t i o n No. 1 1 6 8 1 6 / 1 9 8 0 ) . For i mp r o v e me n t i n a d h e s -
i on wi t h r u b b e r s , t h e r e ha ve b e e n p r o p o s e d a me t h o d o f
t r e a t i n g
t h e
p o l y e s t e r
wi t h a c h e m i c a l l y a c t i v e
e poxy
o r
i s o c y a n a t e c ompound i n t he
s t e p s
of
s p i n n i n g and
d r a w i n g
( c f . J a p a n e s e P a t e n t P u b l i c a t i o n No. 4 9 7 6 8 / 1 9 7 3 ) and
a
me t h o d of
t r e a t i n g
t h e p o l y e s t e r
wi t h t he a bove c h e m i c a l l y
a c t i v e c o mp o u n d i n d i p p i n g p r o c e s s
( c f . J a p a n e s e P a t e n t
La i d
Open A p p l i c a t i o n No. 1 1 6 8 1 6 / 1 9 8 0 ) .
Th e s e
p r o p o s e d
me t h o d s
can i mp r o v e s o me
p r o p e r t i e s t o some e x t e n t . Ho we v e r t h e r e i s
u s u a l l y a
t r a d e - o f f of
p r o p e r t i e s ,
and
so
i t i s not p o s s i b l e t o
o p t i m i s e
a l l t he
p r o p e r t i e s s i m u l t a n e o u s l y .
Among
t he knowm me t h o d s , t he me t h o d uf l o w e r i n g
t he i n t r i n i s i c
v i s c o s i t y
has
a
d r a wb a c k t h a t t h e
t e n a c i t y
of c or d and
f a t i g u e r e s i s t a n c e a r e d e t e r i o r a t e d i n r e t u r n
i o r
i mp r o v e me n t
of d i me n s i o n a l
s t a b i l i t y
i n t he
us e t h e r e o f
as a
t i r e r e i n f o r c e m e n t . B e s i d e s , t h e f i b e r s o b t a i n e d
by d r a w i n g
POY as
d i s c l o s e d i n U. S. P a t e n t 4 , 1 9 5 , 0 5 2 show d e t e r i o r a t e d
t o u g h n e s s i n r e t u r n f or i mp r o v e me n t of d i me n s i o n a l
s t a b i l i t y
in t he
us e t h e r e o f
as a
t i r e r e i n f o r c e m e n t .
Mo r e o v e r , t h e s e
p o l y e s t e r
f i b e r s
a r e
i n f e r i o r i n t he c h e mi c a l
s t a b i l i t y i n
c o mp a r i s o n wi t h t he c o n v e n t i o n a l
h i g h t e n a c i t y p o l y e s t e r
f i b e r s , p a r t i c u l a r l y show d e t e r i o r a t i o n wi t h a m i n e s
c o n t a i n e d i n r u b b e r s
or
wi t h
w a t e r , b e c a u s e t h e s e f i b e r s
c o n t a i n at t he s u r f a c e r e g i o n t h e t i e - m o l e c u l e c h a i n w h i c h
c o n t r i b u t e s
h i g h l y t o t h e t e n a c i t y of f i b e r s . The me t h o d o f
i mp r o v i n g t he d i me n s i o n a l
s t a b i l i t y by f o r m i n g
t h r e e - d i m e n s i o n a l
c r o s s l i n k i n g wi t h e l e c t r o n
r a y
i r r a d i a t i o n
or
wi t h c r o s s l i n k i n g a g e n t s
ha s a l s o
a
d r a wb a c k t h a t t h e
t o u g h n e s s
and f a t i g u e r e s i s t a n c e of
y a r n
a r e d e t e r i o r a t e d i n
r e t u r n f or i mp r o v e me n t of d i m e n s i o n a l
s t a b i l i t y l i k e w i s e ,
and i t i s me r e l y an i mp r o v e me n t by t r a d e - o f f of
i . e .
an i mp r o v e me n t of
one p r o p e r t y at t he s a c r i f i c e o f
o t h e r p r o p e r t i e s .
B e s i d e s , t he me t h o d of i mp r o v i n g c h e m i c a l
s t a b i l i t y by l o we r i n g t h e c a r b o x y l
g r o u p
c o n t e n t and t h e
me t hod of i mp r o v i n g
t he a d h e s i o n of
p o l y e s t e r
f i b e r
a r e
i n s u f f i c i e n t f or i mp r o v i n g d i m e n s i o n a l s t a b i l i t y f o r t h e
p u r p o s e
of u s i n g t he f i b e r s
as a
r e i n f o r c e m e n t i n
h e a v y d u t y
v e h i c l e s and
can not g i v e t h e d e s i r e d p o l y e s t e r f i b e r s .
I t ha s
now b e e n f ound t h a t i t i s p o s s i b l e t o
make p o l y e s t e r
f i b r e s
h a v i n g h i g h
t h e r ma l d i m e n s i o n a l
s t a b i l i t y
and g e n e r a l l y h a v i n g a l s o o t h e r d e s i r a b l e
p h y s i c a l p r o p e r t i e s , e s p e c i a l l y h i g h
c h e mi c a l s t a b i l i t y
a n d
h i g h
t e n a c i t y , b y
me l t
s p i n n i n g p o l y e t h y l e n e t e r e p h t h a l a t e ,
s o l i d i f y i n g
t h e
s pun
f i l a m e n t s and t h e n d r a wi n g t h e
y a r n
i f t h e
p o l y e t h y l e n e t e r e p h t h a l a t e has p a r t i c u l a r p r o p e r t i e s
and i f t h e s p i n n i n g and
d r a wi n g i s c o n d u c t e d u n d e r
s p e c i f i c
c o n d i t i o n s . The r e s u l t a n t
y a r n
c a n ha ve h i g h
t e n a c i t y
and h i g h t h e r ma l d i m e n s i o n a l s t a b i l i t y and c h e m i c a l
s t a b i l i t y
and i s
v e r y
u s e f u l
as a r e i n f o r c e m e n t of r u b b e r s
f o r i n s t a n c e i n
t y r e s ,
V - b e l t s and
c o n v e y o r
b e l t s .
The
y a r n a c c o r d i n g t o t he i n v e n t i o n i s
c h a r a c t e r i s e d i n t h a t t h e p o l y e s t e r
has
an i n t r i n s i c
v i s c o s i t y
of 0. 8 or mor e and t h e dr awn
y a r n
has a
y a r n
t e n a c i t y
of 8. 5 g/ d or mo r e , an a v e r a g e
b i r e f r i n g e n c e o f
0. 19 or mor e
and
a b i r e f r i n g e n c e v a r i a t i o n , c a l c u l a t e d
by d i v i d i n g
t h e d i f f e r e n c e of
a v e r a g e
b i r e f r i n g e n c e b e t w e e n
s u r f a c e and c e n t r e of
a m o n o - f i l a m e n t by
t h e
a v e r a g e
b i r e f r i n g e n c e ,
of 0 . 0 5 5 or l e s s , and t he d r a wn
y a r n ,
a f t e r
b e i n g h e a t t r e a t e d a t c o n s t a n t l e n g t h a t 240 C f o r 1 m i n u t e
has
a d r y
h e a t s t r i n k when
f r e e l y
h e a t t r e a t e d a t 1 7 5 C
f o r 30 mi n u t e s of 3% or l e s s .
The i n v e n t i o n a l s o i n c l u d e s
p r o c e s s e s
f o r
ma k i n g p o l y e s t e r y a r n s
h a v i n g d e s i r a b l e
e s p e c i a l l y
t h o s e me n t i o n e d a b o v e , a n d i s c h a r a c t e r i s e d i n
t h a t t h e s o l i d i f i c a t i o n and d r a wi n g ar e so c o n d u c t e d t h a t
t he b i r e f r i n g e n c e v a r i a t i o n of t he
y a r n ,
d e f i n e d
as a b o v e ,
i s 0 . 0 5 5 or l e s s .
In one
me t h o d of t he i n v e n t i o n t he s o l i d i f -
i c a t i o n and
d r a wi n g i s c o n d u c t e d
by q u e n c h i n g wi t h a i r a t
a b o v e 35C and
i n i t i a t i n g t he
d r a wi n g
i n t he
p r e s e n c e
o f
s u p e r
h e a t e d s t e a m or i n c o n t a c t wi t h a h e a t e d s u r f a c e
wh i l e i n a n o t h e r
p r o c e s s
t he s o l i d i f i c a t i o n i s c o n d u c t e d
w i t h o u t u s i n g q u e n c h i n g a i r and t h e
y a r n
i s b u n d l e d 20
t o 100 cm
b e l o w t he
p o s i t i o n
of s o l i d i f i c a t i o n and t h e
b u n d l e d
y a r n
i s t h e n d r a wn . Be s t r e s u l t s a r e a c h i e v e d
i n s uc h me t h o d s when t h e
s p i n n i n g i s c o n d u c t e d t h r o u g h a
s p i n n e r e t
at a t h r o u g h p u t of not mor e
t h a n 3. 5 g / m i n u t e
f o r e a c h o r i f i c e of t h e
s p i n n e r e t and t h e d r a wi n g i n v o l v e s
p u l l i n g
out t he
s pun y a r n
at a s p i n n i n g s t r e s s of
1 . 5 x 1 0
t o
7 . 5 x 1 0
d y n e / c m2 . The i n v e n t i o n i n c l u d e s a l s o
y a r n s
made by
t h i s
p r o c e s s
and t he
p r o c e s s e s
d e s c r i b e d i n mo r e
d e t a i l b e l o w. I t a l s o i n c l u d e s
y a r n s
made f r om t h e
d e s c r i b e d n o v e l
y a r n s
and f r om t he
y a r n s
made by
t h e
d e s c r i b e d
p r o c e s s e s
and whi c h ha ve be e n s u b j e c t e d t o f u r t h e r
p r o c e s s i n g ,
f o r i n s t a n c e
h e a t i n g or a p p l i c a t i o n
of s u r f a c e
t r e a t m e n t s . The i n v e n t i o n a l s o i n c l u d e s a r t i c l e s
c o mp r i s i n g
r u b b e r r e i n f o r c e d
by
a l l s uc h
y a r n s .
The p r e f e r r e d p o l y e s t e r
f i b r e s of t h e
i n v e n t i o n ha ve h i g h
t h e r ma l d i me n s i o n a l s t a b i l i t y a n d
c h e m i c a l s t a b i l i t y as
we l l as h i g h t e n a c i t y and
a r e i n t h e
f or m of
a dr a wn
y a r n
p r o d u c e d by m e l t - s p i n n i n g a
p o l y e s t e r c o mp r i s i n g p r e d o mi n a n t l y p o l y e t h y l e n e t e r e p h t h -
a l a t e , s o l i d i f i c a t i o n t he
s pun y a r n
wi t h c o o l i n g and t h e n
d r a wi n g
t h e
y a r n ,
and have t he f o l l o w i n g p r o p e r t i e s :
( i ) i n t r i n s i c
v i s c o s i t y :
0. 8 or
mo r e ,
( i i ) c o n t e n t of d i e t h y l e n e g l y c o l : 2 . 5 %
by
mol e or l e s s of
t e r e p h t h a l i c a c i d r e s i d u e ,
I
( i i i ) c o n t e n t of
c a r b o x y l
g r o u p :
30
e q u i v a l e n t / 1 0 6
g or l e s s ,
( i v)
a v e r a g e
b i r e f r i n g e n c e : 0. 190
or m o r e ,
(v)
y a r n
t e n a c i t y : 8. 5 g/ d or mor e ,
a n d
( vi ) v a l u e o b t a i n e d
by d i v i d i n g t he d i f f e r e n c e o f
a v e r a g e
b i r e f r i n g e n c e b e t we e n s u r f a c e and c e n t e r o f
mo n o f i l a me n t by
a v e r a g e
b i r e f r i n g e n c e : 0 . 0 5 5 or l e s s ,
and f u r t h e r has t h e f o l l o w i n g p r o p e r t i e s when i t i s
h e a t - t r e a t e d at c o n s t a n t l e n g t h a t 240C f or one
m i n u t e :
(a) dr y h e a t s h r i n k when
f r e e l y
h e a t - t r e a t e d a t
175C f or 30 mi n u t e s : 3. 0 %
or l e s s , a n d
(b) wor k l o s s when t he h y s t e r e s i s l oop
i s
me a s u r e d at a s t r e s s b e t we e n 0. 6
g/ d and 0. 05 g/ d u n d e r
c o n d i t i o n s of l e n g t h of t e s t s a mp l e of 10 i n c h , s t r a i n r a t e
of 0. 5 i n c h / m i n u t e and a t e m p e r a t u r e
of 150 C: 2. 0 x
1 0 - 5
i n c h . p o u n d / d e n i e r or
l e s s .
Mo r e o v e r ,
when t he f i b e r has
a c a r b o x y l
g r o u p
c o n t e n t of 20
e q u i v a l e n t / 1 0 6
g or
l e s s and i s s u b j e c t e d t o a
s u r f a c e t r e a t m e n t wi t h a c h e m i c a l l y a c t i v e
epoxy
o r
i s o c y a n a t e c ompound in t he s p i n n i n g and d r a wi n g s t e p s ,
t h e
f i b e r s hows mor e i mp r o v e d p r o p e r t i e s
s u i t a b l e f or u s i n g
t h e r e o f as a
r e i n f o r c e m e n t of r u b b e r
g o o d s .
The
p r o c e s s
of t he p r o d u c t i o n
of t he f i b e r a n d
t h e o r e t i c a l b a c k g r o u n d t h e r e o f
a r e e x p l a i n e d b e l o w .
i As a
r e s u l t of i n t e n s i v e s t u d y of t he
p r e s e n t
i n v e n t o r s , i t ha s be e n f ound t h a t when t he
p h a s e
of f i b e r i n
whi c h
no c r y s t a l l i n e d i f f r a c t i o n i s o b s e r v e d by wi de a n g l e
X- r a y
d i f f r a c t i o n i s d e f i n e d
as a mo r p h o u s , t he f i b e r
o b t a i n e d by d r a wi n g an u n d r a wn
y a r n
wh i c h i s i n t h e s t a t e i n
wh i c h m o l e c u l e s
a r e
o r i e n t a t e d in
some e x t e n t wh i l e b e i n g
a mo r p h o u s
( f o r i n s t a n c e , p o l y e t h y l e n e t e r e p h t h a l a t e h a v i n g a
b i r e f r i n g e n c e of 10 x
1 0
or mor e) shows s ma l l e r h e a t
s h r i n k i n c o mp a r i s o n
wi t h t h e f i b e r o b t a i n e d by d r a wi n g a n
u n d r a wn
y a r n
wh i c h i s
a mo r p h o u s and i s n o t o r i e n t a t e d
( wh e r e i n b o t h f i b e r s
a r e
dr a wn so as t o show t h e s a me
b i r e f r i n g e n c e and
a r e
h e a t - t r e a t e d at a t e m p e r a t u r e n e a r t o
t h e m e l t i n g p o i n t f o r
some
mi n u t e s a t c o n s t a n t l e n g t h
i n
o r d e r t o e l i m i n a t e t h e d i f f e r e n c e of t h e r ma l h i s t o r y
i n t h e
d r a wi n g p r o c e s s ) . I t i s a s s u me d t h a t when t h e a mo r p h o u s
u n d r a wn f i b e r wh i c h has mo l e c u l a r o r i e n t a t i o n i n
some e x t e n t
( but o r i e n t a t i o n - i n d u c e d c r y s t a l l i z a t i o n doe s n o t o c c u r ) i s
d r a wn ,
t h e d r a wn
y a r n
s hows
a
s ma l l s u b s t a n t i v e r e s i d u a l
s t r a i n c a u s e d by d r a wi n g
i n c o mp a r i s o n
wi t h t h e dr a wn
y a r n
o b t a i n e d by d r a wi n g t h e a mo r p h o u s
f i b e r i n wh i c h m o l e c u l e s
show r a n d o m o r i e n t a t i o n or s l i g h t o r i e n t a t i o n . B e s i d e s , i t
i s r e p o r t e d by
Ya s u d a e t al t h a t t he mo l e c u l a r o r i e n t a t i o n
of
s pun y a r n
i n m e l t - s p i n n i n g p r o c e s s
d e p e n d s on t h e
s p i n n i n g
s t r e s s at t h e s o l i d i f i c a t i o n
p o i n t t h e r e o f ( c f .
Ya s uda e t a l , S e n - i - G a k k a i - s h i , Vol . 34, P - 2 0 , 1 9 7 8 ) . B a s e d
on
t h e s e b a c k g r o u n d s ,
t h e
p r e s e n t
i n v e n t o r s ha ve i n t e n s i v e l y
s t u d i e d on
t h e c o n d i t i o n s of s p i n n i n g and d r a wi n g s t e p s
a n d
ha ve f o u n d t h e f o l l o w i n g
f a c t s :
(A) Unde r t h e c o n d i t i o n s of m e l t - s p i n n i n g w h e r e i n
t he
y a r n
i s s o l i d i f i e d at h i g h s p e e d , t he d i f f e r e n c e o f
t e n s i l e v i s c o s i t y of
p o l y me r me l t in each f i l a me n t
b e c o m e
l a r g e
b e c a u s e of t he
l a r g e d i f f e r e n c e of
t e mp e r a t u r e
b e t w e e n
t he i n n e r and o u t e r l a y e r s of e a c h f i l a me n t , wh i c h r e s u l t s
i n
o c c u r r e n c e
of d i f f e r e n c e of s p i n n i n g s t r e s s b e t we e n t h e
i n n e r and o u t e r l a y e r s of f i l a m e n t at t he s o l i d i f i c a t i o n
p o i n t
t h e r e o f and t h e n i n
e n l a r g e d
d i f f e r e n c e o f
b i r e f r i n g e n c e b e t we e n t h e i n n e r and o u t e r l a y e r s of f i l a m e n t
( i . e . d i f f e r e n c e of
d e g r e e of o r i e n t a t i o n of t he m o l e c u l a r
c h a i n ) . A c c o r d i n g l y , t h e maxi mum dr aw r a t i o i s d e t e r m i n e d
me r e l y by
t he s u r f a c e a r e a of t h e f i l a me n t whe r e o r i e n t a t i o n
p r o g r e s s e s
q u i c k l y as c o mp a r e d
wi t h i n n e r
p a r t
of a
f i l a m e n t
by d r a wi n g , and t he i n n e r
p a r t
wh e r e o r i e n t a t i o n doe s n o t
p r o g r e s s
s a t i s f a c t o r y s hows l o we r t e n a c i t y as c o mp a r e d
w i t h
s u r f a c e
a r e a ,
and h e n c e , t h e
y a r n
can h a r d l y show h i g h
t e n a c i t y .
(B) Ho we v e r , when t h e
of a i r f o r
q u e n c h i n g t he mo l t e n f i l a m e n t i s r a i s e d and f u r t h e r t h e
s o l i d i f i c a t i o n p o i n t of
y a r n
i s
k e p t away
f r om t h e s p i n n e r e t
so as t o d e c r e a s e t he d i f f e r e n c e of t he
t e m p e r a t u r e
b e t w e e n
i n n e r and o u t e r l a y e r s of f i l a m e n t at t he s o l i d i f i c a t i o n
p o i n t , t he d i s t r i b u t i o n of m o l e c u l a r o r i e n t a t i o n
d e g r e e o f
spun
f i l a m e n t s b e c o me s
n a r r o w e r ,
and t h e r e b y t he dr a wn
y a r n
o b t a i n e d f r om t he
spun y a r n can
show
h i g h t e n a c i t y e v e n
t h o u g h i t i s
p r o d u c e d t h r o u g h POY.
The p o l y e s t e r of t h e
p r e s e n t
i n v e n t i o n s h o u l d h a v e
95 %
by mol e or mor e
of
p o l y e t h y l e n e t e r e p h t h a l a t e
u n i t
a s
t he
c o mp o n e n t
u n i t and s h o u l d ha ve an
i n t r i n s i c v i s c o s i t y o f
0. 80
or mo r e , p r e f e r a b l y 0. 80 t o 2. 0 (when me a s u r e d at 3 0 C
i n
a
mi xe d s o l v e n t of p h e n o l / t e t r a c h l o r o e t h a n e = 6/ 4) i n
vi e w of u t i l i t i e s
as h i g h t e n a c i t y f i b e r s i n v a r i o u s
i n d u s t r i e s .
The
p o l y e s t e r y a r n
i s o c c a s i o n a l l y h e a t - t r e a t e d a t
a t e m p e r a t u r e n e a r t o t h e me l t i n g p o i n t d u r i n g
u s a g e
t h e r e o f , and t h e me l t i n g p o i n t of
p o l y e s t e r
l o we r s w i t h
i n c r e a s e of c o n t e n t of d i e t h y l e n e g l y c o l c o mp o n e n t ,
a n d
h e n c e ,
t h e c o n t e n t of d i e t h y l e n e g l y c o l
of t h e
p o l y e s t e r i s
a v e r y
i m p o r t a n t f a c t o r . Thus , t h e
p o l y e s t e r
f i b e r of t h e
p r e s e n t
i n v e n t i o n s h o u l d ha ve a c o n t e n t of d i e t h y l e n e g l y c o l
c o mp o n e n t
of 2. 5 %
by
mol e
or
l e s s of t h e
t e r e p h t h a l i c a c i d
r e s i d u e .
I n o r d e r t o us e t he p o l y e s t e r
f i b e r of t he
p r e s e n t
i n v e n t i o n
as an
r e i n f o r c e m e n t f or r u b b e r
g o o d s , t h e
p o l y e s t e r
f i b e r s h o u l d ha ve
a c o n t e n t of c a r b o x y l
g r o u p
o f
30
e q u i v a l e n t / 1 0 6
g or l e s s , p r e f e r a b l y
20
e q u i v a l e n t / 1 0
g
or l e s s , mor e p r e f e r a b l y
12
g or l e s s , f o r
e f f e c t i v e l y p r e v e n t i n g u n d e s i r a b l e d e t e r i o r a t i o n o f
p r o p e r t i e s due t o a t t a c k i n g of a mi n e s a n d / o r wa t e r c o n t a i n e d
i n r u b b e r
goods or
wi t h w a t e r .
The p o l y e s t e r
f i b e r s h o u l d ha ve
a y a r n
t e n a c i t y o f
8. 5 g/ d or mo r e ,
and f or s uch a p u r p o s e ,
t h e
p o l y e s t e r
f i b e r
s h o u l d ha ve
an a v e r a g e
b i r e f r i n g e n c e of 0 . 1 9 0
or mo r e ,
p r e f e r a b l y
of 0 . 1 9 0 t o 0 . 2 1 0 , i n a d d i t i o n t o o t h e r
r e q u i r e m e n t s .
The p o l y e s t e r
f i b e r i s p r e f e r a b l y
p r o d u c e d by s p i n n i n g t he s t a r t i n g p o l y e s t e r u n d e r a
c o m p a r a t i v e l y h i g h s p i n n i n g s t r e s s , i . e . u n d e r a s p i n n i n q
s t r e s s at a
s o l i d i f i c a t i o n p o i n t of 1. 5 x
1 0
t o 7. 5 x
107
d y n e / c m2 ,
f o l l o we d by d r a wi n g as i s e x p l a i n e d h e r e i n a f t e r ,
wh e r e i n t he d i f f e r e n c e of b i r e f r i n g e n c e s b e t we e n t he s u r f a c e
and c e n t e r of mo n o f i l a me n t of
s pun y a r n
s h o u l d be 10 %
o r
l e s s in o r d e r t o make t h e
a v e r a g e
b i r e f r i n g e n c e of d r a wn
f i l a me n t 0. 190 or mor e , o t h e r w i s e , t he d r a wi n g
i s
v e r y
d i f f i c u l t in i n d u s t r i a l s c a l e .
Ac c o r d i n g t o e x p e r i me n t b y
t he
p r e s e n t i n v e n t o r s , when
a s pun y a r n h a v i n g a
d i f f e r e n c e
of b i r e f r i n g e n c e
b e t we e n t h e s u r f a c e and c e n t e r o f
mo n o f i l a me n t of 10 %
or l e s s i s dr a wn t o o b t a i n
a h i g h
t e n a c i t y
y a r n
h a v i n g a y a r n t e n a c i t y
of 8. 5 g/ d or mor e ,
t h e
d i f f e r e n c e of b i r e f r i n g e n c e s b e t we e n t he s u r f a c e and c e n t e r
of mo n o f i l a me n t of dr a wn
y a r n
i s l e s s t h a n 5. 5 %.
T h e r e f o r e , t he
y a r n
has u n i f o r m d i s t r i b u t i o n ( not m a i n l y
l o c a t e d at t he s u r f a c e a r e a ) of t i e - m o l e c u l a r c h a i n s w h i c h
c o n t r i b u t e t o t he t e n a c i t y of f i b e r and h e n c e
can
m a i n t a i n
t h e h i g h t e n a c i t y
t h e r e o f
e ve n
i f i t i s
k e p t at a n
a t mo s p h e r e whe r e t he
y a r n
i s d e t e r i o r a t e d f r om t he s u r f a c e
t h e r e o f , wh i l e t he p o l y e s t e r t i r e
y a r n
dr a wn wi t h POY w h i c h
i s p r o d u c e d by p r i o r a r t can not ma i n t a i n t he
t e n a c i t y .
Thus ,
i t i s i mp o r t a n t t h a t t h e
p o l y e s t e r
f i b 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 p e c i f i e d d i f f e r e n c e o f
b i r e f r i n g e n c e b e t we e n t he s u r f a c e and c e n t e r of f i l a me n t o f
dr awn
y a r n .
As i s d i s c l o s e d in B r i t i s h P a t e n t No. 1 , 5 8 5 , 9 9 4 b y
t h e
p r e s e n t
i n v e n t o r s , t he
p r o p e r t i e s , p a r t i c u l a r l y d y n a mi c
of t h e h i g h t e n a c i t y
y a r n
u s e f u l
as a
r e i n f o r c e m e n t f o r r u b b e r
goods a r e i m p o r t a n t a f t e r
h e a t - t r e a t e d i n d i p p i n g
p r o c e s s ,
b e c a u s e
e ve n
i f t h e
p r o p e r t i e s
b e f o r e d i p p i n g
may
ha ve b i g d i f f e r e n c e
owi ng t o
t h e d i f f e r e n c e of p r o d u c t i o n s t e p s ,
t h e p r o p e r t i e s a f t e r
d i p p i n g a r e
l e s s d i f f e r e n t . Th u s , t h e
p r o p e r t i e s
s uc h a s
l ow s h r i n k a g e and low wor k l o s s of t h e
p o l y e s t e r f i b e r o f
t h e
p r e s e n t
i n v e n t i o n
a r e i mp o r t a n t f o r u s i n g a c t u a l l y
i n
some u t i l i t i e s , and t h e p o l y e s t e r f i b e r b e f o r e d i p p i n g d o e s
n o t a l wa y s r e q u i r e t o ha ve low s h r i n k a g e and low wor k l o s s .
Thus , i n c a s e of
h e a t - t r e a t i n g a t c o n s t a n t l e n g t h
a t 240 C f o r one
mi n u t e ( i n d i p p i n g p r o c e s s ) , t he dr awn
y a r n
of t h e
p r e s e n t
i n v e n t i o n has a dr y h e a t s h r i n k of 3. 0 %
o r
l e s s when t he
y a r n
i s f r e e l y h e a t - t r e a t e d a t 175C f or 30
mi n u t e s and
a
wor k l o s s of 2. 0 x
10- 5
i n c h
p o u n d / d e n i e r o r
l e s s ( i . e . 0 . 0 2 0 0 i n c h . p o u n d or l e s s
p e r
1000 d e n i e r s ) wh e n
t h e h y s t e r e s i s l o o p
i s me a s u r e d at a s t r e s s b e t we e n 0. 6 g / d
and 0 . 0 5 g/ d u n d e r c o n d i t i o n s of
l e n g t h of t e s t s a mp l e of 10
i n c h ,
s t r a i n r a t e of 0. 5 i n c h / mi n u t e and
a t e m p e r a t u r e
o f
150 C. Thus ,
t h e
p o l y e s t e r
f i b e r of t h e
p r e s e n t
i n v e n t i o n
s hows h i g h t e n a c i t y
wh i l e i t has low s h r i n k a g e and low wo r k
l o s s , and t h e h i g h t e n a c i t y
y a r n
of t h e
p r e s e n t
i n v e n t i o n i s
p a r t i c u l a r l y
u s e f u l
as a
r e i n f o r c e m e n t f o r r u b b e r
g o o d s , f o r
i n s t a n c e ,
f o r t i r e , V b e l t ,
c o n v e y o r
b e l t , or
t he l i k e .
The d i f f e r e n c e of
b i r e f r i n g e n c e b e t we e n t h e
s u r f a c e and c e n t e r of mo n o f i l a me n t i s me a s u r e d
by t he me t h o d
of S h i mi z u e t al ( c f . S h i mi z u et a l , S e n - i - G a k k a i - S h i , V o l .
37, T- 1 3 5 , 1 9 8 1 ) , and t he wor k l o s s i s me a s u r e d by t h e
me t hod d i s c l o s e d i n U. S. P a t e n t 4 , 1 9 5 , 0 5 2 .
As a
r e s u l t of i n t e n s i v e
s t u d y by t h e
p r e s e n t
i n v e n t o r s , t h e d e s i r e d
p o l y e s t e r f i b e r
can
be
p r o d u c e d i n
i n d u s t r i a l s c a l e
by
t h e POY s p i n n i n g
wi t h
a q u e n c h i n g a i r
h a v i n g a c o m p a r a t i v e l y h i g h t e m p e r a t u r e ,
and d r a wi n g t he POY
by s p i n - d r a w p r o c e s s
wh e r e i n two d r a wi n g s t a g e s a r e
p r o v i d e d ,
and h i g h t e m p e r a t u r e s t e a m b e i n g u s e d i n t he f i r s t
d r a wi n g s t a g e ,
and
a c o n t a c t - h e a t t r a n s f e r d e v i c e s uc h
a s
hot r o l l
or
h o t p l a t e b e i n g us e d i n t he s e c o n d d r a w i n g
s t a g e .
Sa i d
p r o c e s s
i s e x c e l l e n t f r om t h e v i e w p o i n t of
e a s y
o p e r a t i o n a b i l i t y
f o r p r o d u c t i o n as
we l l
as
e c o n o m i c a l
v i e w p o i n t .
G e n e r a l l y s p e a k i n g ,
t he d r a wi n g of POY by a
s p i n - d r a w p r o c e s s
s h o u l d be done at an e x t r e me l y h i g h s p e e d .
A c c o r d i n g l y , t h e d r a wi n g
i s
v e r y
d i f f i c u l t , and h e n c e , t h e
d r a wi n g
of POY by a s p i n - d r a w
p r o c e s s
i s n o t s u i t a b l e f r o m
e c o n o mi c a l v i e w p o i n t . For m t h i s v i e w p o i n t , t h e m e t h o d
d i s c l o s e d i n U. S. P a t e n t 4 , 1 9 5 , 0 5 2 i s c a r r i e d o u t by f i r s t
st age drawi ng at o n - l i n e and t h e r e a f t e r
s u b j e c t i n g to t he s e c o n d
s t a g e
d r a wi n g a t o f f - l i n e , wh i c h i s not t h e s p i n - d r a w
p r o c e s s .
Ac c o r d i n g t o t he p r i o r a r t of s p i n - d r a w
p r o c e s s ,
t he d r a wi n g of POY wh i c h mus t be dr awn at a h i g h s p e e d c a n
not g i v e s a t i s f a c t o r y
r e s u l t i n
an i n d u s t r i a l s c a l e . F o r
i n s t a n c e when two d r a wi n g s t a g e s a r e a p p l i e d t o wh e r e i n
a
c o n t a c t t y p e
h e a t t r a n s f e r d e v i c e s uc h
as
h o t r o l l i s u s e d
i n e a c h
s t a g e ,
t he
o p e r a b i l i t y i s i n f e r i o r
as i s shown i n
Ex a mp l e 1, ' D' h e r e i n a f t e r . B e s i d e s , when t he
d r a wi n g
i s
c a r r i e d o u t by u s i n g
h e a t e d s t e a m i n
o n l y one d r a wi n g s t a g e ,
t oo l a r g e a mount of s t e a m i s
r e q u i r e d as
i s shown i n
E x a mp l e
1, ' E' h e r e i n a f t e r . Th u s , b o t h me t h o d s
a r e
r a t h e r
u n s a t i s f a c t o r y .
The
p r e s e n t
i n v e n t o r s ha ve f o u n d
an i mp r o v e d
p r o c e s s
f o r p r o d u c i n g
t h e d e s i r e d
p o l y e s t e r f i b e r
h a v i n g
e x c e l l e n t t h e r ma l d i m e n s i o n a l s t a b i l i t y and c h e m i c a l
s t a b i l i t y as
we l l as h i g h t e n a c i t y
wh i c h i s e c o n o mi c a l a n d
i s c a r r i e d o u t i n i mp r o v e d o p e r a t i o n a b i l i t y i n t he d r a w i n g
p r o c e s s .
A
p r o c e s s
of t h e
p r e s e n t
i n v e n t i o n
c o m p r i s e s
m e l t - s p i n n i n g a p o l y e s t e r c o mp r i s i n g e t h y l e n e t e r e p h t h a l a t e
as
t h e ma i n r e p e a t i n g
u n i t and h a v i n g 0. 8
or mor e of
a n
i n t r i n s i c v i s c o s i t y ( me a s u r e d at 30C i n
a
mi xe d s o l v e n t o f
p h e n o l / t e t r a c h l o r o e t h a n e
= 6/ 4) t h r o u g h a s p i n n e r e t i n
a n
e x t r u d i n g a mount of n o t mor e t h a n 3. 5 g / mi n u t e
pe r
e a c h
o r i f i c e of t h e s p i n n e r e t , q u e n c h i n g t h e
s pun y a r n
wi t h
a
q u e n c h i n g
a i r of 35 t o 80 C, p u l l i n g out t h e
s pun y a r n
i n
a
s p i n n i n g s t r e s s a t a
s o l i d i f i c a t i o n
p o i n t t h e r e o f of 1. 5 x
107
t o 7. 5 x
1 0
d y n e / c m2 ,
s u b j e c t i n g t he
y a r n
t o t h e
f i r s t d r a wi n g by p a s s i n g t h r o u g h a
d e v i c e f or
f i x i n g t h e
d r a wi n g p o i n t wh e r e i n h e a t e d s t e a m of 400 t o 650C i s u s e d
b e t we e n a f i r s t
g o d e t
r o l l and
a s e c o n d g o d e t r o l l at a
d r a w
r a t i o (D) of t he f o l l o w i n g f o r m u l a :
wh e r e i n Y i s
a
v a l u e of t h e
f o l l o w i n g f o r m u l a :
Y = 6. 834 x
10-4
x
B2 -
0 . 0 8 7 4 x B + 4 . 8 1 6 ( 2)
wh e r e i n B i s
an a v e r a g e
b i r e f r i n g e n c e of t he
s pun y a r n
x
103,
s u b j e c t i n g t he r e s u l t i n g
y a r n
t o t he s e c o n d d r a w i n g
b e t we e n a s e c o n d g o d e t
r o l l and
a
t h i r d
g o d e t r o l l at a
of 180C t o a me l t i n g p o i n t t h e r e o f and at
a
dr aw r a t i o n of 1. 05 t o 1 . 2 0 , and t h e n
wi n d i n g
up
t h e d r a wn
y a r n
d i r e c t l y or o p t i o n a l l y
a f t e r
b e i n g s l i g h t l y r e l a x e d
wi t h
a
f o u r t h g o d e t
r o l l t o g i v e a p o l y e s t e r
f i b e r
h a v i n g
e x c e l l e n t t h e r ma l d i m e n s i o n a l
s t a b i l i t y and c h e m i c a l
we l l
as h i g h t e n a c i t y .
The
p o l y e s t e r
f i b e r of t he
p r e s e n t
i n v e n t i o n i s
i n t e n d e d t o be u s e d ma i n l y as a h i g h t e n a c i t y
f i b e r i n
v a r i o u s i n d u s t r i e s , and h e n c e , t h e f i b e r s h o u l d ha ve 95 % b y
mol e or mor e of e t h y l e n e t e r e p h t h a l a t e u n i t
as
t he
r e p e a t i n g
u n i t and s h o u l d ha ve an
i n t r i n s i c
v i s c o s i t y of 0. 8
or mo r e .
Wh e n t he i n t r i n s i c v i s c o s i t y of t he f i b e r i s l e s s t h a n 0 . 8 ,
i t has l o we r
t e n a c i t y and i s not s u i t a b l e f or s uc h
a
p u r p o s e .
In t he s p i n n i n g s t e p
i n t he a bove
p r o c e s s
of t h e
p r e s e n t i n v e n t i o n , t he s t a r t i n g p o l y e s t e r
s h o u l d be
s p u n
) t h r o u g h a s p i n n e r e t at a t h r o u g h p u t pe r
e a c h o r i f i c e of n o t
mor e
t h a n 3. 5 g / mi n u t e . When t h e a mount i s
o v e r
3 . 5
g / mi n u t e ,
t he
spun y a r n
s hows
a l a r g e
d i f f e r e n c e o f
b i r e f r i n g e n c e s of e a c h f i l a me n t b e t we e n t he i n n e r and o u t e r
l a y e r s , wh i c h r e s u l t s i n l e s s e f f e c t i v e
q u e n c h i n g w i t h
h i g h t e m p e r a t u r e q u e n c h i n g
a i r and i n low b i r e f r i n g e n c e o f
t he
spun y a r n ,
and h e n c e , t h e r e can n o t be o b t a i n e d t h e
d e s i r e d h i g h t e n a c i t y f i b e r wi t h low s h r i n k wh i c h i s u s e f u l
as a
r e i n f o r c e m e n t f or r u b b e r g o o d s .
The mo l t e n t h r e a d s j u s t e x t r u d e d f r om s p i n n e r e t s
a r e q u e n c h e d
wi t h h o t a i r d i r e c t l y ( i . e . wi t h o u t p a s s i n g
t h r o u g h a q u e n c h c o l l a r )
or
a f t e r p a s s i n g t h r o u g h a q u e n c h
c o l l a r . Th a t i s , t h e
s pun y a r n
i s
q u e n c h e d wi t h
a q u e n c h i n g
a i r h a v i n g a c o m p a r a t i v e l y h i g h t e m p e r a t u r e s uc h as
35 t o
80 C, p r e f e r a b l y
60 t o 80C at an
a i r
v e l o c i t y o f 20 t o 100
c m/ s e c o n d u n t i l
a
p o i n t of t he
y a r n .
Ac c o r d i n g t o t h e q u e n c h i n g i n t h e a b o v e - me n t i o n e d
ma n n e r ,
t he t e m p e r a t u r e
d i f f e r e n c e b e t we e n t h e i n n e r and o u t e r
l a y e r s
of t h e f i l a m e n t at t h e s o l i d i f i c a t i o n
p o i n t t h e r e o f
i s s i g n i f i c a n t l y d e c r e a s e d , wh i c h r e s u l t s i n
e x t r e m e l y
d e c r e a s e d d i f f e r e n c e of
d e g r e e
of o r i e n t a t i o n of m o l e c u l a r
c h a i n of t he
s pun y a r n
b e t we e n t h e i n n e r and o u t e r l a y e r s o f
t he f i l a me n t . For i n s t a n c e , when t h e
o f
q u e n c h i n g
a i r i s v a r i e d f r om 20C t o 50 C, t he d i f f e r e n c e o f
b i r e f r i n g e n c e
b e t we e n t h e s u r f a c e and c e n t e r of t h e
mo n o f i l a me n t of t h e
s pun y a r n
d e c r e a s e s f r om 15 % t o 5 %.
When t he t e m p e r a t u r e
of t h e q u e n c h i n g a i r i s . l o w e r t h a n
3 5 C , t h e dr a wn
y a r n
has l o we r t e n a c i t y and t h e
o p e r a b i l i t y
of t he
p r o c e s s
i s a l s o l o we r e d . On t h e
o t h e r ha nd, when t h e
of t h e
q u e n c h i n g a i r i s
h i g h e r
t h a n 80C, t he u t i l i t y c o s t t h e r e o f i s i n c r e a s e d a n d
f u r t h e r t he d i s t a n c e b e t we e n t he
s p i n n e r e t
s u r f a c e and t h e
p o s i t i o n
of s o l i d i f i c a t i o n p o i n t of t he
y a r n
i s
e x t r e m e l y
e l o n g a t e d ,
and h e n c e , t he
p r o c e s s
can not p r a c t i c a l l y b e
us e d i n an
i n d u s t r i a l s c a l e .
In
p r o c e s s e s
of t he
p r e s e n t i n v e n t i o n , t h e
s p i n n i n g s t r e s s of t he
s pun y a r n
at t he s o l i d i f i c a t i o n
p o i n t
of t he
y a r n
i s
s i g n i f i c a n t , b e c a u s e t h e
of t he
s pun y a r n
d e p e n d s on t he
s p i n n i n g
s t r e s s at t he s o l i d i f i c a t i o n
p o i n t .
The
s pi nni ng s t r e s s of t h e
s pun y a r n
a f t e r s o l i d i f i c a t i o n t h e r e o f i s
s i mp l y and m a i n l y
i n c r e a s e d wi t h t he s p i n n i n g s t r e s s owi ng t o a i r f r i c t i o n ,
b u t i t has
no
r e l a t i o n wi t h t h e o r i e n t a t i o n of m o l e c u l a r
c h a i n . A c c o r d i n g l y ,
i t i s d e s i r a b l e t o c o n t r o l t he s p i n n i n g
s t r e s s at t he s o l i d i f i c a t i o n
p o i n t
of t he
y a r n
i n o r d e r t o
c o n t r o l t he b i r e f r i n g e n c e of
s pun y a r n .
Mai n f a c t o r s
a f f e c t i n g t he s p i n n i n g s t r e s s at s o l i d i f i c a t i o n
p o i n t o f
y a r n
a r e
t he a mount of p o l y me r e x t r u d e d f r o m
e a c h o r i f i c e , d i s t a n c e b e t we e n t h e s p i n n e r e t and t h e
p o s i t i o n
whe r e t he
y a r n
i s
e x p o s e d t o t he
q u e n c h i n g a i r , a n d
s p e e d
of s p i n n i n g . In t he
p r e s e n t i n v e n t i o n , p r e f e r a b l y
t h e
s p i n n i n g
c o n d i t i o n s
a r e c o n t r o l l e d so as t o d e f i n e t h e
s p i n n i n g s t r e s s at s o l i d i f i c a t i o n p o i n t
in t he
r a n g e
of 1 . 5
7 7
x
1 0
t o 7. 5 x
1 0
d y n e / c m2 ,
p r e f e r a b l y
2. 0 x
1 0
t o 6. 5 x
1 0 d y n e / c m2 .
When t he s p i n n i n g s t r e s s at s o l i d i f i c a t i o n
p o i n t
i s l owe r t h a n 1. 5 x
1 0 d y n e / c m2 ,
i t i s d i f f i c u l t t o
o b t a i n t he d e s i r e d
p o l y e s t e r f i b e r h a v i n g low s h r i n k w h i c h
i s one
of t he mos t i m p o r t a n t p r o p e r t i e s
in t he
p r e s e n t
p o l y e s t e r
f i be r . When the
s pi nni ng s t r e s s at s o l i d i f i c a t i o n
p o i n t
i s
l a r g e r
t h a n 7. 5
x
1 0 d y n e / c m2 ,
t he
s pun y a r n
i s a l r e a d y
c r y s t a l l i z e d
( d e t e r mi n e d
by a
wi de a n g l e X- r a y d i f f r a c t i o n ) ,
and h e n c e ,
t h e
s pun y a r n may
have
an ext r emel y l a r g e
d i s t r i b u t i o n i n a
f i l a me n t t h e r e o f and t h e
p o l y e s t e r
f i b e r o b t a i n e d a f t e r dr a wi ng ma y have
l o w t e n a c i t y
The a t t a c h e d F i g u r e 1 s hows t h e r e l a t i o n b e t we e n t h e
s p i n n i n g s t r e s s at t h e s o l i d i f i c a t i o n
p o i n t and t h e
(An) of t h e u n d r a wn
y a r n
( POY) .
In t he
p r e s e n t i n v e n t i o n , i t i s
d e s i r a b l e t o dr aw t h e
s pun y a r n
by u s i n g t wo d r a w i n g s t a g e s
i n a s p i n - d r a w p r o c e s s
i n o r d e r t o p r o d u c e t he d e s i r e d h i g h
t e n a c i t y y a r n
h a v i n g e x c e l l e n t t h e r ma l d i me n s i o n a l s t a b i l i t y
c h e mi c a l s t a b i l i t y and ot her
p r o p e r t i e s in
an e c onomi c a l
manner .
As a
r e s u l t of i n t e n s i v e s t u d y on
t h e
t w o s t a g e
d r a wi n g s y s t e m,
i t has b e e n f ound t h a t t he f i r s t
d r a wi n g i s
p r e f e r a b l y
c a r r i e d o u t by u s i n g a h e a t e d s t e a m of 400 t o
650C a t a
dr aw r a t i o
as
d e f i n e d by t he f o r mu l a ( 1) , and t h e
s e c o n d d r a wi n g
i s
p r e f e r a b l y
c a r r i e d out a t a t e m p e r a t u r e
o f
180C t o a me l t i n g p o i n t of t h e
y a r n
at a dr aw r a t i o of 1 . 0 5
t o 1 . 2 0 .
In t he f i r s t d r a wi n g s t a g e ,
t he
s pun
y a r n ma y b e
h e a t e d wi t h t h e h e a t e d s t e a m at
400 t o 650 C. ' T h e
of s t e a m i s
i mp o r t a n t , s i nce i f t h e
i s l o we r t h a n 4 0 0 C, e x c e s s s t e a m i s
r e q u i r e d , and i f
the t e mpe r a t ur e
is t oo low i t
may
not be
pos s i bl e to draw t he
y a r n
to the de s i r e d draw r a t i o . On t he o t h e r
h a n d ,
when t he
of s t e a m i s
too h i g h
t he
y a r n
i s mo l t e n and h e n c e t he d e s i r e d f i b e r
can not b e
o b t a i n e d .
The f o r mu l a (1) f or
s h o wi n g t he o p t i mu m dr aw r a t i o
i s d e r i v e d i n t h e f o l l o w i n g ma n n e r :
S e v e r a l k i n d s of u n d r a wn
y a r n s
(POY) a r e d r a wn
wi t h a d r a wi n g ma c h i n e at a f e e d i n g s p e e d of 100 m / m i n u t e ,
a
s u r f a c e t e m p e r a t u r e
of t he f e e d i n g r o l l of t he f o r m u l a :
wh e r e i n IV means an
i n t r i n s i c v i s c o s i t y of t he
s t a r t i n g
p o l y me r
s o l u t i o n , and /\nPOY
means an a v e r a g e b i r e f r i n g e n c e
of POY,
at a t e m p e r a t u r e
of t he hot
p l a t e
of 230 C, and at a
of t h e d r a w - r o l l of 140 C, in t h i s
s t e p ,
t h e
dr aw r a t i o at b r e a k i s me a s u r e d by d r a wi n g
t he
y a r n s b y
i n c r e a s i n g
t he
s p e e d
of t he dr aw r o l l . Ba s e d
upon
t he d r a w
r a t i o at b r e a k (Y) and t he b i r e f r i n g e n c e of t he
s pun y a r n ,
s e c o n d a r y r e g r e s s i o n a n a l y s i s i s made t o l e a d t he f o r m u l a
( 2) , and t h e n , t h e f o r mu l a (1) i s g i v e n b a s e d
upon
t h e
f o r mu l a ( 2 ) .
When t he f i r s t
d r a wi n g
i s c a r r i e d out u n d e r t h e
above c o n d i t i o n s , i t
can
be done
v e r y e f f e c t i v e l y
u s i n g a
mi ni mum a mount of s t e a m
pe r
t he we i g h t of t h e f i n a l
f i b e r
p r o d u c t .
The s e c o n d
d r a wi n g
may
be c a r r i e d out at
a t e mp e r a t u r e
of 180 C t o a me l t i n g p o i n t of t he
y a r n , p r e f e r a b l y 200 t o
2 4 0 C. When t he
t e m p e r a t u r e i s l o we r t h a n 180 C,
t h e r e ma y
be a t e nde nc y
f or
una c c e pt a bl e br eakage of f i l a me nt s . When
t h e
i s
h i g h e r t h a n t h e
m e l t i n g p o i n t
of t he
y a r n ,
t he d r a wi n g i s i mp o s s i b l e b e c a u s e
of m e l t i n g of
y a r n .
The s e c o n d
d r a w i n g ma y b e
o u t a t a
dr aw r a t i o of 1. 05 t o 1 . 2 0 . When t h e dr aw r a t i o i s
h i g h e r
t h a n 1 . 2 0 , t he dr a w r a t i o i s
o v e r t h e maxi mum d r a w
r a t i o , wh i c h r e s u l t s i n much
o c c u r r e n c e of b r e a k i n g o f
f i l a m e n t s , and on t he o t h e r h a n d , when t h e dr aw r a t i o i s
l o we r t h a n 1 . 0 5 , t he
t e n a c i t y
of t he
yarn
is r e d u c e d .
Af t e r d r a wi n g ,
t h e dr awn
y a r n
i s
p r e f e r a b l y t a k e n
o f f a t a s p e e d
of 5 , 5 0 0 m/ mi n u t e or l e s s . When t h e
s p e e d o f
t a k i n g
o f f i s
o v e r 5 , 5 0 0 m/ mi n u t e , t he
d r a wi n g s p e e d ma y b e
so h i g h t h a t i t r e s u l t s i n i nc r e a s e d
br eakage o f
f i l a m e n t s and i n
d i f f i c u l t y i n o p e r a t i o n .
A l t e r n a t i v e l y , t h e p o l y e s t e r f i b 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 of t h e
p r e s e n t
i n v e n t i o n
can b e
p r o d u c e d by t h e f o l l o w i n g
p r o c e s s .
The a l t e r n a t i v e
p r o c e s s c o mp r i s e s m e l t - s p i n n i n g a
p o l y e s t e r c o mp r i s i n g e t h y l e n e t e r e p h t h a l a t e as t h e ma i n
r e p e a t i n g
u n i t and h a v i n g 0. 8
or mor e of
v i s c o s i t y ( me a s u r e d at 30C in
a
mi xe d s o l v e n t o f
p h e n o l / t e t r a c h l o r o e t h a n e = 6/ 4) t h r o u g h a s p i n n e r e t i n
t h r o u g h p u t
of not mor e
t h a n 3. 5 g / mi n u t e
p e r
e a c h o r i f i c e o f
t he s p i n n e r e t , q u e n c h i n g t he mo l t e n f i l a m e n t s wi t h
a
q u e n c h i n g
a i r of 35 t o 80C, p u l l i n g out t he
spun y a r n
in
a
y a r n
s p i n n i n g s t r e s s at a
p o i n t
t h e r e o f 1. 5 x
7
1 0
t o 7. 5 x
1 0 d y n e / c m2 ,
and
s u b j e c t i n g t he
s pun ya r n
t o a
m u l t i p l e d r a wi n g
wi t h h e a t e d r o l l s
s u b s e q u e n t l y t o t he a b o v e
q u e n c h i n g s t e p or
a f t e r b e i n g wound
on a wi n d i n g r o l l t o
g i v e
t h e d e s i r e d
p o l y e s t e r
f i b e r
h a v i n g t h e r ma l d i m e n s i o n a l
s t a b i l i t y and c h e mi c a l s t a b i l i t y as
we l l
as h i g h t e n a c i t y .
In t h e m u l t i p l e d r a wi n g of t h e a bove a l t e r n a t i v e
p r o c e s s ,
t h e numbe r of
d r a wi n g s t a g e s
i s not l i mi t e d but i s
u s u a l l y
t h r e e
s t a g e s .
The m u l t i p l e d r a wi n g i s c a r r i e d o u t
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 i n e a c h d r a wi n g s t a g e .
The f i r s t
d r a wi n g s t a g e
is p r e f e r a b l y done at a
s u r f a c e t e m p e r a t u r e
of t he f i r s t d r a wi n g r o l l ( t he f i r s t
6 godet r o l l ) of not h i g h e r t h a n t h e
of t h e
f o r m u l a :
wh e r e i n IV and nPOY
ar e as
d e f i n e d i n t h e a bove f o r m u l a
( 3) , b u t not l o we r t h a n 69 C, and at a
dr aw r a t i o (D) of t h e
f o r m u l a :
wh e r e i n Y i s as d e f i n e d in t he f o r mu l a ( 2 ) .
The s e c o n d d r a wi n g s t a g e i s p r e f e r a b l y done at a
s u r f a c e
of t he s e c o n d d r a wi n g r o l l ( t he s e c o n d
6 godet r o l l ) of 120 t o 180C and a t a
dr aw r a t i o of 1. 15 t o
1 . 5 0 .
The t h i r d
d r a wi n g s t a g e
i s
p r e f e r a b l y done at a
s u r f a c e
of t he t h i r d
d r a wi n g
r o l l ( t he t h i r d
g o d e t r o l l ) of 180 t o 240C and at a dr aw r a t i o of 1. 05 t o
1 . 2 0 .
A c c o r d i n g t o t h i s m u l t i p l e d r a wi n g s y s t e m,
t h e
d r a wi n g t e m p e r a t u r e
i n t h e f i r s t d r a wi n g s t a g e
s h o u l d b e
h i g h e r t h a n t h e g l a s s t r a n s i t i o n
of t h e
y a r n ,
b u t
on
t h e o t h e r h a n d , i t i s n o t
s u i t a b l e
t o dr aw i t at s u c h
a h i g h t e m p e r a t u r e as
i n t h e c o n v e n t i o n a l
p r o c e s s ,
b e c a u s e
t he
y a r n
t o be dr a wn i s POY and h e n c e i t i s
c r y s t a l l i z e d
b e f o r e d r a wi n g or at e a r l y s t a g e
of t h e d r a wi n g i f i t i s
done at a t oo h i g h t e m p e r a t u r e as
p r o c e s s ,
wh i c h r e s u l t s i n i n s u f f i c i e n t dr aw r a t i o i n l a t e r
s t a g e . Th u s ,
i t i s d e s i r a b l e t o s p e c i f y t he s u r f a c e
of t h e f i r s t
g o d e t r o l l b a s e d
on
t h e IV a n d n
of
y a r n .
B e s i d e s , when t h e dr aw r a t i o a t t h e f i r s t
d r a w i n g
s t a g e
i s l e s s t h a n 60 % of t he maxi mum dr aw r a t i o
Y, t h e
down
yarn
may
c ont a i n
p a r t i a l l y
u n d r a wn
pa r t s , w h i c h i n a y r e s i l t i n
s i g n i f i c a n t u n e v e n n e s s of
y a r n
and l e s s
o p e r a b i l i t y
When t h e dr aw r a t i o i s
o v e r
85 % of t he ma xi mum
dr aw r a t i o Y, t h e d r a wi n g a t t h e l a t e r
s t a g e may
become l e s s
e f f e c t i v e and l e s s
o p e r a b l e .
The s e c o n d a n d
s u b s e q u e n t d r a wi n g s
may
be c a r r i e d out u n d e r t he
s a me
c o n d i t i o n s
as
p r o c e s s ,
wh e r e i n t h e
of t h e l a t e r r o l l i s a b o u t 30C h i g h e r t h a n t h a t
of t he f o r me r r o l l . Th a t i s , t he a b o v e - m e n t i o n e d
t e mp e r a t u r e r a n g e
and dr aw r a t i o
r a n g e
a r e s u i t a b l e .
Mo r e o v e r ,
t he
p r e s e n t
i n v e n t o r s have f ound t h a t
t he d e s i r e d
p o l y e s t e r
f i b e r
h a v i n g e x c e l l e n t t h e r m a l
d i me n s i o n a l s t a b i l i t y and c h e mi c a l
we l l
as h i g h
t e n a c i t y can a l s o be p r o d u c e d by a n o t h e r
p r o c e s s
wh e r e i n POY
h a v i n g
l e s s d i f f e r e n c e of mo l e c u l a r o r i e n t a t i o n b e t we e n t h e
i n n e r and o u t e r l a y e r s
of f i l a me n t t h e r e o f i s us e d and t h e
POY i s
s pun
at a c o m p a r a t i v e l y l o we r s p i n n i n g s p e e d ,
w h i c h
i s c h a r a c t e r i s e d i n t h a t t he
s pun y a r n
i s
q u e n c h e d
s p o n t a n e o u s l y ,
i . e . w i t h o u t
u s i n g
any
s p e c i f i c q u e n c h i n g
a i r .
I t i s known t h a t POY i s t h e r m a l l y s t a b l e ( c f .
J a p a n e s e
P a t e n t P u b l i c a t i o n No. 6 7 2 9 / 1 9 8 0 ) and t h a t t h e
f i b e r p r o d u c e d by d r a wi n g POY i s a l s o
t h e r m a l l y s t a b l e . I t
i s i n d u s t r i a l l y a d v a n t a g e o u s t o p r o d u c e POY at a
c o m p a r a t i v e l y l o we r s p i n n i n g s p e e d ,
b e c a u s e t he s p e e d of t h e
f i n a l t a k e - o f f
s t e p
i s a l s o made s l o w .
In o r d e r t o p r o d u c e a h i g h l y
o r i e n t a t e d POY at a
c o m p a r a t i v e l y l o we r s p i n n i n g s p e e d ,
t h e
s pun y a r n may
b e
q u e n c h e d
wi t h
a q u e n c h i n g a i r
h a v i n g a h i g h e r t e mp e r a t u r e a s
me n t i o n e d a b o v e , b u t i t r e s u l t s d i s a d v a n t a g e o u s l y i n
i n c r e a s e of
e n e r g y
c o s t . From t h i s v i e w p o i n t , i n t h i s
a l t e r n a t i v e
p r o c e s s ,
t he mo l t e n f i l a m e n t s e x t r u d e d f r om t h e
s p i n n e r e t i s q u e n c h e d s p o n t a n e o u s l y ,
i . e . w i t h o u t
u s i n g
a n y
s p e c i f i c q u e n c h i n g
a i r
c o n t r a r y t o t he common in t h i s f i e l d .
Tha t i s , t he f u r t h e r a l t e r n a t i v e
p r o c e s s
of t h e
p r e s e n t
i n v e n t i o n c o mp r i s e s m e l t - s p i n n i n g a p o l y e s t e r
c o mp r i s i n q e t h y l e n e t e r e p h t h a l a t e as t he mai n
r e p e a t i n q
u n i t
and h a v i n g 0. 8
or mor e of an
i n t r i n s i c
v i s c o s i t y ( m e a s u r e d
a t 30C i n
a
mi xe d s o l v e n t of p h e n o l / t e t r a c h l o r o e t h a n e =
6/ 4) t h r o u g h a s p i n n e r e t in a t h r o u g h p u t of n o t mor e t h a n
3. 5 g / m i n u t e p e r
e a c h o r i f i c e of t he s p i n n e r e t , q u e n c h i n g
t he
s p u n y a r n
w i t h o u t
u s i n g
any
q u e n c h i n g a i r , p u l l i n g o u t
t h e
s pun y a r n
i n t he s p i n n i n g s t r e s s at t he s o l i d i f i c a t i o n
p o i n t
of 1. 5 x
1 0
t o 7. 5 x
107
d y n e / c m2 ,
b u n d l i n g t he
y a r n
at 20 t o 100 cm b e l o w t h e p o s i t i o n of s o l i d i f i c a t i o n of t h e
y a r n
and t h e n s u b j e c t i n g t o d r a wi n g by a s p i n - d r a w me t h o d
v i a t h e f i r s t
g o d e t r o l l at a s p e e d of 1 , 5 0 0 m/ mi n u t e
o r
h i g h e r , by
wh i c h t h e d e s i r e d
p o l y e s t e r
f i b e r h a v i n g
e x c e l l e n t t h e r ma l d i me n s i o n a l s t a b i l i t y and c h e m i c a l
s t a b i l i t y as we l l
as h i g h t e n a c i t y can be p r o d u c e d
i n
v e r y
l o we r c o s t .
Th i s a l t e r n a t i v e
p r o c e s s
and t e c h n i c a l b a c k g r o u n d
t h e r e o f a r e e x p l a i n e d b e l o w .
When t h e s p i n n i n g
i s c a r r i e d out w i t h o u t
u s i n g
a n y
q u e n c h i n g a i r , t h e e x t r u d e d mo l t e n f i l a m e n t s
a r e
c o o l e d
v e r y
s l o wl y and t he s o l i d i f i c a t i o n p o i n t b e c o me s f a r f r om t h e
s p i n n e r e t ,
wh i c h r e s u l t s in i n c r e a s e d _
s p i n n i n q s t r e s s a t
s o l i d i f i c a t i o n p o i n t and in i n c r e a s e d
b i r e f r i n g e n c e of POY.
Mo r e o v e r ,
t e m p e r a t u r e b e t we e n t h e i n n e r
and o u t e r l a y e r s of f i l a me n t at t h e s o l i d i f i c a t i o n p o i n t
t h e r e o f i s r e ma r k a b l y d e c r e a s e d , wh i c h r e s u l t s i n r e m a r k a b l e
d e c r e a s e of d i f f e r e n c e of mo l e c u l a r o r i e n t a t i o n b e t we e n t h e
i n n e r and o u t e r l a y e r s of f i l a me n t . When t h e
s pun ya r n
i s
c o o l e d wi t h
a q u e n c h i n q a i r , t he
q u e n c h i n g c o n d i t i o n s
a r e
d i f f e r e n t
among
t he f i l a m e n t s and h e n c e t he d e g r e e o f
mo l e c u l a r o r i e n t a t i o n i s d i f f e r e n t
among
t he f i l a m e n t s ,
wh i c h a r e mor e s i g n i f i c a n t
when
a s p i n n e r e t h a v i n g
ma ny
o r i f i c e h o l e s i s u s e d . Ho we v e r , when no q u e n c h i n g a i r i s
us e d as
in t he a l t e r n a t i v e
p r o c e s s
of t he
p r e s e n t i n v e n t i o n ,
s uch d i f f e r e n c e s do not o c c u r . A c c o r d i n g l y , t he POY by t h e
p r e s e n t
i n v e n t i o n has
good u n i f o r m i t y and t he maxi mum d r a w
r a t i o b e c o me s
l a r g e r t h a n t h e
c a s e
of t he c o n v e n t i o n a l POY
p r o c e s s
when t he
y a r n s
show t h e
same a v e r a g e
i n b o t h
p r o c e s s e s ,
and t h e f i b e r o b t a i n e d
by t he
p r e s e n t
i n v e n t i o n has h i g h e r t e n a c i t y .
The a l t e r n a t i v e
p r o c e s s
of t he
p r e s e n t
i n v e n t i o n
can g i v e
POY 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 of
y a r n
in
g o o d
p r o d u c t i v i t y A p a r t i c u l a r a d v a n t a g e of t h i s
>p r o c e s s
i s t h a t t he c o s t f or
a p p a r a t u s
i s l a r g e l y s a v e d
b e c a u s e n e i t h e r
e n e r g y
f o r s u p p l y i n g a q u e n c h i n g
a i r
n o r
d e v i c e f or s u p p l y i n g t he q u e n c h i n g
a i r i s r e q u i r e d .
Ho we v e r ,
in t h i s
p r o c e s s ,
t he
s pun y a r n
o c c a s i o n a l l y s h a k e s d u e t o t he a c c o mp a n y i n g a i r , whi c h
c a u s e s
o c c u r r e n c e of u n d e s i r a b l e d e n i e r
u n e v e n n e s s
in
l o n g i t u d i n a l
d i r e c t i o n of
y a r n
( c f . W. S t e i n ; I n t . Te x t . B u l l . , Wo r l d
Ed . , S p i n n i n g (3) 259, 1 9 8 1 ) . As a
r e s u l t of i n t e n s i v e
s t u d y of t he
p r e s e n t i n v e n t o r s , i t has be e n f ound t h a t t h e
s ha ke of
s pun y a r n
owi ng t o t he
a c c o mp a n y i n g a i r
can
b e
p r e v e n t e d by a r r a n g i n g a
d e v i c e f o r b u n d l i n g
y a r n
at t h e
p o s i t i o n of 20 t o 100
cm
b e l o w t he s o l i d i f i c a t i o n
p o i n t
o f
y a r n .
When t he
p o s i t i o n of
a r r a n g i n g t he b u n d l i n g
d e v i c e i s
s h o r t e r t h a n 20
cm f r om t he s o l i d i f i c a t i o n
p o i n t o f
f i l a m e n t , t h e
y a r n o c c a s i o n a l l y ha ngs on t h e d e v i c e , and o n
t he o t h e r h a n d , when t h e p o s i t i o n of a r r a n g i n g t h e b u n d l i n g
d e v i c e i s mor e
f a r t h a n 100 c m, t h e u n d e s i r a b l e
s h a k i n g
o f
y a r n
can n o t e f f e c t i v e l y be
p r e v e n t e d . The a c c o mp a n y i n q
F i g u r e
2 s hows t h e r e l a t i o n b e t we e n t he Us t e r u n e v e n n e s s
U %
of POY and t h e d i s t a n c e b e t we e n t he s o l i d i f i c a t i o n
p o i n t
a n d
t h e p o s i t i o n
of
b u n d l i n g .
In t h i s
p r o c e s s ,
t he s t a r t i n g p o l y e s t e r
s h o u l d
ha ve
an
i n t r i n s i c v i s c o s i t y of 0. 8 or mor e ;
t h e t h r o u g h p u t
of t he p o l y e s t e r
s h o u l d be not mor e
p e r
e a c h o r i f i c e of t h e
s p i n n e r e t ; and t he
s p i n n i n g s t r e s s at
a
s o l i d i f i c a t i o n p o i n t of f i l a me n t s h o u l d be i n t he
r a n g e
o f
7
1. 5 x
1 0
t o 7. 5 x
1 0
d y n e / c m ,
b e c a u s e of t h e r e a s o n s a s
e x p l a i n e d
i n t h e a bove o t h e r
p r o c e s s .
B e s i d e s , when t h e
s p i n n i n q s p e e d
i s l o we r t h a n 1, 500 m/ mi n u t e , t h e o b t a i n e d
f i b e r s hows l e s s mo l e c u l a r o r i e n t a t i o n and h e n c e l e s s
t h e r ma l d i m e n s i o n a l s t a b i l i t y .
The
p r e s e n t
i n v e n t i o n i s i l l u s t r a t e d
by t h e
f o l l o w i n g E x a mp l e s
b u t s h o u l d not be c o n s t r u e d t o be l i m i t e d
t h e r e t o .
E x a m p l e 1
P o l y e t h y l e n e t e r e p h t h a l a t e ( i n t r i n s i c v i s c o s i t y :
1 . 0 , d i e t h y l e n e g l y c o l c o n t e n t : 1 . 0 % by mo l e , c a r b o x y l
g r o u p
c o n t e n t : 10
e q u i v a l e n t / 1 0 6
g) was
s pun
and dr a wn u n d e r
t he c o n d i t i o n s as
shown i n Ta b l e 1 .
The
p r o c e s s e s ,
A, B a n d C wer e
e f f e c t i v e in
a n
i n d u s t r i a l vi e w
p o i n t , but t he
p r o c e s s
D,
wh e r e i n
a
hot r o l l
was
us e d i n t h e f i r s t d r a wi n g s t a g e
b u t
no
h e a t e d s t e a m wa s
u s e d , s howe d some
b r e a k i n g of
y a r n
and h e n c e
was not s o
s u i t a b l e f o r i n d u s t r i a l p r o d u c t i o n of t he f i b e r . T h e
p r o c e s s
E, wh e r e i n h e a t e d s t e a m was us e d but two d r a w i n g
s y s t e m was not a p p l i e d t o , r e q u i r e d t o o muc h
h e a t e d s t e a m and
an e x t r e me l y h i g h u t i l i t y c o s t , and h e n c e ,
i t was n o t s u i t a b l e f or i n d u s t r i a l
p r o d u c t i o n of t he f i b e r ,
e i t h e r . B e s i d e s , t he
p r o c e s s
F, wh e r e i n t he
t h r o u g h p u t o f
t he s t a r t i n g pol ymer was l a r ge r t han 3.5 g/ mi nut e
per
each o r i f i c e
of t he s p i n n e r e t and t he f i n a l
w i n d i n g - u p s p e e d was h i g h e r
t h a n 5 , 5 0 0 m/ mi n u t e , s howed r e ma r k a b l e b r e a k i n g of
ya r n
a n d
bad o p e r a b i l i t y In o r d e r t o make t he f i n a l
w i n d i n g - u p
s p e e d l o we r t h a n 5 , 5 0 0 m/ mi n u t e , i t
was n e c e s s a r y
t o
i n c r e a s e t h e
b i r e f r i n g e n c e of
s pun y a r n
t o be s e n t t o t h e
f i r s t g o d e t r o l l wh i l e
k e e p i n g t he
s p i n n i n g s p e e d as low a s
p o s s i b l e . For s uc h
p u r p o s e ,
i t i s
n e c e s s a r y
t o c o n t r o l t h e
i n t r i n s i c v i s c o s i t y of t h e
p o l y me r t o 0. 8
or mo r e ,
t h e
e x t r u d i n g t e mp e r a t u r e
in t he
r a n g e
of 280 t o 325 C, and t h e
t h r o u g h p u t t o not more t h a n 3. 5 g / mi n u t e
p e r
e a c h o r i f i c e .
In c a s e of t he
p r o c e s s
G wh i c h
was done by a
c o n v e n t i o n a l
s p i n - d r a w me t h o d , t he s p i n n i n g s t r e s s at a s o l i d i f i c a t i o n
p o i n t was
v e r y
l ow, and t he o b t a i n e d
y a r n
has
a h i g h d r y
h e a t s h r i n k a g e .
Exa mpl e 2
As t o t he f i b e r s
p r o d u c e d by t he
p r o c e s s e s
A and C
i n Ta b l e 1 in Exa mpl e
1 ( f i b e r s of t he
p r e s e n t i n v e n t i o n )
and t he f i b e r p r o d u c e d by
t he
p r o c e s s
G ( t he c o n v e n t i o n a l
h i g h t e n a c i t y
f i b e r
as a r e f e r e n c e ) , t he c h a r a c t e r i s t i c s
a s
a
t i r e c o r d wer e c o mp a r e d .
Each f i b e r was made
a c o r d of two f o l d e d
y a r n
h a v i n g a number of t w i s t of 40 x 40 ( T/ 10 cm) , and t h e
r e s u l t i n g c o r d was d i p p e d
i n
a
r e s o r c i n o l - f o r m a l i n - l a t e x
t r e a t i n g l i q u i d c o n t a i n i n g Vu l c a b o n d E ( ol d name: P e x u l ,
ma n u f a c t u r e d by VULNAX) ( t r e a t i n g t e m p e r a t u r e : 240C) Th e
d i p p e d
c o r d c h a r a c t e r i s t i c s of t h e s e t h r e e c o r d s w e r e
c o mp a r e d .
The r e s u l t s a r e shown i n Ta b l e 2 .
As i s c l e a r f r om t h e a bove Ta b l e 2, t h e f i b e r s
o b t a i n e d by
t he
p r e s e n t
i n v e n t i o n s howe d t he
same
t e n s i l e
s t r e n g t h and c h e mi c a l s t a b i l i t y as t h o s e of t he c o n v e n t i o n a l
h i g h t e n a c i t y p o l y e s t e r
f i b e r and s howe d r e ma r k a b l e i m p r o v e d
d i me n s i o n a l s t a b i l i t y .
Ba s e d
on
t h e s e t e s t s , i t i s c o n f i r me d t h a t t h e
p r e s e n t
i n v e n t i o n
can g i v e
t h e e x c e l l e n t f i b e r i n
c o m p a r a t i v e l y
low c o s t .
Ex a mp l e 3
P o l y e t h y l e n e t e r e p h t h a l a t e ( i n t r i n s i c
v i s c o s i t y :
1 . 0 , d i e t h y l e n e g l y c o l
c o n t e n t : 1. 0 % by mo l e , c a r b o x y l
g r o u p
c o n t e n t : 10
e q u i v a l e n t / 1 0 6
g) was
spun
and dr awn u n d e r
t he c o n d i t i o n s
as
shown in Ta b l e 3. The r e s u l t s
a r e s h o wn
i n Ta b l e 3, H - M.
The
p r o c e s s
H,
wh e r e i n t he t h r o u g h p u t
of
p o l y me r
pe r
e a c h o r i f i c e
was o v e r
3. 5 g / mi n u t e , s howed b i g
d i f f e r e n c e of b i r e f r i n g e n c e
b e t we e n t he s u r f a c e and c e n t e r
of t he f i l a me n t of
s pun y a r n
and l e s s e f f e c t of t he h i g h
t e m p e r a t u r e q u e n c h i n g
a i r ( p o s i t i v e q u e n c h i n g at a h i g h
t e m p e r a t u r e ) ,
and h e n c e , t he
s pun y a r n
had l o w e r
b i r e f r i n g e n c e and t he d e s i r e d p o l y e s t e r f i b e r h a v i n g h i g h
t e n a c i t y and low s h r i n k c o u l d not be o b t a i n e d .
In b o t h of t he
p r o c e s s
J wh e r e i n t he s p i n n i n g
s t r e s s at a
s o l i d i f i c a t i o n p o i n t was s ome wha t l o we r t h a n 1 . 5
x
1 0 d y n e / c m2 ,
and t he
p r o c e s s
I wh e r e i n t he s p i n n i n g
s t r e s s at a
s o l i d i f i c a t i o n p o i n t was r e ma r k a b l e l o we r t h a n
1. 5 x
107
d y n e / c m2 ,
t he
dr y
h e a t s h r i n k a g e of t he f i b e r s
wa s
l a r g e ,
and h e n c e , t h e r e c o u l d not be o b t a i n e d t he d e s i r e d
p o l y e s t e r
f i b e r h a v i n g a
low s h r i n k .
In c a s e
of t he
p r o c e s s
K wh e r e i n t he
s p i n n i n g
s t r e s s at a
p o i n t was l a r g e r t h a n 7. 5 x
1 0
d y n e / c m2 ,
t he
s pun y a r n was a l r e a d y c r y s t a l l i z e d ( me a s u r e d
by a
wi de a n g l e X- r a y d i f f r a c t i o n ) , and t he b i r e f r i n g e n c e
d i s t r i b u t i o n i n t he f i l a me n t of
s pun y a r n
be c a me r e m a r k a b l y
l a r g e ,
and h e n c e , b r e a k i n g
of dr a wn
y a r n
o c c u r r e d f r e q u e n t l y
6 and t he f i b e r o b t a i n e d a f t e r d r a wi n g s howed
e x t r e me l y
l o w e r
t e n a c i t y .
In c a s e
of t h e
p r o c e s s
L of t he
p r e s e n t
i n v e n t i o n
wh e r e i n t he t e m p e r a t u r e of q u e n c h i n g a i r
was 50C, t h e r e
c o u l d be o b t a i n e d t h e d e s i r e d f i b e r wh i l e t he b r e a k i n g o f
y a r n was
o b s e r v e d i n
some e x t e n t ,
but
on t he o t h e r h a n d , i n
c a s e
of t he
p r o c e s s
M wh e r e i n t he
of q u e n c h i n g
a i r was
30C wh i c h i s l o we r t h a n t he
r a n g e
of t he
p r e s e n t
i n v e n t i o n , t he
p r o d u c e d f i b e r had l o we r t e n a c i t y and t h e
b r e a k i n g
of
y a r n
o c c u r r e d
v e r y
f r e q u e n t l y .
Ex a mp l e 4
1 . 0 , d i e t h y l e n e g l y c o l c o n t e n t : 1. 0 % by mo l e , c a r b o x y l
g r o u p
c o n t e n t : 10
e q u i v a l e n t / 1 0 g )
was me l t - s p u n and d r a wn
u n d e r t h e c o n d i t i o n s
as shown i n Ta b l e 4 .
As i s c l e a r f r om Ta b l e 4, t he dr awn
y a r n s
p r o d u c e d
by
t h e
p r o c e s s e s
N t o Q wer e ma r k e d l y s u p e r i o r t o t h e
r e f e r e n c e
y a r n
p r o d u c e d by t h e c o n v e n t i o n a l
p r o c e s s
R i n t h e
t h e r ma l s t a b i l i t y and f u r t h e r we r e ma r k e d l y s u p e r i o r t o t h e
r e f e r e n c e
y a r n
( l ow s h r i n k a g e y a r n ) p r o d u c e d by
t h e
c o n v e n t i o n a l POY
p r o c e s s
S ( c f . 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
No. 1 1 9 6 1 4 / 1 9 8 1 ) i n
t e n a c i t y and c h e mi c a l s t a b i l i t y .
The "% Br o k e n Bonds " u s e d in Ta b l e 4
as an
i n d e x
of r e s i s t a n c e t o h y d r o l y s i s me a ns t h e r a t i o of s c i s s i o n o f
e s t e r b o n d s by h y d r o l y s i s t o t o t a l e s t e r bonds and i s
c a l c u l a t e d by
t h e f o l l o w i n g f o r m u l a :
wh e r e i n [ ] f i n a l means an
i n t r i n s i c v i s c o s i t y of f i b e r a f t e r
b e i n g d e t e r i o r a t e d , and [ ] i n i t i a l means an
i n t r i n s i c
v i s c o s i t y
of f i b e r b e f o r e d e t e r i o r a t i o n .
The a b o v e f o r mu l a (4) was d e r i v e d b a s e d
on t h e
f o l l o w i n g
r e l a t i o n b e t we e n t h e i n t r i n s i c
v i s c o s i t y ( me a s u r e d
at 25C i n
a
mi x e d s o l v e n t of p h e n o l / t e t r a c h l o r o e t h a n e =
6 / 4 ) : [ n
]25CP/TCE=6/4 and t h e n u mb e r
a v e r a g e
m o l e c u l a r
we i g h t : Mn
( c f . L. D. Moor e J r . ; C l e v e l a n d
A. C. S.
Me e t i n g 4 / 1 9 6 0 , Vo l .
1,
pa ge
2 3 4 ) .
Ex a mp l e 5
1 . 0 , d i e t h y l e n e g l y c o l c o n t e n t : 0. 9 % by mol e , c a r b o x y l
g r o u p
c o n t e n t : 12
e q u i v a l e n t / 1 0 6
g) was me l t - s p u n by a d d i n g
u n d e r
p r e s s u r e
t r i b u t y l p h o s p h i n e ( 0. 03 %
by we i g h t ) a n d
o r t h o - p h e n y l p h e n o l g l y c i d y l e t h e r ( 0. 5 % by we i g h t ) t o a
mo l t e n p o l y me r
i n
an e x t r u d e r , e x t r u d i n g t he mo l t e n m i x t u r e
f r om o r i f i c e s of
a s p i n n e r e t ( numbe r of o r i f i c e : 380) at a
p o l y me r t e m p e r a t u r e of 315C and i n
a t h r o u g h p u t of 2 . 1 7
g / mi n u t e
p e r
e a c h o r i f i c e , and t he
spun y a r n we r e q u e n c h e d
wi t h
a q u e n c h i n g a i r of 60C i n a d i s t a n c e b e t we e n t h e
s p i n n e r e t
s u r f a c e and q u e n c h i n g p o s i t i o n of 28
cm and at a
v e l o c i t y of a i r of 0. 5 m/ s e c o n d . The
q u e n c h e d
s pun y a r n
wer e
f i n i s h e d wi t h
s p i n n i n g
l u b r i c a n t
c o n t a i n i n g 20 %
b y
we i g h t of e p o x y l a t e d g l y c e r i n and t h e n
wer e s u p p l i e d t o t h e
f i r s t g o d e t r o l l at a s p e e d
of 1720 m/ mi n u t e , i n wh i c h t h e
spun y a r n s
had
an a v e r a g e
b i r e f r i n g e n c e of 0 . 0 2 3 , a
b i r e f r i n g e n c e of s u r f a c e
a r e a
of f i l a me n t of 0 . 0 2 4 , and
a
b i r e f r i n g e n c e of c e n t e r of f i l a m e n t of 0 . 0 2 3 , i . e . t h e
d i f f e r e n c e of
b i r e f r i n g e n c e b e t we e n s u r f a c e
a r e a
and c e n t e r
of f i l a me n t
b e i n g me r e l y
0 . 0 0 1 . The
r e s u l t i n g
s pun y a r n s
wer e i mme d i a t e l y dr awn at a
dr a w r a t i o of 2. 86
by u s i n g
h e a t e d s t e a m of 445 C, and t h e n we r e wo u n d - u p at a r a t e o f
4920 m/ mi n u t e t o g i v e t h e
d e s i r e d f i b e r of t he
p r e s e n t
i n v e n t i o n ( t h i s
p r o c e s s
i s r e f e r r e d t o i n Ta b l e 5
as " T " ) .
For c o mp a r i s o n
p u r p o s e ,
p o l y e t h y l e n e t e r e p h t h a l a t e
( i n t r i n s i c v i s c o s i t y : 1 . 0 , d i e t h y l e n e g l y c o l c o n t e n t : 0. 9 %
by
mo l e , c a r b o x y l g r o u p
c o n t e n t : 12
e q u i v a l e n t / 1 0 6
g) wa s
me l t - s p u n by e x t r u d i n g a mo l t e n p o l y me r f r om o r i f i c e of a
s p i n n e r e t ( numbe r of o r i f i c e : 190) at
a p o l y me r t e m p e r a t u r e
of 315C and i n a t h r o u g h p u t of 3. 07 g / mi n u t e
p e r
e a c h
o r i f i c e , and t he
s pun y a r n s
we r e p a s s e d t h r o u g h a
h e a t e d
t u b e at 350 C f o r
a
d i s t a n c e of 30
cm and
we r e q u e n c h e d
w i t h
a q u e n c h i n g
a i r of 20C a t an
a i r v e l o c i t y of 0. 5 m / s e c o n d ,
and t h e n we r e s u p p l i e d t o t h e f i r s t g o d e t r o l l a t a s p e e d o f
614 m/ mi n u t e , i n wh i c h t h e
s pun y a r n s
had
an a v e r a g e
of 0 . 0 0 2 4 and u n i f o r m
b i r e f r i n g e n c e w i t h i n t h e
f i l a m e n t s . The
r e s u l t i n g
s pun y a r n s we r e i mme d i a t e l y d r a wn
a t a
dr aw r a t i o of 5. 7
by u s i n g h e a t e d s t e a m of 445C a n d
we r e wo u n d - u p at a r a t e of 3500 m/ mi n u t e t o g i v e a
f i b e r
( t h i s
p r o c e s s
i s r e f e r r e d t o i n Ta b l e 5
as " U" )
The c h a r a c t e r i s t i c s of t h e f i b e r s
a r e
shown i n
Ta b l e 5 .
The f i b e r s o b t a i n e d a b o v e
wer e e a c h made
a c o r d o f
two f o l d e d
y a r n
h a v i n g a
numbe r of t wi s t of 40
x 40 ( T / 1 0
cm), and t he r e s u l t i n g c o r d s we r e e a c h d i p p e d i n
a
r e s o r c i n o l - f o r m a l i n - l a t e x d i p p i n g l i q u i d (one
s t e p d i p p i n g
s ys t e m) at a t e m p e r a t u r e
of 2 4 0 C.
S e p a r a t e l y , t he f i b e r p r o d u c e d by t he
p r o c e s s
U
was d i p p e d
i n a t w o - s t e p d i p p i n g
s o l u t i o n c o n t a i n i n g
Vu l c a b o n d E ( ol d
name: P e x u l , ma n u f a c t u r e d
by VULNAX) a t a
of 2 4 0 C .
The d i p c o r d c h a r a c t e r i s t i c s of t h e t h r e e c o r d s t h u s
o b t a i n e d we r e c o mp a r e d . The r e s u l t s a r e shown i n Ta b l e 6 .
As i s c l e a r f r o m Ta b l e 6, t h e f i b e r of t he
p r e s e n t
i n v e n t i o n p r o d u c e d by
t h e
p r o c e s s
T s howe d s i m i l a r
t e n a c i t y
t o t h a t of t h e h i g h t e n a c i t y f i b e r
p r o d u c e d by t h e
p r o c e s s
and s howed
h i g h l y i mp r o v e d c h e m i c a l
s t a b i l i t y
and t h e r ma l d i me n s i o n a l s t a b i l i t y . Mo r e o v e r , wh e n
t he f i b e r of t h e
p r e s e n t
i n v e n t i o n
was s u b j e c t e d t o s u r f a c e
t r e a t m e n t wi t h
an
epoxy
r e s i n , e t c . ,
i t be c a me
mo r e
e f f e c t i v e
as a
t i r e c o r d .
Ex a mp l e 6
P o l y e t h y l e n e t e r e p h t h a l a t e ( i n t r i n s i c
v i s c o s i t y :
1 . 0 , d i e t h y l e n e g l y c o l c o n t e n t : 1. 2 %
by mo l e , c a r b o x y l
g r o u p
c o n t e n t : 20
g) was
mo l t e n wi t h
a n
e x t r u d e r and t h e n
s pun
u n d e r t he c o n d i t i o n s
as
shown i n
Ta b l e 7. The p r o p e r t i e s of t he
y a r n s
t h u s o b t a i n e d
a r e
shown i n Ta b l e 7 .
As i s c l e a r f r om Ta b l e 7 t he
p r o c e s s e s
V t o X
c o u l d g i v e POY h a v i n g h i g h e r b i r e f r i n g e n c e at a
l o w e r
s p i n n i n g s p e e d
i n c o mp a r i s o n wi t h t he r e f e r e n c e
p r o c e s s
Y
wh e r e i n a q u e n c h i n g a i r (a c o n v e n t i o n a l c o o l
q u e n c h i n g a i r )
was
u s e d . B e s i d e s , t he POY p r o d u c e d by t he
p r o c e s s e s
V t o X
s howed a
s ma l l e r d i f f e r e n c e of b i r e f r i n g e n c e b e t we e n t h e
i n n e r and o u t e r l a y e r s of f i l a me n t and s u p e r i o r u n i f o r m i t y
i n c o mp a r i s o n wi t h t he POY p r o d u c e d by t he c o n v e n t i o n a l
p r o c e s s
Y and f u r t h e r , t he
y a r n s
of t he
p r o c e s s e s
V t o X
showed t he
same q u a l i t y l e v e l
as
t h e
y a r n
of t h e
p r o c e s s
Y i n t he Us t e r
u n e v e n n e s s (U %) .
Exa mpl e
7
The e f f e c t of t h e p o s i t i o n of
b u n d l i n g of
y a r n s o n
t he p r o p e r t i e s
t h e r e o f was e x a m i n e d .
The
p r o c e s s
V i n
Exa mpl e 6
was r e p e a t e d e x c e p t
t h a t t h e p o s i t i o n
of b u n d l i n g of
y a r n was v a r i e d , and t h e n ,
t he r e l a t i o n of t he d i s t a n c e b e t we e n t he s o l i d i f i c a t i o n
p o i n t
of
y a r n
and t he p o s i t i o n of b u n d l i n g of
y a r n
and t h e
Us t e r u n e v e n n e s s was
d e t e r mi n e d . The r e s u l t s
a r e
shown t h e
a t t a c h e d F i g u r e
2. As i s c l e a r f r om F i g u r e 2, i t i s
p r e f e r a b l e t o s e t t he p o s i t i o n of b u n d l i n g of
y a r n
t o 20 t o
100 cm b e l o w t he s o l i d i f i c a t i o n
p o i n t f r om t he
v i e w p o i n t o f
d e p r e s s i n g t he o c c u r r e n c e
of d e n i e r
u n e v e n n e s s .
Exa mpl e
8
The same p o l y e t h y l e n e t e r e p h t h a l a t e as
i n
E x a mp l e
6
was s pun
u n d e r t h e
same
c o n d i t i o n s
as
i n t he
p r o c e s s
W i n
Ex a mp l e 6. The
spun y a r n
was p a s s e d t h r o u g h t he f i r s t g o d e t
r o l l ( a t room t e mp e r a t u r e ) and was i mme d i a t e l y dr a wn w i t h
h e a t e d s t e a m of 550C at a
dr aw r a t i o of 2. 21 and
p a s s e d
t h r o u g h t h e s e c o n d g o d e t r o l l ( p e r i p h e r a l s p e e d : 4 4 2 0
m/ mi n u t e , t e mp e r a t u r e :
2 0 0 C) , and f u r t h e r , was dr a wn at a
dr aw r a t i o of 1. 149 b e t we e n t h e s e c o n d g o d e t r o l l and t h e
t h i r d g o d e t r o l l ( p e r i p h e r a l s p e e d : 5080 m / m i n u t e ,
t e m p e r a t u r e :
2 2 0 C) , and was r e l a x e d wi t h t he f o u r t h
g o d e t
r o l l ( p e r i p h e r a l s p e e d :
5000 m/ mi n u t e , t e m p e r a t u r e : 1 4 0 C)
i n a
r a t i o of 1. 6 %, and f i n a l l y was t a k e n o f f t o g i v e t h e
y a r n
of t he
p r e s e n t
i n v e n t i o n ( t h i s
p r o c e s s
i s r e f e r r e d t o
in Ta b l e 8
as " Z" ) . The p r o p e r t i e s of t he
y a r n a r e
shown i n
Ta b l e 8
t o g e t h e r
wi t h t he d a t a of t he r e f e r e n c e
y a r n
p r o d u c e d by
t h e
p r o c e s s
R i n Ta b l e 4 .
As i s c l e a r f r om T a b l e 8, t he f i b e r
p r o d u c e d b y
t h e
p r e s e n t p r o c e s s
Z s howed s u p e r i o r t h e r ma l s t a b i l i t y i n
c o mp a r i s o n
wi t h t he f i b e r
p r o d u c e d by t he c o n v e n t i o n a l
p r o c e s s
R.
The s o l i d i f i c a t i o n
p o i n t of
y a r n
i n t h e a b o v e
Ex a mp l e s was me a s u r e d i n t h e f o l l o w i n g ma n n e r .
As t o t h e f i l a m e n t
s pun
f r om s p i n n e r e t s u r f a c e ,
t h e d i a m e t e r t h e r e o f was me a s u r e d wi t h
a
d e v i c e f o r
me a s u r i n g t h e o u t e r d i a me t e r ( ma n u f a c t u r e d by Zi mmer
C o . ) ,
and t he v a r i a t i o n of d i a me t e r
a l o n g a
f i l a me n t
was o b s e r v e d .
When no v a r i a t i o n of d i a me t e r
was o b s e r v e d , i t
was d e f i n e d
as
t he p o i n t of c o mp l e t e l y
s o l i d i f i c a t i o n of t he f i l a me n t ( y a r n ) .
1. A
p o l y e s t e r
f i b r e
y a r n h a v i n g h i g h t h e r m a l
d i me n s i o n a l
s t a b i l i t y ,
c h e mi c a l
s t a b i l i t y and
t e n a c i t y
and f o r me d by me l t
s p i n n i n g p o l y e t h y l e n e t e r e p h t h a l a t e ,
s o l i d i f y i n g
t h e
s pun
f i l a m e n t s and t h e n d r a wi n g t he
y a r n
c h a r a c t e r i s e d i n t h a t t he
p o l y e s t e r
has
v i s c o s i t y
of 0. 8
or mor e ,
and t he dr a wn
y a r n
has
a
y a r n
t e n a c i t y
of 8. 5 g/ d or mo r e , an
a v e r a g e b i r e f r i n g e n c e
of 0. 19 or mor e and
by d i v i d i n g
b i r e f r i n g e n c e b e t we e n t h e
s u r f a c e and t h e c e n t r e of t h e mo n o f i l a me n t
by
a v e r a g e
b i r e f r i n g e n c e ,
of 0. 055
or l e s s , and t h e d r a w n
y a r n ,
a f t e r b e i n g h e a t t r e a t e d at c o n s t a n t l e n g t h 240C f o r
1 mi n u t e , has a d r y
h e a t s h r i n k when f r e e l y h e a t t r e a t e d
at 175C f o r 30 mi n u t e s of 3% or
l e s s .
2. A
y a r n a c c o r d i n g t o c l a i m 1 c h a r a c t e r i s e d
i n t h a t t he
p o l y e s t e r c o n t a i n s 2. 5% mo l a r
or
l e s s d i -
e t h y l e n e g l y c o l b a s e d on t e r e p h t h a l i c a c i d r e s i d u e s a n d
c o n t a i n s 30 e q u i v a l e n t s or
l e s s of
c a r b o x y l
g r o u p s p e r
1 0 g
and t he dr a wn
y a r n ,
a f t e r b e i n g
h e a t t r e a t e d a t
c o n s t a n t l e n g t h at 240C f o r 1 mi n u t e , has a wor k l o s s
when t he
h y s t e r e s i s
l oop i s me a s u r e d at a s t r e s s b e t w e e n
0. 6 g/ d and 0. 05 g/ d u n d e r c o n d i t i o n s of
l e n g t h o f
t e s t s a mp l e
of 10 i n c h , s t r a i n r a t e of 0. 5 i n c h / m i n u t e
and a t e m p e r a t u r e
of 150C: 2. 0 x
1 0
i n c h . p o u n d / d e n i e r
or
l e s s .
3. A
y a r n
a c c o r d i n g t o c l a i m 1 or c l a i m 2
p o l y e s t e r c o n t a i n s not mor e t h a n
20, and p r e f e r a b l y n o t
mor e t h a n 12, e q u i v a l e n t s c a r b o x y l
g r o u p s p e r
106
g .
4. A
p r o c e s s
f o r t he p r o d u c t i o n of
p o l y e s t e r
y a r n
h a v i n g h i g h t h e r ma l d i me n s i o n a l s t a b i l i t y , c h e m i c a l
t e n a c i t y , wh i c h c o mp r i s e s m e l t - s p i n n i n g
a p o l y e s t e r c o m p r i s i n g e t h y l e n e t e r e p h t h a l a t e as
t h e
ma i n r e p e a t i n g u n i t , s o l i d i f y i n g t he
s pun
f i l a m e n t s a n d
t h e n d r a wi n g
t h e
y a r n
c h a r a c t e r i s e d i n t h a t t h e
p o l y e s t e r
ha s an
i n t r i n s i c
v i s c o s i t y ( me a s u r e d a t 30C i n a m i x e d
s o l v e n t of p h e n o l / t e t r a c h l o r o e t h a n e = 6/ 4) of 0. 8 o r
mo r e ,
and t h e
p r o c e s s
c o mp r i s e s s p i n n i n g t h r o u g h a s p i n n -
e r e t a t a t h r o u g h p u t of n o t mor e
p e r
s p i n n e r e t , q u e n c h i n g
t he
s pun y a r n
wi t h q u e n c h i n g a i r of 35 t o 80C
( p r e f e r a b l y 60 t o 8 0 C ) ,
p u l l i n g o u t t h e
s p u n y a r n
i n a s p i n n i n g s t r e s s at a
p o i n t
t h e r e o f of 1. 5 x
107
t o 7. 5 x
107
d y n e / c m2 , s u b j e c t i n g t h e
y a r n
t o t he f i r s t d r a wi n g b y
p a s s i n g t h r o u g h a
d e v i c e f o r f i x i n g t h e
d r a wi n g p o i n t
w h e r e i n h e a t e d s t e a m of 400 t o 650C i s us e d b e t w e e n
a
f i r s t g o d e t
r o l l and a s e c o n d g o d e t r o l l at a d r a w
r a t i o (D) of t h e f o l l o w i n g f o r m u l a :
w h e r e i n Y i s a
v a l u e of t h e f o l l o w i n g f o r m u l a :
wh e r e i n B i s an
a v e r a g e
of t he
s pun y a r n
x
103,
s u b j e c t i n g
t h e r e s u l t i n g
y a r n
t o t he s e c o n d d r a w i n g
b e t we e n a s e c o n d g o d e t
r o l l and
a
t h i r d g o d e t
r o l l at a
of 180 C t o a me l t i n g p o i n t
t h e r e o f and a t a
dr aw r a t i o of 1. 05 t o 1 . 2 0 , and t h e n wi n d i n g
up
t he d r a wn
y a r n
d i r e c t l y or o p t i o n a l l y a f t e r b e i n g r e l a x e d wi t h
a
f o u r t h g o d e t r o l l .
5. A
p r o c e s s
f or t he
p r o d u c t i o n
of
p o l y e s t e r
y a r n
h a v i n g h i g h t h e r ma l d i me n s i o n a l s t a b i l i t y , c h e m i c a l
s t a b i l i t y
and
t e n a c i t y ,
wh i c h
c o mp r i s e s m e l t - s p r i n n i n g
a p o l y e s t e r c o mp r i s i n g e t h y l e n e t e r e p h t h a l a t e as t h e
ma i n r e p e a t i n g u n i t , s o l i d i f y i n g
t h e
s pun
f i l a m e n t s a n d
t h e n d r a wi n g t h e
y a r n
p o l y e s t e r
has an i n t r i n s i c v i s c o s i t y ( me a s u r e d a t 30C i n
a
mi x e d
s o l v e n t of p h e n o l / t e t r a c h l o r o e t h a n e = 6/ 4) of 0 . 8
or mor e
and t h e
p r o c e s s c o m p r i s e s s p i n n i n g t h r o u g h a
s p i n n e r e t
a t a t h r o u g h p u t
of not mor e
t h a n 3. 5 g / m i n u t e
p e r
e a c h o r i f i c e of t he
s p i n n e r e t , q u e n c h i n g t h e
s pun y a r n
wi t h a q u e n c h i n g
a i r of 35 t o 80 C, p u l l i n g o u t t h e
s p u n
y a r n
a t a s p i n n i n g s t r e s s at a s o l i f i f i c a t i o n
p o i n t
t h e r e -
of 1. 5 x
107
t o 7. 5 x
10 7
d y n e / c m2 , and
s u b j e c t i n g t h e
s pun y a r n
t o a m u l t i p l e d r a wi n g
wi t h h o t r o l l s
s u b s e q u e n t l y
t o t h e a b o v e q u e n c h i n g s t e p or
a f t e r
b e i n g wound
on a
wi n d i n g
r o l l .
6. A
p r o c e s s
a c c o r d i n g t o c l a i m 5, wh e r e i n t h e
f i r s t h o t r o l l u s e d i n t he m u l t i p l e d r a wi n g s t e p
has a
s u r f a c e
of not h i g h e r t h a n t h e
o f
t h e f o r m u l a :
wh e r e i n IV me a ns an
i n t r i n s i c v i s c o s i t y of t h e
s t a r t i n g
p o l y me r ,
and AnPOY
means an a v e r a g e b i r e f r i n g e n c e of
a
p a r t i a l l y
o r i e n t a t e d
y a r n .
7. A
p r o c e s s
f o r t h e p r o d u c t i o n of
a p o l y e s t e r
f i b r e h a v i n g h i g h t h e r ma l d i m e n s i o n a l
s t a b i l i t y ,
w h i c h
c o mp r i s e s m e l t - s p i n n i n g a p o l y e s t e r c o mp r i s i n g e t h y l e n e
t e r e p h t h a l a t e as t h e ma i n
r e p e a t i n g u n i t , s o l i d i f y i n g
t h e
s p u n
f i l a m e n t s and t h e n d r a wi n g t he
y a r n
c h a r a c t e r i s e d
i n t h a t t h e p o l y e s t e r has an i n t r i n s i c
v i s c o s i t y ( me a s u r e d
at 30C i n a mi x e d s o l v e n t of p h e n o l / t e t r a c h l o r o e t h a n e =
6/ 4) of 0. 8 or mor e
and t h e
p r o c e s s c o mp r i s e s s p i n n i n g
t h r o u g h a s p i n n e r e t at a t h r o u g h p u t of n o t mor e t h a n
3. 5 g / m i n u t e
p e r
s p i n n e r e t , q u e n c h i n g
t h e
s p u n y a r n
w i t h o u t u s i n g
any q u e n c h i n g a i r , p u l l i n g
o u t t h e
s p u n y a r n
i n a s p i n n i n g s t r e s s of 1. 5 x
1 0
t o 7 . 5
x
107
d y n e / c m2 , b u n d l i n g
t h e
y a r n
a t 20 t o 100 cm b e l o w
t h e p o s i t i o n
of s o l i d i f i c a t i o n of t he
y a r n
and t h e n
s u b j -
e c t i n g t o d r a wi n g by a s p i n - d r a w p r o c e s s
v i a t h e f i r s t
g o d e t
r o l l a t a s p e e d
of 1 , 5 0 0 m/ mi n u t e
or h i g h e r
8. A
p r o c e s s
f o r ma k i n g a p o l y e s t e r
f i b r e
y a r n
h a v i n g h i g h t h e r ma l d i m e n s i o n a l
s t a b i l i t y ,
c h e m i c a l
t e n a c i t y c o m p r i s i n g m e l t - s p i n n i n g p o l y -
e t h y l e n e t e r e p h t h a l a t e , s o l i d i f y i n g t h e
s pun
f i l a m e n t s
and t h e n d r a wi n g t h e
y a r n ,
s o l i d i f i c a t i o n and
d r a wi n g a r e so c o n d u c t e d t h a t t h e
b i r e f r i n g e n c e v a r i a t i o n of t h e
y a r n ,
c a l c u l a t e d
a s
d e f i n e d i n c l a i m 1, i s 0 . 0 5 5 or l e s s .
9. A
p r o c e s s
a c c o r d i n g t o c l a i m 8 c h a r a c t e r i s e d
i n t h a t t h e s o l i d i f i c a t i o n i s c o n d u c t e d
by q u e n c h i n g w i t h
a i r at a b o v e 35C and t he d r a wi n g i s i n i t i a t e d i n t h e
p r e s e n c e
of
s u p e r
h e a t e d s t e a m or i n c o n t a c t wi t h
a h e a t e d
s u r f a c e or
t he s o l i d i f i c a t i o n i s c o n d u c t e d w i t h o u t
u s i n g
q u e n c h i n g
a i r and t he
y a r n
i s b u n d l e d 20 t o 100 cm b e l o w
t he p o s i t i o n of s o l i d i f i c a t i o n and t he b u n d l e d
y a r n
i s
t h e n d r a w n .
10. A
p r o c e s s a c c o r d i n g t o c l a i m 8
or c l a i m 9
p o l y e s t e r i s
s pun
t h r o u g h a
s p i n n e r e t
at a t h r o u g h p u t of not mor e t h a n 3. 5 g / m i n u t e
p e r
e a c h o r i f i c e of t he
s p i n n e r e t
and t he
s pun y a r n
i s
p u l l e d out wi t h
a s p i n n i n g s t r e s s of 1. 5
x
1 0
t o 7 . 5
x
107
d y n e / c m 2 .
11. A
p r o c e s s a c c o r d i n g t o
any
of c l a i ms 4
t o 10 c h a r a c t e r i s e d i n t h a t t he p o l y e s t e r c o n t a i n s
2.5% mo l a r or
l e s s d i e t h y l e n e g l y c o l
b a s e d
on t e r e p h t h a l i c
a c i d r e s i d u e s and c o n t a i n s not mor e
t h a n
30, p r e f e r a b l y
not mor e
t h a n 20 and mos t p r e f e r a b l y not mor e
t h a n 1 2 ,
e q u i v a l e n t s c a r b o x y l
g r o u p s pe r
106
g
and t h e
dr a wn
y a r n
has an a v e r a g e b i r e f r i n g e n c e of 0. 19 or mo r e
and
as
d e f i n e d i n
c l a i m 1, of 0 . 0 5 5 or l e s s , and t he dr awn
y a r n
a f t e r
b e i n g
h e a t t r e a t e d at c o n s t a n t l e n g t h at 240C f o r 1 m i n u t e
has a dr y
h e a t s h r i n k when f r e e l y h e a t t r e a t e d at 1 7 5 C
f o r 30 mi n u t e s of 3% or l e s s and
p r e f e r a b l y
a l s o h a s
a wor k l o s s when t he h y s t e r e s i s l o o p i s me a s u r e d a t
a s t r e s s b e t we e n 0. 6 g/ d and 0. 05 g/ d u n d e r c o n d i t i o n s
of l e n g t h
of t e s t s a mp l e of 10 i n c h , s t r a i n r a t e
of 0. 5 i n c h / m i n u t e and a t e m p e r a t u r e
of 150 C: 2. 0 x
1 0 - 5
i n c h . p o u n d / d e n i e r or
l o s s .
12. Yar n made
by a p r o c e s s
a c c o r d i n g t o
any
o f
c l a i ms 4 t o 1 1 .
13. Ya r n , or a p r o d u c t c o n t a i n i n g
y a r n ,
o b t a i n e d
f r om
y a r n
any
of c l a i ms 1 t o 3
or 1 2 .
14. Yar n a c c o r d i n g t o
any
of c l a i ms 1 t o 3, 12
or 13 a n d wh i c h has b e e n s u b j e c t e d , d u r i n g s p i n n i n g a n d / o r
d r a wi n g , t o s u r f a c e t r e a t m e n t wi t h an
e poxy c ompound o r
an i s o c y a n a t e c o mp o u n d .
15. An a r t i c l e , p r e f e r a b l y a t y r e , c o m p r i s i n g
r u b b e r r e i n f o r c e d
by
y a r n
y a r n
i s
y a r n
any
of c l a i ms 1 t o 3, 12, 13 or
1 4 .

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