® European Patent Office © Publication number: 0 2 5 9 9 6 0 K m S * Office europeen des brevets ^ 2

& c u n U r c A i V PATENT APPLICATION

Application number: 87306352.3 © Int. CI.3: C 08 J 3 /22 © Date of filing: 17.07.87 C 08 K 13/02

@ — •»« umi iiibu unuer nuie B8 EPC. A decision will be taken by the Examining Division.

% Priority: 01.09.86 GB 8621094

uaieoTpuDiicatron of application: 16.03.88 Bulletin 88/11

w) Designated Contracting States: AT BE CH DE ES FR GB GR IT LI LU NL SE

n) Applicant: IMPERIAL CHEMICAL INDUSTRIES PLC Imperial Chemical House Mlllbank London SW1P3JFIGB)

5) Inventor: Trotoir, Jean-Paul 236RuedesBruyeres B-5043 Waret-la-Chaussee(BE)

jj) Representative: James, David Gomer et al, Imperial Chemical Industries PLC Legal Department- Patents Po Box 6 Bessemer Road Welwyn Garden City Herts, AL7 1 HD(GB)

zy ruiyni«ouaravoconcenxraie. jj) A polymer concentrate contains 15-80% by weight of a quid, pasty or waxy additive, 5-50% by weight of a particu- ste solid and at least 5% by weight of a polymer. The particu- Jte solid is finely divided and typically has a particle size in he micrometre range. The concentrate is prepared by adding ie additive to the particulate solid whilst mixing using a olids device, adding the polymer whilst continuing to mix, referably at the same speed, subjecting the mixture to an levated temperature to melt the polymer, cooling and grin- ing the cooled mixture.

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1 S. 34011

~ » WMV^aillRAXB

The p re sen t i n v e n t i o n r e l a t e s to a polymer c o n c e n t r a t e c o n t a i n i n g a high l eve l of a d d i t i v e s and to a method for t h e

5 i n c o r p o r a t i o n of a d d i t i v e s in p o l y m e r s . The i n c o r p o r a t i o n of a d d i t i v e s in polymers is well-known "and

there is e x t e n s i v e use of a d d i t i v e s in p r e sen t polymer t e c h n o l o g y . A d d i t i v e s which are used inc lude a n t i f o g agen t s , a n t i s t a t i c a g e n t s , a n t i o x i d a n t s , p l a s t i c i s e r s , UV s t a b i l i s e r s , n o n - i o n i c s u r f a c t a n t s and

0 the l i k e .

Some a d d i t i v e s may be added during the p o l y m e r i s a t i o n p roces s but th i s may lead to s u b s t a n t i a l drawbacks for example in t h e e f f i c i e n c y of the p o l y m e r i s a t i o n p r o c e s s , by i n t e r a c t i o n with t h e p o l y m e r i s a t i o n c a t a l y s t , i n c o m p a t i b i l i t y with o ther a d d i t i v e s used i n

5 the p o l y m e r i s a t i o n process and r e s t r i c t i o n in subsequent t r e a t m e n t . A f l e x i b l e method of i n c o r p o r a t i n g the a d d i t i v e s is to b l e n d

them with a t h e r m o p l a s t i c polymer. For th is purpose there is o f t e n used a p r e - b l e n d of the a d d i t i v e and the polymer which c o n t a i n s a high l e v e l of the a d d i t i v e and which can, t h e r e f o r e , serve as a

) m a s t e r b a t c h or c o n c e n t r a t e . The use of a m a s t e r b a t c h or c o n c e n t r a t e is a g e n e r a l l y p r e f e r r e d t e c h n i q u e , p a r t i c u l a r l y with l i q u i d or p a s t e a d d i t i v e s the use of which gives r i s e to dosing problems r e q u i r i n g s p e c i a l me te r ing pumps which may need to be heated if the a d d i t i v e i s a v i s cous s u b s t a n c e .

; In gene ra l m a s t e r b a t c h e s have been ob ta ined with a maximum loading of 10 to 15% by weight of a d d i t i v e in the m a s t e r b a t c h , t h e maximum a c h i e v a b l e loading depending on the na tu re of the a d d i t i v e s i n c o r p o r a t e d and, e s p e c i a l l y , t h e i r s l i p p i n g p r o p e r t i e s and a l so , due to d i f f e r e n c e s in the a b s o r p t i o n , on the kind of polymer to be t r e a t e d . However, i t has been found d i f f i c u l t to ob ta in a c o n c e n t r a t e having a high c o n c e n t r a t i o n of a d d i t i v e s , tha t is g r e a t e r than about 15% by weight of a d d i t i v e s .

\J C iJ © © W W

34011

According to tne p r e s e n t i n v e n t i o n urei.= j-= r " ' " 1 - " "

polymer c o n c e n t r a t e which c o n t a i n s 15 to 80% by weight of at l e a s t

one a d d i t i v e , which is a l i q u i d , or a pa s ty , waxy and /o r l u b r i c a t i n g

s o l i d , 5 to 50% by weight of a p a r t i c u l a t e so l i d and at l e a s t 5% by

> weight of a po lymer .

The c o n c e n t r a t e t y p i c a l l y c o n t a i n s at l e a s t 20% by weight o f

the a d d i t i v e or mixture of a d d i t i v e s , p r e f e r a b l y at l e a s t 40%, and

e s p e c i a l l y at l e a s t 50%, by weight of the a d d i t i v e . The c o n c e n t r a t e

in g e n e r a l w i l l conta in not more than 70% by weight of the a d d i t i v e .

0 A p a r t i c u l a r l y p r e f e r r e d c o n c e n t r a t e is one c o n t a i n i n g 50 to 70% by

weight of the a d d i t i v e or mix tu re of a d d i t i v e s .

The c o n c e n t r a t e t y p i c a l l y c o n t a i n s at l e a s t 10% by weight o f

the polymer . In genera l the amount of polymer in the c o n c e n t r a t e

does' not exceed 70% by weight and p a r t i c u l a r l y does not exceed 50% by

5 we igh t . E s p e c i a l l y p r e f e r r e d c o n c e n t r a t e s are those in which t h e

amount of polymer is not more than 40% by weigh t , for example

c o n c e n t r a t e s c o n t a i n i n g at l e a s t 10% and not more than 40% by w e i g h t

of p o l y m e r .

The amount of the p a r t i c u l a t e so l id w i l l t y p i c a l l y be a t

10 l e a s t 10% by weight of the c o n c e n t r a t e . It is g e n e r a l l y p r e f e r r e d

tha t the c o n c e n t r a t e c o n t a i n s not more than 40% by weight of t h e

p a r t i c u l a t e s o l i d , e s p e c i a l l y not- more than 30% by weight of t h e

p a r t i c u l a t e so l i d . P a r t i c u l a r l y p r e f e r r e d c o n c e n t r a t e s con ta in a t

l e a s t 10%, and not more than 20%, by weight of the p a r t i c u l a t e s o l i d .

?5 a p a r t i c u l a r l y p r e f e r r e d c o n c e n t r a t e in accordance with t h e

p r e s e n t i n v e n t i o n con t a in s 50 to 70% by weight of the a d d i t i v e o r

a d d i t i v e mix tu re , 10 to 40% by weight of the polymer and 10 to 20% by

weight of the p a r t i c u l a t e s o l i d , the t o t a l of a d d i t i v e , polymer, and

p a r t i c u l a t e so l id being 100% by w e i g h t .

30 The a d d i t i v e s t ha t can be p r e s e n t in the c o n c e n t r a t e

a c c o r d i n g to the i n v e n t i o n are very d i v e r s i f i e d and inc lude l i q u i d s ,

pa s t e or waxy low-mel t ing s o l i d s or l u b r i c a t i n g m a t e r i a l s , t h e s e

a d d i t i v e s being of the type which can be used as a n t i f o g a g e n t s ,

c l a r i f y i n g agen t s , a n t i o x i d a n t s , U.V. s t a b i l i s e r s , i n f r a - r e d

3 s. 34011 0 2 5 9 9 6 0

aDso rae r s , b i o c i d e s , a n t i s t a t i c a g e n t s , p l a s t i c i s e r s , f lame r e t a r d a n t s or for any o ther purpose in which the use of s o l i d a d d i t i v e is d i f f i c u l t or i m p o s s i b l e . S p e c i f i c a d d i t i v e s which may be p r e sen t in the c o n c e n t r a t e inc lude p o l y a l k y l e n e g l y c o l s ,

5 e t h o x y l a t e d f a t t y a c id s , for example the n a t u r a l l y occur r ing f a t t y ac ids such as coconut f a t t y ac id , e t h o x y l a t e d amines, for example , the s y n t h e t i c h igher a lky l pr imary amines, e s t e r s such as s o r b i t a n monolaura te and g l y c e r o l e s t e r s , c h l o r i n a t e d p a r a f f i n , o r g a n i c p h o s p h a t e s , organic p h o s p h i t e s such as t r i n o n y l p h e n y l p h o s p h i t e , and

L0 U.V. s t a b i l i s e r s such as benzophenone, b e n z o t r i a z o l e or h i n d e r e d amine l i g h t s t a b i l i s e r s . P r e f e r r e d a d d i t i v e s i n c l u d e

p o l y e t h o x y l a t e d amines such as d i e t h o x y l a t e d s y n t h e t i c amines, a convenien t amine of th i s type being a mixture c o n t a i n i n g a lkyl g r o u p s having from 13 to 15 carbon atoms, such amines being used alone or i n

15 combina t ion with g l y c e r o l f a t t y acid e s t e r such as g l y c e r o l m o n o s t e a r a t e or monoolea te , p o l y o x y l a t e d a l c o h o l s , p o l y e t h y l e n e g lyco l and s u l p h a t e s of a l c o h o l s c o n t a i n i n g a mixture of a lkyl g r o u p s having from 13 to 15 carbon atoms. A mixture of a d d i t i v e s may a d v a n t a g e o u s l y be used, for example a mixture of p o l y e t h o x y l a t e d

20 amine with a g l y c e r o l f a t t y acid e s t e r .

Polymers that may be p r e s e n t in the c o n c e n t r a t e i n accordance with the p r e sen t i n v e n t i o n are t h e r m o p l a s t i c po lymers which i nc lude , but are not r e s t r i c t e d to, p o l y s t y r e n e , high impac t p o l y s t y r e n e , a s t y r e n e - a c r y l o n i t r i l e c o p o l y m e r ,

25 a c r y l o n i t r i l e - b u t a d i e n e - s t y r e n e copolymers , p o l y m e t h y l m e t h a c r y l a t e , l i n e a r low-, low- and h i g h - d e n s i t y p o l y e t h y l e n e , v iny l c h l o r i d e polymers and copolymers , and p ropy lene polymers and copo lymers .

The p a r t i c u l a t e so l id is t y p i c a l l y an i no rgan ic so l id wh ich remains so l id at t e m p e r a t u r e s in excess of those used to process t h e

30 polymer component of the m a s t e r b a t c h . The p a r t i c u l a t e so l id may be

a m a t e r i a l which is known as a f i l l e r for polymers and s u i t a b l e m a t e r i a l s inc lude calcium ca rbona t e ; s i l i c a t e s , for example n a t u r a l l y occu r r ing s i l i c a t e s such as t a l c ; and oxides such a s magnesium oxide, aluminium oxide and, e s p e c i a l l y , s i l i c a . The

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p a r t i c u l a t e s o l i d is used in a form which is such tha t the s o l i d h a s

a high absorbance c a p a c i t y for the a d d i t i v e , Thus, the p a r t i c u l a t e

s o l i d is p r e f e r a b l y a f i n e l y d iv ided m a t e r i a l and t y p i c a l l y at l e a s t

80% of the p a r t i c l e s of the s o l i d have a p a r t i c l e s ize of not more

5 than 50 m i c r o m e t r e s . P r e f e r r e d p a r t i c u l a t e s o l i d s are those a t

l e a s t 80% of the p a r t i c l e s of which have a p a r t i c l e s ize of not more

than 20 m i c r o m e t r e s , p a r t i c u l a r l y not more than 10 m i c r o m e t r e s .

E s p e c i a l l y p r e f e r r e d p a r t i c u l a t e so l id s have a weight a v e r a g e

p a r t i c l e s ize of not more than 10 mic romet re s . The p a r t i c u l a t e

L0 s o l i d , in a d d i t i o n to being a f i n e l y d iv ided m a t e r i a l is p o r o u s .

F u r t h e r m o r e , the p a r t i c u l a t e s o l i d t y p i c a l l y has a s p e c i f i c s u r f a c e

a rea of at l e a s t 10 m2/g. Use fu l r e s u l t s have been o b t a i n e d u s i n g

p a r t i c u l a t e s o l i d s having a s p e c i f i c su r f ace area of at l e a s t 50 m2/g

and e s p e c i a l l y at l e a s t 100 m2/g. It is e s p e c i a l l y p r e f e r r e d t h a t

15 the p a r t i c u l a t e s o l i d is s i l i c a .

A wide range of s i l i c a s which are commerc ia l ly a v a i l a b l e a r e

u s e f u l as the p a r t i c u l a t e s o l i d in the c o n c e n t r a t e of the 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 a hydrophobic grade of s i l i c a with a w e i g h t

average p a r t i c l e s ize in the micrometre range is used. P r e f e r a b l y

20 the c o n c e n t r a t e c o n t a i n s 10 to 20% by weight of s i l i c a . T y p i c a l

s i l i c a grades i n c l u d e commerc ia l ly a v a i l a b l e S i p e r n a t 50S ,

S i p e r n a t 22 and A e r o s i l 200 ( a l l a v a i l a b l e from Degussa) , C a b - O - S i l

TS 720 (Cabot Corp.) and Gasi l 644, a l l of these m a t e r i a l s b e i n g

c h a r a c t e r i s e d by good a b s o r p t i v e c a p a c i t y .

25 The c o n c e n t r a t e can be i n c o r p o r a t e d in to a polymer to give a

m a s t e r b a t c h compos i t i on or to give a de s i r ed f i n a l c o m p o s i t i o n . The

c o n c e n t r a t e can be i n c o r p o r a t e d in to a polymer us ing known

compounding machines for po lymer ic m a t e r i a l s such as, for example, a

Banbury mixer or, p a r t i c u l a r l y , an e x t r u d e r . The c o n c e n t r a t e and

30 the po lymer ic m a t e r i a l may be added to the compounding m a c h i n e

s e p a r a t e l y at r a t e s to give the de s i r ed l e v e l of a d d i t i v e in t h e

m a s t e r b a t c h or f i n a l compounded polymer which is to be p r o d u c e d .

The c o n c e n t r a t e of the p r e sen t i n v e n t i o n is a compounded

polymer c o n c e n t r a t e in the form of free f lowing g r a n u l e s having a

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nign concenc or l i q u i d pas te or waxy a d d i t i v e . The g r a n u l e s of t h e c o n c e n t r a t e are t y p i c a l l y n o n - b r i d g i n g and have a r e g u l a r flow r a t e .

The p r o d u c t i o n of the c o n c e n t r a t e is a f u r t h e r f e a t u r e o f the p r e sen t i n v e n t i o n .

5 Thus, a cco rd ing to a f u r t h e r aspect of the p r e s e n t i n v e n t i o n there is p rov ided a p roces s which c o m p r i s e s (A) mixing t o g e t h e r at l e a s t one i i q u i d , paste or waxy a d d i t i v e and

a p a r t i c u l a t e s o l i d us ing a so l id s mixing d e v i c e ; (B) adding to the mix tu re a powdered polymer and c o n t i n u i n g to mix

10 to ob ta in an e s s e n t i a l l y homogeneous m i x t u r e ; (C) s u b j e c t i n g the mix ture to i n t e n s i v e mixing for a time s u f f i c i e n t

to cause me l t ing of the polymer; and (D) cool ing and s u b - d i v i d i n g the r e s u l t i n g m i x t u r e .

The mixing in s teps (A) and (B) is very c o n v e n i e n t l y L5 e f f e c t e d us ing the same a p p a r a t u s . Any s o l i d s mixing device may be

used. The mixing may be e f f e c t e d at a slow speed, for example at 30 to 60 r .p .m. , for example using a Hobart mixer. A l t e r n a t i v e l y , mixing can be e f f e c t e d at a high speed, t y p i c a l l y in excess o f 500 r . p . m . , for example 1500 r . p . m . , using a high speed mixer such a s

10 a Henschel mixer or an I t a l high speed m i x e r . In step (A), the a d d i t i v e , or mixture of a d d i t i v e s , is added

to the p a r t i c u l a t e s o l i d at a ra te such that a f ree f lowing powder mixture is o b t a i n e d . The r a t e of a d d i t i o n of the a d d i t i v e o r a d d i t i v e mixture is dependent on the speed of mixing, the type, and

15 p r o p o r t i o n , of a d d i t i v e or a d d i t i v e mix tu re , the n a t u r e of t h e p a r t i c u l a t e s o l i d and the q u a n t i t y of m a t e r i a l s which are being mixed t o g e t h e r . In g e n e r a l , if mixing is e f f e c t e d at a speed of 30 t o 60 r . p . m . , e f f e c t i v e mixing of the a d d i t i v e , or a d d i t i v e mix tu re , and the p a r t i c u l a t e so l i d can be a t t a i n e d in a time of 30 seconds u s i n g

JO up to about lOOg of m a t e r i a l s . If mixing is e f f e c t e d at a speed i n excess of 500 r . p . m . , a mixing time of not more than two minutes i s g e n e r a l l y s u f f i c i e n t and, at h igher speeds, s h o r t e r t imes of not more than one minute , for example, as l i t t l e as 20 seconds may be u s e d . However, i t w i l l be a p p r e c i a t e d that the time of mixing is d e p e n d e n t ,

at l e a s t to some e x t e n t , on tne cou«.a H««' l t*4 w* —

mixed t o g e t h e r , l a r g e r q u a n t i t i e s r e q u i r i n g longer times to a c h i e v e

e f f e c t i v e m i x i n g .

In s tep (B) a powdered polymer is added to the p r e m i x e d

> a d d i t i v e , or a d d i t i v e m i x t u r e , and p a r t i c u l a t e s o l i d . The powdered

polymer is c o n v e n i e n t l y added under the same a g i t a t i o n c o n d i t i o n a s

used for step (A). T y p i c a l l y , u s ing the same a g i t a t i o n c o n d i t i o n s

in s tep (A) and step (B) , the time of a d d i t i o n of the polymer, a n d / o r

t o t a l a g i t a t i o n time to o b t a i n an e s s e n t i a l l y homogeneous m ix tu r e , i s

D not more than the time r e q u i r e d to a ch i eve e f f e c t i v e mixing i n

s tep (A) . In genera l the time of mixing in step (B) i s

s u b s t a n t i a l l y less than the time of mixing in step (A) , for example

75% of the time of step (A) or even 60%, or l e s s , of the time o f

s tep " (A) .

5 It w i l l be a p p r e c i a t e d t ha t s t eps (A) and (B) can b e

e f f e c t e d in a con t inuous manner by adding the v a r i o u s components , i n

s u c c e s s i o n , to an a p p r o p r i a t e s o l i d s mixing d e v i c e .

Steps (C) and (D) are a l so c o n v e n i e n t l y e f f e c t e d in a

c o n t i n u o u s manner, for example by the use of an e x t r u d e r feeding a

;0 g r a n u l a t i n g device or an i n t e n s i v e mixer such as a Banbury m i x e r

which produces a sheet which is passed to a c u t t i n g device to form

g r a n u l e s . The i n t e n s i v e mixing may be e f f e c t e d with h e a t i n g but i t

w i l l be a p p r e c i a t e d t ha t many i n t e n s i v e mixing p rocedu re s g e n e r a t e

s u b s t a n t i a l heat and i t may be n e c e s s a r y to apply only a small amount

15 of h e a t i n g .

The t e m p e r a t u r e a t t a i n e d dur ing step (C) should be

s u f f i c i e n t to e f f e c t me l t ing of the polymer. The a d d i t i v e , o r

mix ture of a d d i t i v e s , used should be s t a b l e at the t e m p e r a t u r e o f

s tep (C) , at l e a s t for the p e r i o d for which th is t e m p e r a t u r e i s

30 m a i n t a i n e d , and also the t e m p e r a t u r e of any subsequent s tage in wh ich

the mix ture is s u b j e c t e d to an e l e v a t e d t e m p e r a t u r e , for example when

forming the f i n a l polymer c o m p o s i t i o n . The t e m p e r a t u r e of step (C)

w i l l be dependent upon the p a r t i c u l a r polymer used and for many

polymers w i l l be at l e a s t about 150°C and may be 200°C or even

35 h i g h e r .

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^^k> vw is e n e c c e a ror a r e l a t i v e l y shor t time which i s dependent to some ex ten t on the t o t a l amount of mixture b e i n g p rocessed and the na tu re of the polymer being used and may be a s l i t t l e as 20 seconds up to s e v e r a l , for example ten, m i n u t e s .

5 In step (D) , the mix ture is allowed to cool to al low a t l e a s t a p a r t i a l s o l i d i f i c a t i o n of the polymer. C o n v e n i e n t l y , u s i n g an e x t r u d e r , the m a s t e r b a t c h mix ture is withdrawn from the e x t r u d e r die as one or more laces which are passed into a water bath and t h e cooled l aces are t h e r e a f t e r g r a n u l a t e d . Procedures for me l t i ng and

0 g r a n u l a t i n g polymer mix tu res are well known and any s u i t a b l e procedure may be used to e f f e c t s t ages (C) and (D) .

In step (A), the weight of the a d d i t i v e , or a d d i t i v e mix tu re , is p r e f e r a b l y at l e a s t equal to the weight of t h e p a r t i c u l a t e s o l i d . It is e s p e c i a l l y p r e f e r r e d that the weight o f

5 the a d d i t i v e , or a d d i t i v e m i x t u r e , is g r e a t e r than the weight of t h e p a r t i c u l a t e s o l i d , for example from 2:1 by weight up to 10:1 by weight , t y p i c a l l y about 3:1 by w e i g h t .

The polymer which is used in step (B) must be in the form o f a powder, tha t is a m a t e r i a l with average p a r t i c l e d imens ions l e s s

0 than one mm. Granu les , p e l l e t s or diced polymer, a l l of which a r e t y p i c a l l y ob t a ined by mel t ing a polymer and then s u b - d i v i d i n g t h e polymer a f t e r i t has at l e a s t p a r t i a l l y r e - s o l i d i f i e d , g e n e r a l l y a r e not a p p r o p r i a t e for the purpose of the i n v e n t i o n s ince such m a t e r i a l s have a p a r t i c l e s ize which is g e n e r a l l y too large to be u s e f u l in t h e

5 p rocess of the p r e s e n t i n v e n t i o n . Some polymers such as low d e n s i t y p o l y e t h y l e n e ob ta ined at high p r e s s u r e using a free r a d i c a l i n i t i a t o r are o b t a i n e d as g ranu les from which powder can be ob t a ined by g r ind ing the g r a n u l e s .

P r e f e r r e d powdered polymers are t h e r m o p l a s t i c polymers such 0 as p ropy lene polymers i n c l u d i n g random propylene c o p o l y m e r s ,

s e q u e n t i a l or s o - c a l l e d block p ropy lene copolymers, p r o p y l e n e homopolymers, p o l y e t h y l e n e i n c l u d i n g l i n e a r low d e n s i t y p o l y e t h y l e n e , p o l y s t y r e n e or p o l y v i n y l c h l o r i d e .

4011

The polymer ueea in *»

type as the polymer with which the c o n c e n t r a t e is to be b l e n d e d .

However, the polymers need not be the same provided t h a t , in t h e

b lend of the polymer and c o n c e n t r a t e , two d i s t i n c t polymer phases do

not r e s u l t .

F u r t h e r a s p e c t s of the p r e s e n t i n v e n t i o n are now d e s c r i b e d ,

by way of example only, in the fo l lowing n o n - l i m i t i n g e x a m p l e s .

Example 1

S i l i c a ( S i p e r n a t 50S, a v a i l a b l e from Degussa and having an

average p a r t i c l e s ize of about 8 mic romet res as de te rmined using a

C o u l t e r coun te r with a 100 mic romet re c a p i l l a r y ) was s t i r r e d a t

60 r . p . m . us ing a Hobart mixer . To the s t i r r e d s i l i c a was added a

m i x t u r e of a lky l d i e t h a n o l a m i n e s in which the a lkyl groups c o n t a i n

from" 13 to 15 carbon atoms. ( 'Atmer ' 163 a v a i l a b l e from I m p e r i a l

i Chemical I n d u s t r i e s PLC, 'Atmer ' is a R e g i s t e r e d Trade Mark). The

'Atmer ' 163 was added to the s i l i c a in a weight r a t i o

•Atmer' 1 6 3 : s i l i c a of 4 .7 :1 over a pe r iod of two minutes w h i l s t

c o n t i n u i n g to s t i r at 60 r . p . m .

A p ropy lene s e q u e n t i a l copolymer powder c o n t a i n i n g a b o u t

3 6.5% by weight of e t h y l e n e ( ' P r o p a t h e n e ' grade GY621M, a v a i l a b l e f rom

I m p e r i a l Chemical I n d u s t r i e s PLC, ' P r o p a t h e n e ' is a R e g i s t e r e d T r a d e

Mark) was then added to the mix tu re over a per iod of one m i n u t e

w h i l s t c o n t i n u i n g to s t i r at 60 r .p .m. The copolymer was added t o

the mix tu re to give a c o m p o s i t i o n of 70% by weight of the a l k y l

5 d i e t h a n o l a m i n e m ix tu r e , 15% by weight of s i l i c a and 15%. by weight o f

the c o p o l y m e r .

The mix ture was then melted us ing a Polymix 150 type two

r o l l m i l l ( a v a i l a b l e from Schwabenthan). with the f ron t r o l l at 210°C

and the r ea r r o l l at 160°C. The molten polymer was g r a n u l a t e d u s i n g

)0 a Pa l lmann type PS/2 g r a n u l a t o r .

Example 2

The p roduc t of Example 1 was i n c o r p o r a t e d into a f u r t h e r

sample of the p ropy lene s e q u e n t i a l copolymer powder ( ' P r o p a t h e n e '

grade GY621M) to give a polymer product c o n t a i n i n g 0.9% by weight o f

0 2 5 9 9 6 0 S. 34011

the a lky l d i e t h a n o l a a i n e mix ture ( 'Atmer ' 163). I n c o r p o r a t i o n was e f f e c t e d us ing a t w o - r o l l f r i c t i o n mi l l with the f ron t r o l l at 210°C

and the r ea r r o l l at 160°C for a time of two m i n u t e s .

The mix tu re ob ta ined was compression moulded to form s h e e t s

5 of t h i c k n e s s 2mm by p r e s s i n g at 160°C and 100 bar for 30 s e c o n d s ,

r a i s i n g the p r e s s u r e to 300 bar , p r e s s i n g at 160°C and 300 bar for 30

seconds, coo l i ng to 90°C over a per iod of 30 seconds w h i l s t

m a i n t a i n i n g an a p p l i e d p r e s s u r e of 300 bar and then e j e c t i n g t h e

moulded s h e e t .

10 The s u r f a c e r e s i s t i v i t y of the sheet was measured by t h e

procedure of ASTM Test Method D257-61 using a K e i t h l y R e s i s t i v i t y

Measuring System c o n s i s t i n g of a power supply, a r e s i s t i v i t y chamber and an e l e c t r o m e t e r .

Before e f f e c t i n g the measurement, the samples were s t o r e d

15 for at l e a s t 24 hours at 50Z r e l a t i v e humidi ty and 20°C and t h e

su r f ace r e s i s t i v i t y was a lso measured at 50% r e l a t i v e humidi ty and 20°C. A v o l t a g e of 500 v o l t s was appl ied ac ross the s u r f a c e of t h e

sample for one minute and the r e s u l t i n g cu r r en t was measured from

which the s u r f a c e r e s i s t i v i t y (in ohms) could be c a l c u l a t e d . Repea t 20 measurements were made, on the same sample, over a per iod of one

month .

For the purposes of comparison, s i m i l a r measurements were made on a sample o b t a i n e d by i n c o r p o r a t i n g the pure a l k y l

d i e t h a n o l a m i n e mix tu re in to the polymer, the p rocedure o t h e r w i s e

25 being as d e s c r i b e d h e r e i n .

The s u r f a c e r e s i s t i v i t y r e s u l t s are given in Table 1.

Table 1

30 Example or Log su r face r e s i s t i v i t y a f t e r (b)

Comp.Ex (a) 1 day 1 week 2 weeks 1 month

2 12.2 11.2 10.6 9 . 8

A 12.4 11.1 10.5 9 . 7

Notes to TaBie I

(a) 2 is a sheet obtained* in accordance with Example 2.

A is a sheet o b t a i n e d by mixing the a d d i t i v e (the a lky l -:

d i e t h a n o l a m i n e mix tu re ) d i r e c t l y into ; the p o l y m e r .

(b) The time is measured from the p r o d u c t i o n of the- s h e e t .

Example 3

A c o n c e n t r a t e was produced by the p rocedure of Example 1 b u t

u s i n g , as the a d d i t i v e , g l y c e r o l m o n o s t e a r a t e ( 'Atmer ' 129, a v a i l a b l e

from I m p e r i a l Chemical I n d u s t r i e s PLC) and the a lky l d i e t h a n o l a m i n e

m i x t u r e in a weight r a t i o of 2:1 to give an a d d i t i v e con ten t of 70% , ,

by weight .

Example 4

The p rocedure of Example 2 was r epea ted using the- p r o d u c t

of Example 3 to ob t a in a polymer p roduc t c o n t a i n i n g 0.9% by weight o f

i the a d d i t i v e m i x t u r e .

By way of compar i son , the su r f ace r e s i s t i v i t y was a l s o

measured using a polymer p roduc t to which the a d d i t i v e s had b e e n

d i r e c t l y added .

The su r face r e s i s t i v i t y r e s u l t s are given in Table 2.

0

Example or T.n* s u r f a c e r e s i s t i v i t y a rce r , ,

Comp.Ex (cl L ^ Z 1 week 2weeks l_month

5 4 12.5 U . 5 10.9 10-2

B 12.2 11.6 11.0 10 .2

Notes to lapie i.

(b) is as de f ined in Notes to Table 1.

jO (c) 4 is a sheet obta ined, in accordance with Example 4. • •

B is a sheet o b t a i n e d by adding the mixture of a d d i t i v e s

d i r e c t l y to the p o l y m e r .

11 0 2 5 9 9 6 0

.34011

Example 5

The p rocedure of Example 1 was r e p e a t e d to ob ta in a c o n c e n t r a t e c o n t a i n i n g 50% by weight of g l y c e r o l m o n o s t e a r a t e , 202 by weight of s i l i c a and 30* by weight of a propylene homopolymer

5 ( ' P r o p a t h e n e ' GW 522M, a v a i l a b l e from I m p e r i a l Chemical I n d u s t r i e s PLC).

Example 6

The p rocedure of Example 1 was r epea t ed using t h e

c o n c e n t r a t e of Example 5, and a q u a n t i t y of a propylene homopolymer 10 ( ' P r o p a t h e n e ' GYM 45, a v a i l a b l e from Impe r i a l Chemical I n d u s t r i e s

PLC) to ob ta in a polymer product c o n t a i n i n g IX by weight of g l y c e r o l m o n o s t e a r a t e .

By way of compar i son , the su r f ace r e s i s t i v i t y was a l s o measured using a polymer c o n t a i n i n g no g l y c e r o l monos tea ra t e and

15 using a polymer p roduc t to which the a d d i t i v e had been added

d i r e c t l y .

The su r f ace r e s i s t i v i t y r e s u l t s are given in Table 3 .

Table 3 20

Example or Log su r f ace r e s i s t i v i t y a f t e r (b)

Gomp.Ex (d) 1 day 1 week 2 weeks 1 month 6 12.1 11.8 11.6 11 .6

C 14.7 15.0 15.0 15 .0 *5 D 11.7 11.9 11.7 11 .8

Notes to Table 3

(b) is as def ined in Notes to Table 1.

(d) 6 is a sheet o b t a i n e d in accordance with Example 6 . JO C is a sheet ob t a ined using a polymer with no added g l y c e r o l

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

D is a sheet o b t a i n e d using a polymer to which the g l y c e r o l monos tea ra te was added d i r e c t l y .

,34011

Examples 7 to U

C o n c e n t r a t e s were prepared a c c o r d i n g to the g e n e r a l

p rocedure of Example 1 but va ry ing one or more of the components and

the p r o p o r t i o n s t h e r e o f .

The compos i t ion of each c o n c e n t r a t e is set out in Table 4 .

Table 4

Example Component l e ;

0 7 PP-1 20

ADEA 60

Si02-1 20

8 PP-1 20

5 SML 60

Si02-1 20

9 PP-1 20

TNPP 60

!0 Si02-1 20

10 pve- i 15

C 70

Si02-1 15

25

11 PVC-2 23

ECA 50

Si02-1 13

DOP 14

30

13 0 2 5 9 9 6 0

S. 34011

Notes to Table 4

(e) PP-1 if a p ropy lene homopolymer powder ( ' P r o p a t h e n e ' GW 522M, a v a i l a b l e from I m p e r i a l Chemical X n d u s t r i a f PLC) .

ADEA if a mix ture of a l ky l d i e t h a n o l a m i n e s in which the a l k y l

groups c o n t a i n from 13 to 15. carbon atoms ( 'Atmer ' 163, a v a i l a b l e from I m p e r i a l Chemical I n d u s t r i a l PLC) .

Si02-1 ia commerc ia l ly a v a i l a b l e hyd rophob ic s i l i c a (S ipe rna t SOS,

a v a i l a b l e from Degussa) . SML is s o r b i t a n mono lau ra t e ( 'Atmer ' 100, a v a i l a b l e f rom

Impe r i a l Chemical I n d u s t r i e s PLC) . TNPP is t r i s n o n y l p h e n y l p h o s p h l t e ( I r g a f o s TNPP, a v a i l a b l e f rom

Ciba-Geigy) . PVC-1 is p o l y v i n y l c h l o r i d e ( ' C o r v i c ' grade PB 1702, a v a i l a b l e f rom

I m p e r i a l Chemical I n d u s t r i e s PLC, ' C o r v i c ' is a R e g i s t e r e d Trade Mark) .

C is a c h l o r i n a t e d p a r a f f i n c o n t a i n i n g 52% by weight o f

c h l o r i n e and having a chain l eng th of 14 to 17 carbon a toms

(Ce rec lo r S 52, a v a i l a b l e from Imper i a l Chemical I n d u s t r i e s

PLC) . PVC-2 is p o l y v i n y l c h l o r i d e (Solv ic grade 258 RE, a v a i l a b l e f rom

Solvay) . ECA is p o l y e t h o x y l a t e d (9) coconut f a t t y acid ( 'Atmer ' 154,

a v a i l a b l e from I m p e r i a l Chemical I n d u s t r i e s PLC) . DOP is d i o c t y l p h t h a l a t e .

Examples 12 to 14

A f u r t h e r s e r i e s of c o n c e n t r a t e s was prepared . using t h e

p rocedure of Example 1 with the fo l lowing m o d i f i c a t i o n s . The s o l i d s

mixing was e f f e c t e d using an I t a l high speed mixer o p e r a t i n g at a

speed of 1500 r .p .m. Blending of the a d d i t i v e s and s i l i c a was

e f f e c t e d over a pe r iod of 20 seconds. The po lyp ropy lene powder was

added over a pe r iod of 10 seconds . The powder mixture was

i n t r o d u c e d into the hopper of a Comacplast counter r o t a t i n g t w i n

screw e x t r u d e r with screws of 75mm d iameter and a t empera tu re p r o f i l e

j S. 34011

from the hopper to tne oie ot iou ^, iru *»» -»

190eq and 180eC. The polymer lace was passed in to a water bath and

then g r a n u l a t e d us ing a p e l l e t i z e r .

The c o n c e n t r a t e s o b t a i n e d by t h i s p r o c e d u r e are set o u t

5 in Table 5 .

Table 5

Example Component (e) (f) LJZlL

0 12 PP-1 30

ADEA • 50

Si02-1 20

13 PP-1 38

.5 . GMS 33 ,

APEA 17

Si02-1 12

14 PP-1 35

20 GMS 50

Si02-1 15

Notes to Table 5

(e) is de f ined in Notes to Table 4 .

25 (£) GMS is g l y c e r o l m o n o s t e a r a t e ( 'Atmer1 129, a v a i l a b l e from

I m p e r i a l Chemical I n d u s t r i e s PLC) .

Example 15

The p rocedure of Example 1 was r e p e a t e d us ing f i n e l y d i v i d e d

30 t a l c (Steamic 00S, a v a i l a b l e from Luzenac) in p lace of s i l i c a .

Seve ra l exper imen t s were e f f e c t e d to de te rmine the h i g h e s t l eve l o f

a d d i t i v e which could be i n c o r p o r a t e d to produce a f r e e - f l o w i n g

g r a n u l a t e d c o n c e n t r a t e . A maximum of 30% by weight of the a l k y l

d i e t h a n o l a m i n e mix ture was ob ta ined in a c o n c e n t r a t e of c o m p o s i t i o n

f% @ 3 '@ i .<> *' ^ 19 S .340U 0 2 5 9 9 6 0

30X by weight of i l k y l d i a t h a n o U m i n a mix ture , 40* by weight of t e l e and 302 by weight of the c o p o l y m e r .

Example 16 * ,; The p rocedure of Example 15 was repea ted us ing f i n e l y

5 d iv ided ca lc ium ca rbona te (Wirindf i l ,-SEM, a v a i l a b l e , f rom I m p e r i a l Chemical I n d u s t r i e s PLC) in place of the t a l c . ' A maximum of 20% by weight of the a lky l d i e t h a n o l a m i n e mixture was ob t a ined in a c o n c e n t r a t e of compos i t ion 20% by weight of a lkyl d i e t h a n o l a m i n e mix tu re , 50% by weight of calc ium ca rbona te and 30% by weight of t h e

10 copolymer. "

Examples 17 to 34 ' @

The p rocedure of Example 1 was r epea ted va ry ing one or more of the components and/or the p r o p o r t i o n s t h e r e o f .

The compos i t ion of each c o n c e n t r a t e ob ta ined is set o u t 15 in Table 6 .

16 S, 340 11

Table 6

Example Component (e) (f) (h | S wt

5 17 PVC-1 25

ADEA 60

Si02-1 15

18 PVC-1 2 °

10 . ADEA 50

Si02-1 20

DOP 1°

19 PP-1 20

15 GMO 65

Si02-1 15

20 PP-1 20

HAL-1 60

20 Si02-1 20

21 PP-1 20

AO ^0

Si02-1 20

25

22 PE-1 35

SMS 50

Si02-1 15

30 23 PE-1 35

GMS 50

Si02-1 15

17 8 .34011

Table 6 ^e$nt ; inued)

Example Component (e) (f!| (h) X wt

5 24 PE-1 35

GMS 50

S10.-2 15

25 PE-1 30

10 GMS 40

ADEA 10

Si02-1 20

26 PE-1 30

15 , GMS 40

ADEA 10

Si02-2 20

27 SAN 30

20 GMS 25

ADEA 25

Si02-1 . 20

28 PS i 35

25 ADEA 50

Si02-1 15

29 PE-2 30

ADEA k . 50

30 Si02-2 20

18

0 2 5 9 9 6 0

3.34011

Table 6 ( c o n t i n u e d )

Example Component (e) (f) ( h ) Z wt

30 SAN

ADEA

S i 0 2 - l

30

50

20

10 31 PE-1

PCS

S i 0 2 - 2

35

50

15

15

32 PS

AS

S i G 2 - l

35

50

15

20

33 PP-2

HALt2

S i 0 2 - 1

30

50

20

25

34 PP-3

GA

PEW

S i 0 2 - 1

30

50

5

15

Notes to Table 6

(e) is as de f ined in Notes to Table 4 .

30 (f) is as de f ined in Notes to Table 5 .

(h) GM0 is g l y c e r o i m o n o - o l e a t e ( 'A tmer ' 1007, a v a i l a b l e f rom

I m p e r i a l Chemical I n d u s t r i e s PLC).

HAL-1 is a h inde red amine l i g h t s t a b i l i s e r (Mark LA-62, a v a i l a b l e

from Adeka Argus) .

19 0 2 5 9 9 6 0

S. 34011

au is an a n t i o x i d a n t (bis 1 2-me t h y l - 4 - ( 3 - n - a l k y l t h l o p r o p l o n y l - • oxy) -5- t - b u t y l p h e n y l ] s u l p h i d e in which the

4 a lky l g roup c o n t a i n s 12 to 14 •carbon atoms and a v a i l a b l e as Mark AO-23 from Adeka Argus) .

5 SMS is s o r b i t a n m o n o s t e a r a t e ( 'Atmer ' 103, a v a i l a b l e f rom I m p e r i a l Chemical I n d u s t r i e s PLC) .

PE-1 is a low d e n s i t y p o l y e t h y l e n e powder (Escorene MP 6 5 3 - 2 0 , a v a i l a b l e from Essochem) .

Si02~2 is commerc ia l ly a v a i l a b l e hydrophobic s i l i c a (FK 310, 10 a v a i l a b l e from Degussa and having an average p a r t i c l e s i z e

of about 4 mic romet res as de te rmined using a C o u l t e r coun te r with a 50 micrometre c a p i l l a r y ) .

SAN is a s t y r e n e - a c r y l o n i t r i l e copolymer (Lus t r an QE 357, a v a i l a b l e from Monsanto) .

15 PS is p o l y s t y r e n e (Gedex 1819 JA-100, a v a i l a b l e f rom CDF-Chimie) .

PE-2 is a l i n e a r low d e n s i t y p o l y e t h y l e n e of d e n s i t y 0 .935g/cm3 (Escorene LL 6301-RQ, a v a i l a b l e from Essochem) .

PGS is p o l y g l y c e r o l s t e a r a t e which is a mix ture of mono- and 20 d i - s t e a r a t e and c o n t a i n s an average of four g l y c e r o l u n i t s

( 'Atmer ' 184, a v a i l a b l e from Impe r i a l Chemical I n d u s t r i e s PLC) .

AS is an a lky l su lphona te in which the a lky l group is a mix ture c o n t a i n i n g from 12 to 16 carbon atoms ( 'Atmer ' 190,

25 a v a i l a b l e from I m p e r i a l Chemical I n d u s t r i e s PLC). HAL-2 is a h inde red amine l i g h t s t a b i l i s e r ( d e s c r i b e d a s

poly [ (6- [ ( 1 , 1 , 3 , 3 - t e t r a m e t h y l b u t y l ) imino ] -1 , 3 , 5 - t r i a z i n e - 2 , 4 - d i y l (2- [ 2 , 2 , 6 , 6 - t e t r a m e t h y l p i p e r i d y l ] imino) -

h e x a m e t h y l - 4 - [ 2 , 2 , 6 , 6 - t e t r a m e t h y l p i p e r i d y l ] i m i n o ) ] and 30 a v a i l a b l e as Chimassorb 944 LD, from Ciba-Geigy) .

PP-2 is a p ropy lene homopolymer ( ' P r o p a t h e n e ' GX 543M, a v a i l a b l e from I m p e r i a l Chemical I n d u s t r i e s PLC) .

PP-3 is a random propylene copolymer c o n t a i n i n g about 3% by weight of e thy lene ( ' P r o p a t h e n e PXC 22265, a v a i l a b l e f rom

35 I m p e r i a l Chemical I n d u s t r i e s PLC) .

, 3 4 0 U

K is g l u t a r i c a c w .

EW is p o l y e t h y l e n e wax having a B r o o k f i e l d v i s c o s i t y at 150°C

of 8500 cps (AC 316A, a v a i l a b l e from A l l i e d Chemicals) .

a, 3 4 o u 0 2 6 9 9 6 0

1. A polymer c o n c e n t r a t e which c o n t a i n s 15 to 80% by weight o f at l e a s t one a d d i t i v e which is a l i q u i d , or a pas ty , waxy a n d / o r

5 l u b r i c a t i n g s o l i d , 5 to 15% by weight of a p a r t i c u l a t e so l id and a t l e a s t 5% by weight of a p o l y m e r .

2. A c o n c e n t r a t e as claimed in claim 1 which c o n t a i n s 50 to 70% by weight of the a d d i t i v e or a d d i t i v e m i x t u r e .

10 @ '

3' A c o n c e n t r a t e as claimed in e i t h e r of claim 1 or claim 2 which con ta in s at l e a s t 10%, and not more than 40%, by weight of t h e p o l y m e r .

L5 4. A c o n c e n t r a t e as claimed in any one of claims 1 to 3 which c o n t a i n s at l e a s t 10% y and not more than 20%,' by weight of t h e p a r t i c u l a t e s o l i d .

5. A c o n c e n t r a t e as claimed in any one of claims 1 to 4 w h e r e i n 10 the a d d i t i v e is a p o l y a l k y l e n e g l y c o l , an e t h o x y l a t e d f a t t y ac id , an

e t h o x y l a t e d amine, an e s t e r , a c h l o r i n a t e d p a r a f f i n , an o r g a n i c p h o s p h i t e , an organic phospha te , a U.V. s t a b i l i s e r or an i n f r a - r e d a b s o r b e r .

15 6 • A c o n c e n t r a t e as claimed in any one of claims 1 to 5 w h e r e i n the polymer is p o l y s t y r e n e , high impact p o l y s t y r e n e , a s t y r e n e - a c r y l o n i t r i l e copolymer, an a c r y l o n i t r i l e - b u t a d i e n e - s t y r e n e copolymer, an e thy lene polymer or copolymer, a v iny l c h l o r i d e po lymer or copolymer or a propylene polymer or c o p o l y m e r .

10

a c o n c e n t r a t e as claimed m any one or claims 1 to 6 w h e r e i n he p a r t i c u l a t e so l id is calcium c a r b o n a t e , a s i l i c a t e or an o x i d e .

,34011

A c o n c e n t r a t e as c laimea in ciaim / wnecexu mis p a i t i w « « . »

o l i d is f i n e l y d iv ided and at l e a s t 80% by weight of the p a r t i c l e s

ave a p a r t i c l e s ize of not more than 10 m i c r o m e t r e s .

i. A c o n c e n t r a t e as claimed in e i t h e r claim 7 or c laim 8

r t iere in the p a r t i c u l a t e so l id is s i l i c a .

,0. A polymer compos i t ion which is a polymer m a s t e r b a t c h or a

i ina l compounded polymer which comprises a polymer in to which h a s

teen i n c o r p o r a t e d a c o n c e n t r a t e as claimed in any one of claims 1

:o 9 .

LI. A p roces s which c o m p r i s e s

[A) m i x i n g t o g e t h e r at l e a s t one l i q u i d , pas t e or waxy a d d i t i v e and

a p a r t i c u l a t e s o l i d using a s o l i d s mixing d e v i c e ;

CB) auiding to the mix ture a powdered polymer and c o n t i n u i n g to mix

fcr> ob t a in an e s s e n t i a l l y homogeneous m i x t u r e ;

CC) s u b j e c t i n g the mix ture to i n t e n s i v e mixing for a time s u f f i c i e n t

f-o cause, me l t i ng of the polymer; and

(D) c o o l i n g and s u b - d i v i d i n g the - r e s u l t i n g m i x t u r e .

L2. A p rocess as claimed in claim 11 where in s t eps (A) and (B)

are e f f e c t e d us ing the same a p p a r a t u s .

13. A p rocess as claimed in e i t h e r claim 11 or claim 12 w h e r e i n

s teps (A) and (B) are e f f e c t e d by mixing at at l e a s t 30 r . p . m .

14. A p roces s as claimed in claim 13 where in mixing is e f f e c t e d

at a r r a t e of at l e a s t 500 r . p . m .

15. A p roces s as claimed in any one of c la ims 11 to 14 w h e r e i n

s tep (CC) is e f f e c t e d in an e x t r u d e r or i n t e n s i v e m i x e r .

23

0 2 5 9 9 6 0

S. 34011

16. A p rocess as claimed in claim 15 wherein the i n t e n s i v e

mixing is e f f e c t e d with h e a t i n g .

5 17. A p rocess as claimed in any one of claims 11 to 18 w h e r e i n

in step (C) the mix tu re is ob ta ined as a polymer l ace , which i s

cooled in a water bath and g r a n u l a t e d .

10

DGJ/BH

1 3 . 7 . 8 7 .

-•partment: Patents „iit Agent: AH Laird

Please address your reply to The Patent Agent

Imperial Chemical Industries, PLC ' @' ,„

POBoxNoS U d i Bessemer Road Welwyn Garden City Hertfordshire AL7 1HD England

Telephone Welwyn Garden (07073) 37 Welwyn Garden (07073) 23400

Telex 264251 Fax Welwyn Garden (07073) 35556

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European P a t e n t O f f i c e Rece iv ing S e c t i o n PO Box 5 8 1 8 P a t e n t l a a n 2 2 2 8 1 - H V - R i j i s w i j k ZH N e t h e r l a n d s

Your ref Our ref s . ^ o h / e p DGJ/BH

FROM: ICI SPECIALITY CHEMICALS

T e l e p h o n e :

T e l e x :

061-71*0-11*60

66781*1/2/3

Tel ext 1818 Date 2 5 . 9 . 8 7 .

Dear S i r s ,

EUROPEAN PATENT APPLICATION No. 87306352. 3 IMPERIAL CHEMICAL INDUSTRIES PLC ICI Case S ^ O H / E P "

The App l i can t has become aware of an e r r o r in claim 1 of t h e above i d e n t i f i e d a p p l i c a t i o n .

In the t h i r d l i n e of claim 1, the amount of p a r t i c u l a t e s o l i d is given as 5 to 15% by we igh t . The upper l i m i t of 15% by weight i s i n c o n s i s t e n t with the c o r r e s p o n d i n g s t a t e m e n t on page 2 of the a p p l i c a t i o n at l i n e ^, the d i s c u s s i o n on page 2 at l i n e s 19 to 2^, and the range s e t out in c la im k. It w i l l be observed t h a t some of the working e x a m p l e s use more than 15% by weight of p a r t i c u l a t e s o l i d , see Examples 5i 7 to 9 , 12, 15, 16, 20, 21, 25 to 27, 29, 30 and 33 -

The App l i can t wishes to amend claim 1 so t h a t the amount o f p a r t i c u l a t e so l id is given as 5 to 50% by we igh t . An amended page 21 showing amended claim 1 is enclosed h e r e w i t h in t r i p l i c a t e d ~

The App l i can t wishes t h i s amendment to be e f f ec t ed when t h e y have r e c e i v e d the European Search Repor t . I t is r e q u e s t e d t h a t t h i s l e t t e r , t o g e t h e r with amended page 21, is a t t a c h e d to the p r i n t e d s p e c i f i c a t i o n of the European pa t en t a p p l i c a t i o n when i t is p u b l i s h e d .

Enc .