Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
1 0 ~
~OECHST AXTIENGESELLSCE[AFT ~OE 92/F374 Dr.D~/St
Description
Cycloolefin polymer molding composition of improved
~tability to chemical degradation
5 The invention relates to a cycloole~in polymer molding
compo~ition of improved ~tability to chemical degradation
which compri~e~ certain organopho~ph~ru~ compounds a~
3tabilizers.
.
Cycloolefin homo- and copolymer~ are a class of polymer
with outstanding properties. They are di~ti~gui~hed,
inter alia, by a sometime~ high heat distortion point,
re~istance to weathering and tran~parency. They can be
proces~ed in the melt, for example by melt pre~sing,
kneading, extru ion or injection molding, ~nd can be
used, ~or 2xample, in the ~orm of ~heet , fibers, film~
and tubes. In particular, optical products, ~uch as
optical disks, op$ical len~e~ and optical fibers, can be
produced ~rom them.
For this, the polymer~ must have a good pro~e~ing
stability, and i~ po~sible ~hould not ~hange their
intrinsic color during proce~ing. It ih fuxthormore
Lmportant that they do not comprise relatively large
amounts of additive3, since otherwi~e th~ transparency to
light euffers ~he additive~ employad sh~uld thu~ have a
high activity in the polymer molding compo3ition, cause
little yellowing and be mi~ible with the polymer.
Efforte are therefore being made to 3tabilize cycloolefin
polymer~ adequately for proces~ing and u~e by very Qmall
amounts of additive~.
It i8 known that ~ynthetic polymer~ have to be protected
against undesirable oxidative, thermal and photochem1cal
damage during prep~ration, proce~sing and use by mean~ of
~tabilizers or ~tabilizer ~y~tem~. Such ~tabilizer~
, .
211~
: - 2 -
comprise, for example, a phenolic antioxidant, which i~
intended to en8ure, in particular, the long-term ~tabil-
ity of the fini~hed component during u~e, and one or more
costabilizers, whi~h regulate the processing stability
and in some cases al~o Eynergistically inten~ify the
action of the phenolic component.
Damage to the polymer during preparation, pro~e~sing and
use manifest~ itself in particular in the vi~c08ity and
appearance. The change in vi~cosity oecurs in parti~ular
during proces~ing of the polymer, while ~he appearance ~
the intri~sic color - can change chiefly during
processing and u~e.
, . . .~,....
Cycloolefin copolymer molding compositions compri~ing
0.01 to 5% by weight of organic pho~phite and/or phospho~
nite ætabilizer sy~tems nd optionally 0.01-1% by weight
of a higher fatty acid metal ~alt which can be u~ed for
optical materials are known (cf. JP 22 76 842,
WO 90 08 173). Among the organic pho phorus-containing
BtabiliZer8 t tri~(2,4-di-t-butylphenyl) pho~phite,
tris(nonylphenyl) phosphite and tetrakis(2,4-di-t-butyl-
phenyl)-4,4'-biphenylene diphosphonite are mentioned.
Such trivalent pho~phorus compounds are in ~ome ca~es not
stable to hydrolysis and may lose their ~tabilizing
property in the cour3e o~ tLme. :
:'
The objeot of the present invention wao thsre~ore to
di~cover ~uitable stabilizer~ ~r cycloolefin polymer
molding compo~itions which ~n6ure stability during
proce~sing and ~tabili~y during u~e without changing the
intrinsic color.
. :'
The object wa~ achieved by uziny particular phosphoru~
containing ~tabilizer~ individually or in combination : ~:
with other additivez.
. ."
~he pre~ent invention therefore relates to the
. ',~
~.~ , ,: :, . :, ::~ '
.f,~,t.s,~.,'~'~' ,., : , , ,
- 211~ 0
- 3
cycloolefin polymer molding compositîon described in the
claims, it~ preparation and it~ u~e.
.,
The synthe~i~ and properties o~ cycloolefin polymer~ have
been the ~ubjeat of many publication~ in r~cent time~. It
5 i8 known that these olefins can be polymerized by means
of variou~ catalysts. The polymerization haro proceed~
via ring opening or with opening of the double bond,
depending on the cataly~t. ~he cycloolefin polymeri2-
ations which proceed with opening of the double bond ean
be catalyzed either by more reeent oataly~t By0kems (ef.
BP 407 870, EP 485 893, EP 203 799) or by a conv~ntional
Ziegler cataly~t ~y~tem (cf. DD 222 317, DD 239 409~
The cycloolefin polymer molding compo~ition aceording to
the invention ~ompri~e~ 30 to 99.99, preferably 95 to
99.975% by weight of a polymer which compri~e ~tructural
unit6 derived from at least one monomer of the ~ormulae
I to VII
4 _ 2 ~ a Q ~ ~
C/ ¦ \~ H~R ' ~; ` `: '
¦¦ R3-C R~
H C\l /C H R 2
H C/ j H ~ C H ~
¦¦ R3-C R~ ¦ CH2 ( I I )
HC\I /CH
C H C H 2
... ......... ~
,; .- .. .......
HC/; \CH ¦ \CH ;~
HC\I /IH ¦ /CH 2
H C/; jC H/; \C H/; \ R
¦I R 3-C--R4 ¦ R5-C R6 ¦ R 7 C R8 1 ( I V ) ~1
HC\I /C ~l / ~IH/ R ;
~ , I , 1: '~,
H C/; \C H \C H
¦¦ R3C--R ¦ I (V)
,, c\¦ ~C H~ / ~R 2
R 6 ~ ~:
' ~
^ 211~1~0
5 ~
; ..:
R 5 :
HC/j \CH/ \ /j \ ,R~ ;
¦¦ R3 C--R4 ¦ ¦ R7-C--R~ ¦ ( V I j, ` :
\ I H~ \ / ~! /C H~ R 2 `
R 6
CH -~ C H
(VII) ~i
( C H 2 ) n ~ :
' ~.'`:,
In the~e formulae, Rl, R2, R3, R~, R5, R6, R7 ~nd R8 are `~
identical or different and are a hydrogen atom or a Cl-C~
alkyl radical, it being po~ ible ~or the ~am8 radicals in
the various formulae to have a different meaning, and n ::
is an integ~r from 2 to 10.
In addition to the ~tructural units derived from at l~ast
one monomer of the formulae I to VII, the cycloole~in
polymers can compris~ other stru~tural unit~ which are
derived from at least one ~cycli~ l-olefin oP the formula ::
VIII
R~ ~lo
~C--C ~ (
~ 1 a
in whioh R9, R', Rl1 and R12 are identical or differe~t and : `
are a hydroge~ atom or a C1_CD_a1kY1 radiCa10 ~:
:
Preferred c~mon~m2rs are ethylene or propylene. Copoly~
15 mers of polycyclic olefins of the formula I ox III and
the acyclic olefin~ o~ the formula VIII are employed in
particular. Particularly preferred cycloolefin3 are
norbornene and tctracyclododeaene, which can be ~ubsti-
tuted by Cl-C~-alkyl, ethylane/norbor~e~e copolymers being
of particular importance. Of the ~onocyclic ole~in~ of
~ ,; 211~1~0
the formula VII, cyclopentene, which can be 0ubstituted,
i8 preferred. Polycyclic olefins, monocyclic olefin~ and
open-chain olefine are al80 to be understood as mixtures
of two or more olefin~ of the particular type. This mean
that cycloolefin homopolymers and copolymera, ~uch as
I bi-, ter- and multipolymers, can be employed.
.,~
Those cycloolefin polymers which have been prepared by
means of metallocene catalysts are pre~erably u~ed for
the cycloolefin polymer molding compoeition ncoording to
the invention. Cycloolefin homo- and copolymere which
comprise structural units derived from monomer~ of the
formulae I to VI or VII are preferably prepared with the
aid of a homogeneou cataly~t. This comprise3 a metallo-
cene, the central atom of which i~ a ~etal from the group
comprising titanium, zir~onium, hafnium, vanadium,
niobium and tantalum, which form3 a sandwich ~tructure
with two mono- or polynuclear ligands bridged with one
another, and an aluminoxane.
The ~tructure and also the polymerization of these
cycloolefin~ are described in detail elsewhere (cf.
EP 407 870, EP 485 893, EP 501 370, ~P 503 422,
DE 42 05 416). These are cycloolefin polymer which in
~ome oa~eB differ in their chemical uniformity and their
polydi~persity.
The molding compo~ition compri~es as a ~tabilizer at
least one organopho~phorus oompound of the fo~mula IX
R13~tP(ORI4)2]n (IX)
in which
n is 1 or 2,
30 Rl4 i8 a linear or branched C~-C20-alkyl radical or a
phenyl radical, which can be ~ubstituted by one or more
linear or bxan~hed C,-C6-alkyl radical~ or by C5-C~cyclo-
alkyl, C6-C~0-aryl or C7-C10-aralkyl radical~
R13~ if n ~ a phenyl or benzyl radical, whioh can
carry 1 to 3 ~ub~tituents, an ~-methylbenzyl, a,a-dime-
thylbenzyl or naphthyl radical or a naphthyl radical
~,", "~
`~ _ 7 _ 2
which carries 1 to S substituents, the ~ubsti~uent~ being
identical or different and being ~ linear or branched -:
C,-C8-alkyl radical, a C,-C~-alkoxy radical, a C~-C,2-
alkylthio radical, a Cl-C8-dialkylamino radical, a C6-C,O
aryl radical, a C6-C,0-aryloxy radical or halogen having
an atomic number of 9 to 35, and
R13, if n ~ 2, i8 a phenylene radical, a biphenylene
radical, a naphthylene radical or a diphenylene oxide
radical, which are unsubstituted or carry 1 to 4 linear
10 or branched C,-C~-alkyl radicals, .
one dibenzo-[c,e]~1,2]-oxaphosphorine of the formula X
~ 3~ - .~
(X)~ :
m
in which R13 ha~ the abovementioned meaning and m is 1
or 2,
or one diarylphosphinous acid aryl ester of the formula
XI
r~ i o--P ~ R l 5
1 1 5
in which the radicals R16 independently of one another, a~
monovalent radicals, are ~ phenyl or naphthyl radical, ~-:
which can carry in each ca3e 1 to 5 sub~tituent~, the
substituent~ being identical or dif~erent and being a
1 20 non-aromatic hydrocarbon radical, an alkoxy radical,
alkylthio radical or dialkylamino radical having in eaoh ; : ~.
case 1 to 8 carbon atomq, aryl or a~yloxy having in each
case 6 to 10 carbon atom~ or halogen having an atomic ~ 1:
: : ~
;' " ' ;~
~ : -~ ". ,
- 8 - 2
number of 9 to 35, and
R1s as a divalent radical iB a phenylene, diphenylene
oxide or biphenylene radi~al, which is un~ubstituted or
is substituted by up to 4 non-aromatic hydrocarbon
radicals having 1 to 8 ~arbon atoms, or a naphthyl~ene
radical, whi::h i~ unsubstituted or carrie~ 1 to - 4 non~
aromatic hydrocarbon radicals having 1 to 8 carbon atom~
as sub~tituents, p i~ 1 or ~ and R1C has the above~
mentioned meaning. :~
Compounds of the formula IX which ar~ preferably employed
are 4-biphenylphosphonous acid bi~-(2~4-di-t-butylpheny~
ester, l~naphthyl-phGsphonous acid bis-(2,4-di-t-butyl-
phenyl) e~ter, benzene-1,4-diphosphonous acid tetra-(2,4-
di-t-butylphenyl) ester, 1-naphthyl-phosphonou~ acid bis~
(2,4-di-t-butylphenyl) e~ter, tetraki,3-(2,4-di-t-butyl-
phenyl) 4,4'-biphenylenediphosphonite, 2,4,6-trLmethyl
phenylphosphonous acid bis-(2,4-di-t-butylphenyl) e~ter
and tetrakis-(2,4-di-t-butylphenyl)-4,4'-diphenyl~ene
oxide diphospho~ite, which has been treated in ~ch case
20 with 0.01 to 5% by weight o~ an oxide, a carbonate, a
bicarbonate or a carboxylate of ~ mstal o~ group~ la, 2a,
2b and 7b of the Periodic Table of the Elements.
Examples of suitable compounds of the formula X are
6-(2',4',6'-trimethylphenyl)-6~-dibenzo- [ c, e J t 1. 2 ]
oxapho~phorine, 6-(4'-methoxy-phenyl)-6EI~
dibenzo L c, e ] [ 1. 2 ] -oxapho~phori~e, 6- ( 2 ' -tolyl ) -6~ m
dibenzo- r c, e ] [ 1 . 2 J -oxapho~phorine, 6- ( 3 ~ -tolyl ) - 6H
dibenzo-[c,e~[1.2]-oxaphosphorine, 6-(4'-t-butyl-phe~yl)- . -~
6~-dibenzo[c,e][1.2~-oxaphosphorine and 6-~4'-methyl-1'~
30 naphthyl)-6~-dibenzo-[c,e][1.2~-oxaphosphorine.
.. . ~.
Examples of suitable compound~ of the formula XI ~re
2,4,6-trimethylphenyl-phenylpho phinous acid 2,4-di-t-
butylphenyl eBter ~ 2,4,6-trimethylphenyl-1-naphthyl-
phosphinou~ acid 2,4-di-t-butylph~nyl ester, bis-~4-
biphenyl)pho~phinous acid 2,4-di-t-butylphenyl e~t~r,
bis-(l-naphthyl)phosphinous acid 2,4-di-t-butylphenyl
.
~": .,.:. :, ~: . . ,~, . , : ., . ~ :.
:`-` 211~
~ g
ester, 4,4'-biphenylene-bis-(1-naphthyl~pho~phinou~ cid
2,4 di t-butylphenyl e~ter), 2,4-trimethylphenyl-4-
methoxyphenylpho~phinou~ acid 2,4,6-tri- -butylphenyl
ester, 2,4-bi~-(4-chlorophenyl)phosphinous acid 2-t-
butylphenyl e~ter, bi~-(2-methoxyphe~yl)-pho~phinous acid
2,4-di-t-butylphenyl e~ter, 1,4-phenylene-~i~-tl-naph-
thylphosphinous acid 2,4,6-tri-t-butylphenyl e~ter), 1,4-
naphthylene-bis~ naphthylpho~phinous acid 2,4-di-t-
butylphenyl e3ter), bis-~4-(N,N-dimethylamino)phenyl~-
pho~phinous acid 2,4-di-t-butylphenyl ester, l~naphthyl-
2-methoxyphenylphosphinous acid 2,4-di-t-butylphenyl
ester, l-naphthyl-4-t-butylphe~ylphoEphinous acid2,6-di-
t-butylphenyl ester and 4,4'-biphenylene-bi~-(2,4,6-tri-
methylphenylpho~phinous acid 2,4-di-t-butylphenyl e~ter). ~;
15 Of the compounds of the formulae IX, X and XI~ the : ;
oxaphosphorines and the pho~phi~ous acid e~ter~ and
phosphonous acid esters are particularly preferred,
especially the phosphinous acid ester3 and phosphonous
acid esters. . :
The stabilization 3ystem furthermore oan compri8e one or
more phenolic antioxidants, one or more light ~tabilizers
or alkali metal and alkaline earth metal ~alts of higher ~ :
fatty acids or phenolate~
Since the individual ~tabilizer~ in the combination i~
the polymer molding compo~ition ~an react in an unknown
manner during proce~ing and u~e, they mu~t be te~ted
individually and i~ the ~tabilizer mixture.
The phenolic antioxidant i~, ~or example~ an e~ter of
' 3,3-bi~-(3'-k-butyl-4'-hydroxyphenyl) butanoic acid of
. 30 the formula XII
-:,
' ~':
. . ~, ~ -,,, "
. ~ ,"" ,. ~
1 0 ~
O H ~ ; ` .
f ~,, t - C 4 H ~,
~ / ' `
r ,O
H3~ H2-c -O - ~~~ ~XII)
~ ' ~
\ t-C4H9
OH r
in which R17 is a C1-CI2-a1kyl radical or a C~C12-alkylene
radical and r i~ l or 2. Preferably, R17 iB a C2-C4alkylene
radical, in particular a C2-alkylene radical.
~owever, the phenolic antioxidant can also be an e~ter of
~-(3,5-di-t~butyl-4-hydroxy-phenyl) propionic acid of the
formula XIII
t C~H9
~ ~ `'',''~,'.;,','''.'.. ',';,
HO--~ ~CH 2--ctl a C~H 6 x I I I ~
:j ~
t~
in which the alcohol oomponent i~ a mono- or polyhydric
~lcohol, such a~, for example meth~nol, octatecanol,
l,6~hexanediol, neopentylglycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pent~erythritol,
tris-hydroxyethyl i~ocyanurate or di-hydroxyethyl-oxalic
acid di ~ de.
~he cycloolefin polymer molding compo~ition to be
stabilized can additionally al80 compri~e the following
-~` 211~0
antioxidants, ~uch as, for example:
:
1. Alkylated monophenols, for example
2,6-di-t-butyl-4-methylphenol, 2-t-butyl-4,6-dLmethyl-
phenol,2,6-di-t-butyl-4-ethylphenol,2,5-di-t-butyl-4-i-
butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2-(a-
methylcyclohexyl) 4,6-dimethylphenol, 2,6-di-octadecyl-4~
methylphenol, 2,4,6-tri-cyclohexylphenol and 2,6-di-t-
butyl-4-methoxymethylphenol.
2. Alkylated hydroquinone~, for example
2,6-di-t-butyl-4-methoxyphenol, 2,5-di-t-butyl-hydro-
quinone, 2,5-di-t-amylhydroquinone and 2,6-diphenyl-4
octadecyloxyphenol. ~ ;~
3. ~ydroxylated thiodiphenyl ether~, for exsmple
2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,2'-thio-bi
(4~octylphenol), 4,4'-thio-bis-(6-t-butyl-3-methylphenol)
and 4,4'-thio-bi~-(6-t-butyl-2-methylphenol). ~:
4. Alkylidene-bi6phenol~, for ex~mple
2,2'-methylene-bis-(6 t-butyl-4-methylphenol)-2,2'o
methylene-bis-(6-t-butyl-4-ethylphenol), 2,2'-methylene- -~
20 bis-[4-methyl-6-(a-methylcyclohexyl)-phenol], 2,2'-
methylene-bis-(4-methyl-6-cyclohexylphenol), 2,2'-methyl~
ene-bi3-(6-nonyl-4-methylphenol), 2,2'-methyle~e-bis-
(4,6-di-t-butylphenol), 2,2'-ethylidene-bis-~4 ~ 6-di-t~
butylphenol), 2,2'~ethylidene-bis-(6-t-butyl-4-isobutyl~
25 phenol), 2,2'-methylene-bis-[6~ methylbenzyl)-4-nonyl- : :
phenol], 2,2'-methylene-bi~-[6-(,a-dimethylbenzyl)-4
nonylphenol], 4 ~ 4'-methylene-bi Ef- ( 2,6-di-t-butylphenol),
4,4'-methylene-bi~-(6-t-bukyl-2-methylphe~ol), 1,1-bi~
(5-t-butyl-4-hydroxy-2-methylphenyl)-butane, 2,6-di-(3-t- :-
butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-
tris-(5-t-~utyl-4-hydroxy-2-methylphenyl)-butane, 1,1-
bi~-(5-t-butyl-4-hydroxy-20methylphenyl)-3-n-dodecyl-
mercaptobutane, di-(3-t-butyl-4-hydroxy-5-methylphenyl~ .
dicyclo-pentadiene, di-t2-(3'-t-butyl-2~-hydroxy-;'-
35 methyl-benzyl)-6-t-butyl-4-methyl-phenyl~ terephthalate
f :' , ~ . . '' . ' '' , ' , ' : : '~
. f . ~
s~ . , , . . .. ., . i, ,. ,, , " .. .. .
2 1 ~
- 12 -
and ethylene glycol bi~-[3,3-bi~-(3~-t-butyl-4'-hydroxy-
phenyl) butyrate].
5. ~enzyl compounds, for example
1,3,5-tri-(3 t 5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trLme-
thylbenzene,di-(3,5-di-t-butyl-4-hydroxybenzyl)~ulfide,
i~ooctyl 3,5-di-t-butyl-4-hydroxybenzylmercaptoacetate,
bis-(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)-dithiol
terephthalate, 1,3,5-tris-(3,5-di t-butyl-4-hydroxy-
benzyl) isocyanurate, 1,3,5-tri~-(4-t-butyl-3-hydroxy-
2,6-dimethylbenzyl) isocyanurate, 3,5-di-t-butyl-40
hydroxybenzyl-pho~phonic acid dioctadecyl e~ter and the
calcium ~alt of 3,5-di-t-butyl-4-hydroxybenzylpho~phonic
acid monoethyl ester.
. ~ ;:,.
6. Acylaminophenol~, for example
4-hydroxy-lauric acid anilide, 4-hydroxy-~tearic acid
anilide, 2,4-bi~-octylmercapto-6-~3,5-di-t-butyl-4-
hydroxy-anilino)-s-triazine and octyl N-(3,5-di-t-butyl-
4-hydroxyphenyl)-~arbamate.
7. Bsters of ~-(5 t-butyl-4-hydroxy-3-methylphenyl)-
propionic acid with mono- or polyhydric alcohol~, ~uch
as, for example, with
methanol, diethylene glycol, octadecanol, triethylene
glyool, 1,6-hexs~ediol, pentaerythritol, neopentylglycol,
tri~-hydroxyethyl i~ocyanurate, thiodiethylene glycol and
dihydroxyethyl-oxalic acid diamide.
8. Amides of ~-(3,5 di-t-butyl-4-hydroxyphenyl)-propionic
acid, ~llch a~, for example,
N,N'-di-(3,5-di-t-butyl-4-hydroxyphenylpropionyl)-hexa-
methylenediamlne, N,N'-di-(3~5-di-t-butyl-4 hydroxy-
phenylpropionyl)-trimethylenediamineand~ di-(3,5-di-
t-butyl-4-hydroxyphenylpropionyl)-hydrazine.
In addition, the polymers to be ~tabilized can al80
contain other additive~ such as, for example:
--` 2 ~
- 13 -
1. W absorbers and light ~tabilizers
1.1 2-(2~-Hydroxyphenyl~-benzotriazoles, such ae, for
example, the 5'-methyl, 3~,5'-di-t-butyl, 5'-t butyl,
5'-(1,1l3,3-tetramethylbutyl~, 5-chloro-3',5'odi-t-butyl,
5-chloro-3'-t-butyl-5~-methyl, 3'-sec-butyl 5'-t-butyl,
4'-octoxy, 3',5'-di-t-amyl and 3',5'-bis(a,a-
dimethylbenzyl) derivative.
1.2 2-Hydroxybenzophenones, for example the 4-hydroxy,
4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy/ 4-benzyl-
oxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dLmethoxy
derivative. -
. ~
1.3 E6ters of optionally substituted benzoic scid6, ~or
example 4-t-butyl-phenylsalicylate, phenyl 3alicylate,
octylphenyl salicylate, dibenzoylre~orcinol, bis-(4-t- - ~
15 butylbenzoyl)resorcinol, benzoylre~orcinol, 2,4-di-t- - -~ ;
butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate and hexa~
decyl 3,5-di-t-butyl-4-hydroxybenzoate. ~ -
. .~
1.4 Acryl~tes, for example
ethyl and i800ctyl ~-cyano~ -diphenylacrylate, methyl
a-carbomethoxycinnamate, methyl and butyl a-cyano~
methyl p-methoxycinnamate, methyl a-carbomethoxy-p-
methoxycinnamate and N-(~-carbomethoxy-9-~yano-vinyl)-2-
methyl-indoline. ~
1 0 5 Nickel compound~, for example ~ ;
nickel complexeR of 2,2'-thio-bi3[4-(1,1,3,3-tetramethyl-
butyl)-phenol], such a~ the 1:1 or 1:2 oomplex, if
appropriate with additional ligand~; such as n-butyl-
amine, triethanolamine or N-cyclohexyldiethanolamine,
nickel alkyldithiocarbamates, nickel salts of 4-hydroxy-
3,5-di-t-butyl-benzylphosphonic acid monoalkyl eeter~,
such as of the methyl or ethyl e~ter, nickel complexes o~
ketoxime~, ~uch a~ of 2-hydroxy-4-methyl-phenyl undecyl
¦ ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-
hydroxypyrazole, if appropriate with additional ligands,
.,
,~ ", ~.i ,,. ,,,," ,,",, .. ,., ",~,,," ,~,
~ . . ~ ~ ' i " :' "''~ '~' ~ ~ ' ' i' '
~ 14 _ 2 ~
and nickel ~alt6 of 2-hydroxy-4-alkoxybenzophenones.
1.6 Sterically hindered amlnes, for example ~y~
1.6.1 bi~(2,2,6,6-tetramethylpiperidyl) seba~ate, bi~
tl,2,2,6,6-pentamethylpiperidyl) ~ebacate, bis-(2,2,6,6-
tetramethylpiperidyl) glutarate, bis-(1,2,2,6,6-penta-
methylpiperidyl) glutarate, bis-(2,2,6,6-te~ramethyl-
¦ piperidyl) succinate, bis-(1,2,2,6,6-pentamethyl~
I piperidyl) ~uccinate, 4-~tearyloxy-2,2,6,6-tetramethyl- ;
piperidine, 4-~tearyloxy-1,2,2,6,6-pentamet~ylpiperidine,
4-~tearoyloxy-2,2,6,6-tetramethylpiperidine, 4-~tearoyl~
oxy-1,2,2,6,6-pentamethylpiperidine, 2,2,6,6-tetramethyl-
piperidyl behenate, 1,2,2,6,6-pentamethylpiperidyl
behenate, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadi3piro~
~5.1.11.2~-heneicoian-21-one, 2,2l3,4,4-pentamethyl-7
oxa-3,20-diazadispiro-[5.1.11.2~-heneico~an-21-one,
2,2,4,4-tetramethyl-3-acetyl-7-oxy-3,20-diazadi~piro~
~5.1.11.2]-heneico~an-21-one, 2,2,4,4-tetramethyl-7~oxa-
3,20-diaza-20~(~-lauryl-~xycarbonylethyl~-21-oxo-di~piro-
[5.1.11.2]-heneicosane, 2,2,3,4,4-pentam~thyl 7-oxa-3,20-
20 diaza-20D(~-lauryloxycarbonylethyl)-21-oxo-di~piro ~-
[5.1.11.2]-heneicosane, 2,2,4,4-tetr~methyl-3-aoetyl 7-
oxa-3,20-diaza-20-(p-lauryloxycarbonyl-ethyl)-21~oxo-
dispiro-[5.1.11.2]-heneicosane, 1,1',3/3',5,5'-hexahydro~
2,2',4,4',6,6'-hexaaza-2,2',6,6'-bi~methano-7,8-dioxo-
4,4'-bi~-(1,2,2,6,6-pentamethyl-4-piperidyl)biphenyl,
N,N',N",N"'-tetraki~-[2,4-bis-tN-~2,2,6,6-tetramethyl-4-
piperidyl)-butylamino]-l, 3 ~ 5-tri~zin-6-yl ] -4, 7-diaza-
decane-1,10-diamine, N,N',N",~"'-tetraki~[2,4-bis[N-
(1,2,2,6, 6-pentamethyl-4 -piperidyl)butylamino~-1,3,5-
triazin-6-yll 4,7-diaz~decane-1,10-diamine t ~ N~-
' tetrakis-[2,4-bi~-tN-(2,2,6,6-tetramethyl-4-pip~ridyl)-
methoxypropylamino]-1,3,5-triazin-6-yl]-4,7-diazadeaan~-
l,10-diamine, N,N',N"/N"'-tetrakis-~2, 4-biB- tN-
(1,2,2,6, 6 -pentamethyl-4-piperidyl)methoxypropylamino]-
1,3,5-triazin-6-yl]-4,7-diazadecane-1,10-diamine, bis-
(1,2,2,6,6-pentamethyl-piperidyl)-n-butyl 3,5-di-t-butyl-
4-hydroxy-benzylmalonate, tri~-(2,2,6,6-tetramethyl~4-
. '.
.,.'.
2 ~
- 1
piperidyl) nitrilotriacetate, te~raki~-(2,2,6,6~tetra~
methyl-4-piperidy~ 2~3~4-bu~anetetracarboxylic acid
and 1,1'~(1,2-etha~ediyl)-bis~(3,3,5,5-tetramethyl-
piperazinone).
. .
1.6.2 Poly-N,N'-bi~(2,2,6,6-tetramethyl~4-piperidyl)-1,8
diazadecylene, the condensation product of 1-(2-hydroxy~
ethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
~uccinic acid, the condensation product of N,N'-bis-
(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine
and 4-t-octylamino-2,6-dichloro-1,3,5-triazine and the
condensation product of N,N'-bi~ (2,2,6,6-tetramethyl-4-
piperidyl)-hexamethylenediamine and 4-morpholino-2,6
dichloro~1,3,5-triazine.
1.7 Oxalic acid diamide~, for example ~ -
4,4'-di-octyloxy-oxanilide, 2,2~-di-octyloxy-5,5'-di-t~
butyl-oxanilide, 2,2'-didodecyloxy-5,5'-di-t-butylox- ~ -~
anilide,2-ethoxy-2~-ethyl-oxanilide,N,N'-bi~-(3-dimeth-
ylaminopropyl) oxalamide, 2-ethoxy-5~t-butyl-2' ethylox-
anilide and it~ mixture with 2-ethoxy 2'-ethyl-5,4-di-t~
butyl-oxanilide, and mixtures of o- and p-mekhoxy- and of
o- and p-ethoxy-di-sub6tituted oxanilides.
2. Metal deactivator~, for example -
N,N'-diphenyloxalic acid diamide,~-~ali~ylyl-N'-~alicyl~
oyl-hydrazine, N,N'-bis-salicyloyl-hydrazine, N,~'-bi~
(3,5-di-t butyl-4-hydroxyphenylpropionyl)-hydra~ine,
3-~ali~yloylamino-1,2,3-triazola ~nd bi~-benzylidene-
oxali~ acid dihydrazide.
3. Pho~phites and phosphonites, for example
- triphenyl ph~sphite, diphenyl alkyl phosphit~s, phe~yl
dialkyl phosphites, trisnonylphanyl pho~ph~te, trilauryl
pho~phite, trioctadecyl pho~phite; di~tearylpenta- -
erythrityl dipho3phite, tris-l2,4~di-t-butylphenyl)
pho~phite, dii~odecyl-pentaerythrityl diphosphite, bi~
t2,4-di-t-butylphenyl) pentaerythrityl diphosphite,
t r i ~ t e a r y l - 8 o r b i t y 1 t r i p h o ~ p h i t e ,
2 1 1 ~
- 16 -
3,9-bis-(2,4-di-t-butylphenoxy)-2,4,8,10-tetraoxa-3,9-
dipho6pha~piro-[5.5]-undecaneandtrie-(2-t-butyl-4-thio-
(2'-methenyl-4'-hydroxy-5~ ot-butyl ) -phenyl-5-methenyl)-
phenyl phosphite.
''"' . ~,~'"':'
4. Peroxida-de~troying compounds, for ex2mple
esters of ~-thio-dipropionic acid, ~uch a~, for ~xample, ~ ;
the lauryl, ~tearyl, myri~tyl or tridecyl ester,
mercaptobenzimidazole, the zinc salt of 2-mercaptobenz-
imidazole, zinc alkyl-dithiocarbamates, dioctadecyl ~;
sulfide, dioctadecyl disulfide and pentaerythritol
tetrakic-(~-dodecylmercapto)-propionate.
.
5. Ba~ic co-stabilizers, for example
melamine, polyvinylpyrrolidone~ dicyandi~;de, triallyl ~ ~
cyanurate, urea derivativeY, hydrazine derivative~, -
amines, polyamines, polyurethanes, alkali metal and
alkaline earth metal salt~ of higher fatty ACid8 or
phenolates, for example Ca stearatey Zn ~t~arate, ~g
stearate, Na ricinoleate, K palmitate, antimony pyro-
catecholate or tin pyrocatecholat~, and hydroxide3 and
oxidea of alkali~e earth metals or of aluminum, for
example CaO, MgO or ZnO.
~ .
6. Nucleating agents, for example
4-t-butylbenzoic acid, adipic acid, diphenylacetic acid
and dibenzylidene~orbitol.
7. Fillers and reinforcing agents, for example
calcium carbonate, ~ilicates, glas~ fiber , a~b~sto~,
talc, kaolin, mica, barium sulfate, metal oxides ~nd
hydroxides, carbon blaak, graphite and high modulu~
fiber~.
....
8. Other additives, for example
plasticizers, lubricants, emulsifiera, pigments, optical
brightener~, flameproofing agents, antiYtatia~ and
blowing agents.
~ 211~1~0 ~
- 17 -
The various additional additive~ of the above~entioned
groups 1 to 6 are added to the polymer~ to be ~tabilized --~
in an amount of from 0.01 to 10, preferably 0.01 to 5% by
weight, based on the total weight of the molding composi-
tion. The proportio~ of additives of group~ 7 and 8 iB
to 80, preferably 10 to 60% by weight, ba~ed on the total
molding composition.
The stabilizers are incoxporated into the cycloolefin
polymer by generally customary method~. In~orporation
10 can be carried out, for example, by mixing the ~ompounds `~
and if appropriate other additives into th0 melt before
or during shaping. Incorporation can al~o be carried out
by application of the dissolved or disper~ed compounds to
the polymer directly ox by mixing in a ~olution, ~u~pen~
sion or emulsion of the polymer, if appropriate with
subsequent evaporation of the solvent. The ~mount to be
added to the polymers i8 0-01 to 10, prefexably 0.025 to
5, in particular 0.02 to 2% by weight, ba~ed on the
cycloolefin pol~mer to be stabilized. `~
The stabilizers can also be added to the polymers to be
stabilized in the form of a masterbatch which comprises
these compounds, for example, in a co~centration o~ from
1 to 50, preferably 2.5 to 20~ by weight.
~he organophosphorus compounds used according t~ the
invention maintain the melt vi~08ity of the mol~ing
composition at the highe t level (very small deviation
from the starting value). ~oreover, they lead to the be~t
initial color~ of te~t ~pecimene and to r~latively little
change in color after kneading experiment~.
The cycloole~in polymer molding composition ~tabilized
according to the invention can be used in variou~ forms,
for example in the form of ~heet~, fiber~, films and
tubes, or a~ binder~ for paints, adhe~ives or putties.
~:'
The following polymere were prepared by standard method~ ~
~ ~ '
; ~ . '
j
f ~ ::~ ::~: `.: ::~ i~.. ,' .~ :" ~ ~ ` : :~ :- ~ ` ` : `
.~ ~ `....... , ` . , - `. . . .
for the example~
Cycloolefin copolymer A1 [COC Al]
A clean and dry 75 dm3 polymerization reactor with a
~tirrer wa~ flu~hed with ~itrogen and then with ethylene.
37 dm3 of benzine fraction (100/110) and 10700 g of
norbornene melt were then initially introduced into the
polymerization reactor. The reactor wa~ brought to a
temperature of 70C, while stirring, and 2.9 bar of
ethylene were forced in.
Thereaftex, 500 cm3 of a toluene ~olution of methyl~
aluminoxane (10.1% by weight of methylaluminoxane of
molecular weight of 1300 g/mol according to cryo~copic
determination] were metered into the x~aotor and the
mixture wa6 ~tirred at 70C for 15 minutes, the ethylene
pressure being kept at 2.9 bar by subsequent metering in>
I~ parallel, 350 mg of diphenylmethylene-(9-fluorenyl~
cyclopentadienyl zirconium dichloride were di~solved in
500 cm3 of a toluene solution of methylaluminoxane (~or
the concentration and quality, see above) and were
preactivated by being left to stand for 15 minute~ The
~olution of the metallocene tcataly~t solution) was then
metered into the reactor. The mixture was polymerized at
70C for 135 minutes, while stirring, the ethylene
pressure being kept at 2.9 bar by sub~equent m~t~ring in.
The content~ of the reactor were then drained rapidly
into a stirred vessel into which 40 dm3 of benzine
fraction (100/110), 1000 g of kieselguhr ~Celite J 100)
and 200 cm3 of ice-water had been initially introduced ~t
70C. Tha mlxture wa~ filtered, 80 that the ~ilter
auxiliary wa~ retained and a clear polymer 801utio~
re~ulted a~ the filtrate. The clear ~olution wa~ precipi-
tated in acetone, the mlxture wa~ stirr2d for 10 ml~utes
and the suspended polymeric ~olid was then filtered off.
To remove re~idual solvent from the pol~mer, the polymer
was extracted by ~tirring twice more with acetone and
~f~ ~: :-:, :- : . ' :, ' .
~; 2 ~
- 19 ~
filtered off. Drying was carried out at 80C in vacuo in
the course of 15 hour~. 3400 9 of polymer were obtained.
Preparation of cycloolefin copolymer A2 tCOC A2]
A clean and dry 75 dm3 polymerization reactor with a
~tirrer was flushed with nitrogen and then with ethylene.
20550 g of norbornene melt were then initially introduced
into the polymerization reactor. The content~ of the
reactor were brought to a temperature of 70C, while
stirring, and 3.5 bar of ethylene were forced in.
Thereafter, 1000 cm3 of a toluene Bolution of methyl-
aluminoxane (10.1% by weight of methylalumi~oxane of
molecular weight 1300 g/mol according to cryoscopic
determination) were then metered into the reactor and the
mixture was stirred at 70C for 15 minutes, the ethylene
pres~ure being kept at 3.5 bar by subsequent metering i~.
In parallel, 350 mg of diphenylmethylene-(9-fluorenyl)-
cyclopentadienyl-zirconium dichloride were dis~olved in
500 cm3 of a toluene solution of methylaluminoxane (for
the concentration and quality, aee above) and were
preactivated by being left to ~tand for 15 ~lnutes. The
eolution of the metallocene (~atalyst solution~ was then
metered into the reactor. The mix~ure was polymeriz~d at
70C for 233 minu~es, while ~tirring, the ethylene
pressure being kept at 3.5 bar by ~ub~equent metering in.
The contents of the reactor were then drained rapidly
into a ~tirred ve3~el into which 40 dm3 of benzine
fraction (100/110), 1000 g of kie~elguhr (~Celite J 100)
and 200 cm3 of ice-water had been initially introduoed at
70C. The mixture was filtered, so that the filter
auxiliary was retained and a clear polymer ~olution
resulted a~ the filtrate. The clear solution wa~ precipi~
. tated in acetone, the mixture w~s 6tirred for 10 minutes
and the polymeric solid was then filtered off.
To remove residual solvent from the polymer, the polymer
was extracted by stirring twice more with acetone and
filtered off. Drying wa~ carried out at 80C in vacuo in
': , ':
', ,: :~'
- 20 _ ~ t l ~ ~ ~ o
the course of 15 hours. 5200 g of polymer were obtained.
The physi~al parameter~ of cycloolefin copolymers A1 and -
A2 can be found in Table 1.
~ .
Table l
5 Cycloolefin Incorporation~ o~
copolymer ethylene norbornene VN ~g
[mol~] [mol%] ~cm3/g] ~C]
A1 54 46 143 145 :~
A2 55 45 141 139
~ determined by '3C-nuclear magnetic re~onance.pectro-
~copy . ~
~N: vi~cosity number in accordance with DIN 53 728
Tg: glass stage during the 2nd heating up; heating up
and cooling rate: 20/mlnute ;
Examples
The organophosphorus compounds liqted below were employed
for the experiment~.
(A) Tetraki3-(2,4-di-t-butylphenyl)-4,4'-biphenylene
dipho~phonite, commercial product
+~\~3/~+
~
,~
Content 40~ (3'P-NMR)
. :~
(~) Tetrakis-~2,4-di-t-butylphenyl)-4,4' biphenylene
dipho~phonite, stabilized toward hydrolysis accord-
ing to DE 42 18 411 with MgO
Content 40% (3lP-NMR)
~ , " ~ . - - : -................. ~ -........ ..
, ~
..... . ... . .. ..
~ 21 - 2~
(C) Tetraki~-(2,4 di-t-butylphenyl)-4~4~-biphenylene
dipho~phonit~; aecording to ~xample 2a D~ 42 lB 411
Content 70% (3~519YP-NMR)
(D~ 6-(2~-Tolyl)-6~-dibenzo-[c,e][1.2~-oxaphosphorine
':: ~; . ' ;~
Content about 97~ (3lP-NMR) :
~E) Bis-~l-naphthyl)phosphinous acid 2,4-di-t-butyl~
phenyl ester
`~
~ 10 Content about 90% ~3lP-NMR)
~ ~, ;. ~.. .. ,:
(Fj l-Naphthyl-pho3phonou~ acid bi~-(2,4-di-t-buty~
., phenyl) e~ter
: ,, .; .~.,,
., ~ ~
~ '~':~ ,,"..'
'' ~
", ,! ", _ 22 2 ~ 1 0 1 ~ ~ ~
~// \~
/
\n~
>=
Content sbout 98~ (3lP-NMR)
The preparation of these co~pounds i5 de~cribed in
US.5,109,043, EP 472 564 and WO 92/003060 Other prepAra-
tion methods are propo~ed in DE 41 24 790 and
DE 42 18 411. ~: .
The amounts of stabilizers shown in he tables were
applied a~ ~olutions to the powder of the cyclool~fin
polymers de~crlbed above and the mlxture wa~ drie~
(130C, 24 hours, vacuum). The polymer~ pretreated in
thi3 way were kneaded with the aid o~ a measurinq kneader
(~Rheocord Sy~tem 40/0Rheomix 600; Baake, ~arl~ruhe)
under the conditions mentioned. Portion~ of the re~ulting
kneaded producta were pressed lvacuum pre~8: ~polyBtat
20Q S; Schwabenthan, ~erlin) to sheet~ ~120 x 1 Dm). ;.~
~15 Sheets were additionally produoed ~rom the ~tartlng .~ ~:
: powder of the cycloolefin copolymer~ (without/with
~tabilizer~
The yellowing of the sheet~ produc0d wa~ measuxed a~ the ~ ~:
Yellowness Index in accordanc~ with ASTM D 1925 70.
'
The other portion of the kneaded product~ wa~ ground and
dried (130C, 24 hour~, vacuum) and the melt ~low index
waB det¢rmined in ~ccordance with DI~ 53 735.
:
The yellowing after ~torage in heat (7 day~ at 100C)
2~
- 23 -
~urthermore was mea~ured.
~he stated amount~ of additive~ employed are parts by
weight per 100 parts by weight (phr) of cycloolefin :
copolymer.
5 The re~ult~ are to be found in Table~ 2 to 12. :
The ~ymbol~ in the table~ have the follo~ing meaning~o
phenol') ethyle~e glyool 3,3-bis-(3'-t-butyl-4'-hyd~oxy-
phenyl)-butanoate
2) HALS S Bindered Amine Light Stabilizer
2,2,4,4-tetramethyl-7--oxa-3,20-diazadispiro-~5.1.11 2]- -~
heneico~an-21-one
3) oligomerized 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-20- ~ :~
(2,3-epoxypropyl)-di6piro-~5.1.11.2]-heneioo~an-21-one
4~ N,N',N",N"'-tetraki~-{2,4-bis-[N (1,2,2,o,6-penta-
methyl-4-piperidyl)-butylamino]~ ,5-tri~zin-6-yl}~4,7-
diazadecane-1,10-diamine -
5~ bi~-(2,2,6,6-tetramethyl-piperidyl)-aebacate
6) condensation product of N,N'-bi~-(2,2,6,6-tetramethyl-
4-piperidyl)-hexamethylenediamineand4 t-octylamino-2~6
dichloro-lr3,5-s-triazine
Table 2
Action of pho~phorus compound~ on the proces~ing ~--
st bility of cycloolefin copolymer A1 ~: :
Xneading condition~: 280C, 40 revolutiona per mlnute~
60 mlnutes
- ., ~,.
~elt flow i~dex MFI 280/5 (melting time of 5 mlnutes)
before kneading: 5 cm3/10 minute
l .
~ ~:
.i 2 ~ 0 a
- 24 -
Bxample Phosphoru~ Othex MFI after
compound additives kneading
Parts by Part~ by cm3/10 miDUt~8
by weight by weight
5 Com-
parison I none 39Ol
Com-
parison II 0.1 (A) 52.5
la 0-1 (B) 47~0
lb 0.1 (C) 32.1
lc 0.1 (B) 0.05 phenol~ 51.0
ld 0.1 (C) 0.05 phenoll) 26.6
,~ .,
Table 3
Change in color (Yellowne~s Index in accordance with
ASTM D 1925-70) after the extreme kneading experiment
(280C, 40 revolution~ per mlnute, 60 m~nutes) on cy~lo~
olefin copolymer Al
Example Phosphoru~ Other YI
~ompound additives unkneaded ~neaded
Parts by Parts by
weight weight
Com-
parison I none 5.3 85.9
Com-
parison II 0.1 (A) 6.7 70.9
la Oo l (13) 8~5 72 ~2
lb 0.1 (C) 6.7 74.6 .
lc 0.1 ~B) 0~05 phenoll~ 8.4 68.3
ld 0.1 (C) 0.05 phenoll~ 5.8 71Og
. .
,'.
..
`~
, . : .. . . . . .
~-~ 2 ~
3 ~
- 25 - -
~able 4
: ' '
Action of phosphorus compound~ on the proce~sing
stability of cycloolefin copolymer A1
Kneading conditions: 240C, 40 revolution~ per minute,
60 minutes
Melt flow index MFI 240/21.6 (melting time of 5 minutes~ :
before kneading: 19.2 cm3/10 minutes
Example Pho~phorus Other MFI after
compound additives kneading
Parts by Parts by am3/10 minutes
by weight by weight
Compari~
~on III none 33.0
2a 0.1 (C) 28.7 ~ ~.15 2b 0.1 (C) 0.05 phenol1~ 26.6
2c 0.1 (C) 0.05 phenol
O.3 HALS2) 21.0 -~-
2d 0.1 (C) 0.05 phenoll~
O.3 ~ALS3) 18.6
20 2e 0.1 (C) 0.05 phenol
0.3 ~ALS4) 20.3
. ~
,"
;
~ ~. `` 2 ~ - 26 -
Table 5
Change in color (Yellowness ~ndex in accordance with
~STM D 1925-70) after the kneading experiment (240C,
40 revolution~ per minute, 60 minutes) on cycloolefin
5 copolymer Al :
... ..
Example Pho~phoru6 Othex YI
compound additives unkneaded kneaded
Parts by Parte by
weight weight :~
10 Compari- ~:
son III none 5.3 54.
2a 0.1 (C~ 5.0 33.6
2b 0.1 (C) 0.05 phenol1~ 6.3 52.0 .~ -2c 0.1 ~C) 0.05 ph~nol~
0.3 ~ALS2) 6.1 30.5 ~-:
2d 0.1 (C) 0.05 phenol"
0.3 8RLS3) 6.6 4~.3
2e 0.1 (C) 0.05 phenol~
0.3 HALS lg.4 55.2
::
, ~
_ 211~10~
- 27 -
Table 6:
Action of phosphoru~ compounds on the processing
~tability of cycloolefin copolymer A2
Kneading conditions: 190C, 40 revolutions per minute,
5 60 minutes :-
Melt ~low index MFI 190/10 (melting time of 5 minute~3
be~ore kneading 10 cm3/10 mlnutes :~
Example Phosphorus Other MFI after
compound additives kneading ~ -
Part6 by Parts by
by weight by weight
Compari~
son IV none 22.6 .~
3a 0.1 (D) 15.4 ~ .
3b 0.1 (D) 0.05 phenoll~ 12.1
3c 0.1 (D) 0.05 phenol~
O.3 HALS2) 13.0
3d 0.1 (D) 0.05 phenol~
O.3 ~ALS3) 12.4
3e 0.1 (D) 0.05 phenol~
O.3 ~ALS5) 19 g
3f 0.1 (D3 0.05 phenol~
0.3 ~ALS6) 12.8
3g 0.1 (D) 0.05 phenol~
0.3 ~ALS4) 12.2
, ::
. .
''' '.~.''
- 28 - 2~
Table 7: ~.
Change in color (Yellownes~ Index in accordance with
ASTM D 1926 ~0t of cycloolefin copolymer A2 after the
kneading experiment ~190C, 40 revolution~ per minute,
60 minutes)
~xample PhoRphorus Other YI
compound additives unkneaded kneaded
Parte by Parts by :
weight weight
10 Compari- ~
eon IV none 3.4 13.8 ~ :
3a 0.1 ~D) 2.1 12.9
3b 0.1 (D~ 0.05 phenol~ 1.0 25.1
3c 0.1 (D) 0.05 phenol~
~.3 ~ALS2) 3.2 20.9
3d 0.1 (D) 0.05 phenol"
0.3 HALS3) 104 26.6
3e 0.1 (D) 0.05 phenol
O.3 ~ALSs) 3.~ 16.2 :
3f 0.1 (D) 0.05 phenol"
0.3 ~ALS6) 1.6 16.4
3g 0-1 (D) 0.05 phenol~
0.3 ~ALS 1.4 15.8
1 0 0
- 29 -
Table 8~
Action of phosphoruæ compounds on the processing3tabili~y of cycloolefin copolymer A2
Kneading condi~ions: 190C, 40 revolutions per minute,
60 mlnute~
Melt ~low index MFI 190/10 (melting tLme of 5 minutes)
before kneading 10 cm3/10 minute~
Example Pho~phorus Other MFI a~ter
compound additives kneading
Part~ by Part~ ~y :~
by weight by weight
Compari~
~on IV none 22.fi
4a 0.1 (E) 12~
15 4b 0.1 (E) 0.05 phenol~ 13.2
4c 0.1 (E) 0.05 phenoll~
O.03 ~ALS2~ 16.4 :~ -
4d 0.1 (E) 0.05 phenol~
O.03 ~ALS3) 12
20 4e 0.1 (E) 0.05 phenol~
0.3 ~ALS5) 13.3 ~-~``:
4f 0.1 (E) 0.05 phenol~
0.3 ~ALS6) 13.2 ~:
4g 0-1 (E) 0.05 phenol
0.3 ~LS4) 18.6 `
: ,~
.. ''~
, ' ~ ~
::
~ ::
'.
,~
~ 2 ;l 1 ~
0 _
Table 9~
Change in color (Yellowness Index in ac~ordanae with
ASTM D 1925-70) of cycloolefin copolymer A2 after the .
kneading experLment (190C, 40 revolutions per minute,
60 minutes)
Example Phosphoru~ Other YI
compound ~dditives unkneaded kneaded
Part~ by Parts by
weight weight
10 Com- -~
parison IV none 3.4 13.8
4a 0.1 (E) 2.2 6.1
4b 0.1 (E) 0.05 phenol1~ 1.1 22.3
4c 0.1 (E~ 0.05 phenol1' :
0.3 ~ALS2) 1.1 9.0 ~:~
4d 0.1 (E) 0.05 phenol~
0-3 ~ALS3) 1 7 10-2
4e 0.1 (E) 0.05 phenol~
0.3 ~ALSs) 1.5 18.3 : ;;;
4f 0.1 (E) 0.05 phenol
0.3 ~ALS6) 1.7 2~.6 `~
4g 0.1 (E) 0.05 phenol
0.3 HALS4) 1.6 19.7
:~
. '~
S ~
Z l l ~ 1 0 0
Table 10
Action of phosphorus compounds on the proce~sing
stability of cycloolefin copolymer A2
Kneading conditions: 190C, 40 revolution~ per mlnute/ : :
5 60 minutes .~
Melt flow index ~FI 190/10 (melting time of 5 minutes) ' -::
before kneading 10 cm3/10 m1nutes ~:
".
~xample Phosphoru~ Other ~FI aft2r
compound additiveskneading
Parts by Part~ by
by weight by weight
Compari- -:
son IV none 22.6
5a 0.1 ~F) 12.3
15 5b 0.1 (F~ 0.05 phenol1) 9O9
5c 0.1 (F) 0.05 phenol
~.03 ~A~S2)19.6 :~
5d 0.1 (F) 0.05 phenol
0.03 ~ALS3)12.5
20 5e 0.1 (F) 0.05 phenol~
0.3 ~A~Ss) 13.0
5f 0 1 (F) 0.05 phenol1)
0.3 ~ALS6) 16.3
5g 0.1 (F) 0.05 phenol1) . ~ :
0.3 ~ALS4)13.8
: ::
: '
.
. ...
. , ;.
:: : :
, : ~
2 1 1 0 1 ~
~ ' ... ~
Table 11~
Change in color (Yellownes~ Index in accordance with
~¦ AS~M D 1925-70) of oycloo}efin copolymer A2 after the
kneading experiment (190C, 40 revolutions per mlnute,
60 minutes)
Ex~mple PhoQphoru~ Other YI
compound additives unkneaded kneaded
Part~ by Parts by
weight weight
10 Com-
parison IV n~ne 3.4 13.8
5a 0.1 (F) 0.~ 7-3
5b 0.1 (F) 0.05 phenol 1.3 9.5
5c o.1 (F) 0.05 phenoll)
0.3 HALS2) 1.0 13.8 :
5d 0.1 (F) 0.05 phenol
0.3 ~ALS3) ~.3 11.4 ~:~
5e 0.1 (F) 0.05 phenol~
O.3 HALSs) 1.4 10.3 :
20 5f 0.1 (F) 0.05 phenol"
~.3 ~ALS6) 1.8 11.4
5g 0.1 (F) 0.05 phenol
0.3 ~ALS4) 1.7 20.3
~ i~
~, ' ~:
~-~ 2~
- 33 ~
:, '.-, :,:
Table 12~
Color development on 1 mm pressed aheets i~mediately
after production and after conditioning (7 day3 at 1~0C)
Example YI immediately YI a~ter 7 days ``~
5 Comparison I 5.3 6.0
2a 5.0 6.1
2b 6.3 6.7
~iC 6.1 7.1
2d 6.6 6.7
2e 19.4 15.0
Comparison IV 3.4 4.7
3a 2.1 4.3
3b 1.0 4.0
3c 3.2 5.3
3d 1.4 3.3
3e 3.1 4.5
3f 1.6 5.3
3g 1.4 3.2
. .
4a 2.2 3.9
4b 1.1 3.3
4~ 1.1 2.7
4d 1.7 2.3
4e 1.5 2.2
4f 1.7 2.9
~g 1.6 2.0
. ,
5a 0.8 2.6
5b 1.3 3.3
~c 1.0 1.4
5d 1.3 1.7
5e 1.4 1.8
5f 1.~ 2.4
59 1.7 2.9
:~
,~
'.
