Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
20677~6
TITLE
VINYL CHLORIDE RESIN COMPOSITIONS
FIELD OF THE INVENTION
The present invention relates to vinyl chloride resin
compositions, and particularly to vinyl chloride resin
compositions having an elevated heat distortion
(deflection) temperature by incorporation of a cycloolefin
polymer thereinto to improve the properties of the molded
0 articles.
BACKGROUND OF THE INVENTION
Vinyl chloride resins such as polyvinyl chloride~
copolymers of vinyl chloride and other monomers, or vinyl
chloride resin derivatives, for example, halogenated
polyvinyl chloride (these resins being merely referred to
vinyl chloride resins hereinafter) have excellent scratch
resistance, flame retarding properties, chemical resistance
and electric characteristics, and show a decreased mold
shrinkage factor. Vinyl chloride resins are therefore used
as material for various molded articles. Molded articles
made of vinyl chloride are used under such peculiar
circumstances as water tanks of electric irons, electronic
oven parts, printed circuit boards, conductive sheets and
helmets.
However, conventional vinyl chloride resins have a
problem that molded products obtained therefrom are
2067756
restricted in their use due to their low heat distortion
temperature, although they are excellent in flame retarding
properties, chemical resistance, a low mold shrinkage
factor, etc.
An object of the present invention is to provide vinyl
chloride resin compositions having an elevated heat
distortion ~deflection) temperature or an elevated head
deformation temperature while excellent properties of
conventional vinyl chloride resin compositions, such as
flame retarding properties and a low mold shrinkage factor,
are maintained.
DISCLOSURE OF THE INVENTION
A vinyl chloride resin composition according to the
present invention comprises
[I] [A] a vinyl chloride resin and
[II] [B] a cycloolefin ring opening polymer or copolymer
formed by ring opening polymerization of a cycloolefin
represented by the following formula [I], or a hydrogenated
product thereof, and/or
[C] a cycloolefin random copolymer of ethylene and a
cycloolefin represented by the following formula [I], said
random copolymer having an intrinsic viscosity [~], as
measured at 135C in decalin, of 0.05 to 10 dl/g and a
glass transition temperature (Tg) of at least 70C,
20~77~6
~k~"''
[I]
wherein n is O or 1, m is O or a positive integer, Rl-
RlB are each independently an atom or a group selected from
the group consisting of hydrogen, halogen and hydrocarbon
groups, Rl5-Rl8, linked together, may form a monocyclic ring
or polycyclic ring which may have a double bond, R15 and Rl6
0 or Rl7 and Rl8 may form together an alkylidene group.
The vinyl chloride resin compositions according to the
present invention comprise a vinyl chloride resin [A], and
a specific cycloolefin ring opening polymer or copolymer,
or a hydrogenated product thereof [B], and/or a specific
cycloolefin random copolymer [C]. Accordingly, it becomes
possible to elevate the heat distortion temperature
thereof, and improve the plastication and decomposition
temperature thereof while the excellent flame retarding
properties and small mold shrinkage factors are maintained.
~he excellent properties of the vinyl chloride resin
[A] are not impaired even when the vinyl chloride resin
2~t~7756
contains the cycloolefin ring opening polymer or copolymer,
or hydrogenated product thereof !B] and/or the cycloolefin
random copolymer [C].
5DETAILEP DESCRIPTION OF THE INVENTION
The vinyl chloride resin compositions according to the
present invention are concretely illustrated below.
The present invention is based on the finding that the
heat distortion temperature of the vinyl chloride resin [A]
is significantly increased when the resin [A~ contains the
cycloolefin ring opening polymer or copolymer, or
hydrogenated product thereof [B] and/or the cycloolefin
random copolymer [C] ([B] and [C] may be generally referred
to cycloolefin copolymers hereinafter).
15The vinyl chloride resin composition according to the
present invention comprises
[I] a vinyl chloride resin [A], and
[II] a cycloolefin ring opening polymer or copolymer
formed by ring opening polymerization of a cycloolefin
represented by the following formula [I], or a hydrogenated
product thereof [B], and/or
a cycloolefin random copolymer of ethylene and a
cycloolefin represented by the following formula [I] [C],
~677~ ~
Rl S R7 Rl 1
- /~ _ Rl 5
~ 1~ ~`~J<R
[I ]
wherein n is O or 1, m is O or a positive integer, Rl-
R18 are each independently an atom or a group selected from
the group consisting of hydrogen, halogen and hydrocarbon
groups, Rl5-Rla, linked together, may form a monocyclic ring
or a polycyclic ring which may have a double bond, Rl5 and
Rl6, or Rl7 and Rl8 may form together an alkylidene group.
The vinyl chloride resin compositions contalning a
cycloolefin polymer have an elevated heat distortion
temperature (HDT measured by the heat deflection method
according to ASTM D 648) while maintaining flame retarding
properties, etc. compared with singly used conventional
vinyl chloride resins. The comparison of Examples 1 to 3
and Comparative Example 1, which are described later, shows
that the vinyl chloride resin in Comparative Example 1
containing no cycloolefin copolymer exhibits a lower heat
distortion temperature than that of the vinyl chloride
resin compositions in Examples 1 to 3 containing a
cycloolefin copolymer. Further, the resin compositions in
2~677~ 6
Examples 1 to 3 have the same excellent tenslle strength at
break and flame retarding properties as the resin in
Comparative Example 1, which shows the physical proterties
of the vinyl chloride resin are maintained in the vinyl
chloride resin compositions according to the present
invention.
In addition, the vinyl chloride resins herein are not
restricted to polyvinyl cnloride, but include copolymers of
vinyl chloride and other polymerizable monomers such as
vinyl acetate and vinylidene chloride, vinyl chloride-
grafted products such as a vinyl chloride-grafted
ethylene/vinyl acetate copolymer, and derivatives of
chlorinated vinyl chloride resins obtained by chlorinating
polyvinyl chloride.
VINYL CHLORIDE RESINS
Typical example of the vinyl chloride resin [A] used
in the vinyl chloride resin compositions according to the
present invention is polyvinyl chloride, but is not
restricted to the polyvinyl chloride. The vinyl chloride
resin [A] may be a copolymer of vinyl chloride and other
polymerizable monomers, or a modified product derived from
vinyl chloride.
(1) Examples of the copolymer of vinyl chloride
include vinyl chloride/vinyl acetate copolymer,
vinyl chlorlde/vinylidene chloride copolymer,
vinyl chloride/(meth)acrylic acid copolymer,
vinyl chloride/(meth)acrylate copolymer,
20~7756
vinyl chloride/maleic acid copolymer,
vinyl chloride/maleate copolymer,
vinyl chloride/acrylonitrile copolymer and
vinyl chloride/a-olefin random copolymer (a-olefin
including ethylene and propylene).
(2) Examples of the vinyl chloride-grafted product
include vinyl chloride-grafted products of ethylene/vinyl
acetate copolymer and butadiene/acrylate copolymer.
Furthermore, the vinyl chloride resin [A] includes
modified (co)polymers prepared by grafting the (co)polymers
described in (1) and (2) with a vinyl monomer such as
styrene and methacrylate.
In addition, the modified product derived from
polyvinyl chloride includes chlorinated vinyl chloride
resin obtained by chlorinating polyvinyl chloride.
The vinyl chloride resin [A] has a melt flow rate, as
measured at 190C under a load of 2.16 kg, of 0.1 to 500
g/10 min, preferably 1 to 100 g/10 min and especially 5 to
50 g/10 min.
The vinyl chloride resin [A] has an average
polymerization degree of 200 to 5000, preferably 300 to
4000 and especially 400 to 3000.
The vinyl chloride resin [A] has, under a load of 18.6
kg, a heat distortion temperature of 40 to 90C, preferably
25 50 to 80C.
The vinyl chloride resin [A] has a glass transition
temperature (Tg) of 40 to 90C, preferably 50 to 80C.
20677~
CYC~OOLEFIN POLYMER CONT~INED IN VIN~L CH~ORIDE RESIN
The cyelo31efin polymers used in the vinyl chloride
resin compositions of the invention include
[B] a ring opening polymer or copolymer of a
cycloolefin represented by the aforementioned formula [I],
or a hydrogenated product thereof, and
[C] a cycloolefin random copolymer obtained by
addition polymerization of ethylene and a cycloolefin
represented by the aforementioned formula [I].
In the above-mentioned formula [I], n is 0 or 1, and m
is 0 or a positive integer, preferably 0 to 3.
R1-R18 each independently represent an atom or a group
selected from the group consisting of hydrogen, halogen and
hydrocarbon groups. The halogen herein includes a fluorine
atom, a chlorine atom, a bromine atom and an iodine atom.
The hydrocarbon groups each include usually an alkyl group
of 1 to 10 carbon atom and a cycloalkyl group of 5 to 15
carbon atoms. Concrete examples of the alkyl group include
methyl, ethyl, isopropyl, isobutyl, n-amyl, neopentyl, n-
hexyl, n-octyl, n-decyl and 2-ethylhexyl. Concrete
examples of the cycloalkyl group include cyclohexyl,
methylcyclohexyl and ethylcyclohexyl.
Furthermore, in the above-mentioned formula [I], R15-
R18, linked with one another (together), may form a
monocyclic ring or a polycyclic ring which may have a
double bond.
4a67~5~
In addition, Rl5 and Rl6, or Rl7 and Rl8 may form an
alkylidene group. The alkylidene group is usuaily one
having 2 to 10 carbon atoms. Concrete examples of the
alkylidene group include ethylidene, propylidene,
5 isopropylidene, butylidene and isobutylidene.
In the aforementioned formula [I], R1s-Rl8, linked
together, may form a monocyclic ring or a polycyclic ring
which may have a double bond.
The cycloolefin represented by the formula [I] can be
0 easily prepared by condensation reaction through Diels-
Alder reaction of cyclopentadienes with corresponding
olefins or cycloolefins.
Concrete examples of the cycloolefin represented by
the above-mentioned formula [I] include the following
compounds.
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Bicyclo [2,2,1]hept-2-ene derivatives such as those
mentioned below.
Bicyclo[2,2,1]hept-2-ene
CH3 6-Methylbicyclo[2,2,1]hept-2-ene
CH3 5,6-Dimethylbicyclo[2,2,1]hept-2-ene
CH3
1-Metylbicyclo[2,2,1]hept-2-ene
2H5 6-Ethylbicyclo[2,2,1]hept-2-ene
nC4H9 6-n-Butylbicyclo[2,2,1]hept-2-ene
iC4Hg 6-Isobutylbicyclo[2,2,1]hept-2-ene
2 ~3 6 7 7 rj 6
CH~
7-Methylbicyclo~2,2,1]hept-2-ene
Tetracyclo[4,4,0,12 5,17 1O]-3-dodecene derivatives
such as those described below.
Tetracyclo[4,4,0,12-5,17 10]-3-
dodecene
CH3
5,10-Dimethyltetracyclo-
[4,4,0,12 5,17 1]-3-dodecene
CH3
CH3 CH3
2,10-Dimethyltetracyclo-
[4,4,0,12 5,17 1]-3-dodecene
CH3 CH3
11,12-Dimethyltetracyclo-
[4,4,0,12 5,17 1]-3-dodecene
~V~77~
c~3
- CH3 2,7,9-Trimethyltetracyclo-
[4,4,0,12-5,17-1]-3-dodecene
CH3
CH3
2HS 9-Ethyl-2,7-dimethyltetracyclo-
[4,4,0,12 5,17 1]-3-dodecene
CH3
CH3 CH3
CH2CH 9-Isobutyl-2,7-dimethyltetracyclo-
[4,4,0,12-5,17-1]-3-dodecene
CH3
CH3 CH3
t CH3 9,11,12-Trimethyltetracyclo-
[4,4,0,12-5,17-lOl-3-dodecene
CH3 CH3
C2H5 9-Ethyl-11,12-dimethyltetracyclo-
[4,4,0,12-5,17-1]-3-dodecene
CH3 CH3 CH3
~t CH2CH 9-Isobutyl-11,12-dimethyltetracyclo-
CH [4,4,0,12 5,17 1]-3-dodecene
2~577~
CH3
- CH3 5,8,9,10-Tetramethyltetracyclo-
CH3 [4,4,0,12-5,17 1]-3-dodecene
CH3
8-Methyltetracyclo[4,4,0,12 5,17-1O]-
3-dodecene
CH3
8-Ethyltetracyclo[4,4,0,12 5,17 l0]-3-
dodecene
C2Hs
C H 8-Propyltetracyclo[4,4,0,12 5,17 1O]-
3 7 3-dodecene
8-Hexyltetracyclo[4,4,0,12 5,17 1]-3-
dodecene
C6H13
8-Stearyltetracyclo[4~4~0~12~5~17~10]-
3-dodecene
C18H37
CH3 8,9-Dimethyltetracyclo-
CH3 [4,4,0,12 5,17 1]-3-dodecene
2~7756
14
C~3 8-Methyl-9-ethyltetracyclo-
2H5 [4,4,0,12-5,17 1]-3-dodecene
8-Chlorotetracyclo[4,4,0,12 5,17 1O]-
CQ 3-dodecene
8-Bromotetracyclo[4,4,0,12 5,17 1O]-3-
Br dodecene
8-Fluorotetracyclo[4,4,0,12 5,17 1O]-
F 3-dodecene
8,9-Dichlorotetracyclo-
[4,4,0,12-5,17 1]-3-dodecene
8-Cyclohexyltetracyclo-
[4,4,0,12 5,17 1]-3-dodecene
CH3 8-Isobutyltetracyclo-
CH2CH [4,4,0,12-5,17-1]-3-dodecene
CH3
8-Butyltetracyclo[4,4,0,12-5,17-10]-3-
4H9 dodecene
20~7756
8-Ethylidenetetracyclo-
=CHCH3 [4,4,0,12 5,17 1] -3-dodecene
CH3 8-Ethylidene-9-methyltetracyclo-
= CHCH3 [4,4,0,12-5,17-1]-3-dodecene
/ C2H5
8-Ethylidene-9-ethyltetracyclo-
CHCH3 [4,4,0,12-5,17-1]-3-dodecene
CH(CH3)2
8-Ethylidene-9-isopropyltetracyclo-
CHCH3 [4,4,0,12-5,17 10]-3-dodecene
~C4Hg
8-Ethylidene-9-butyltetracyclo-
CHCH3 [4,4,0,12-5,17-10]-3-dodecene
8-n-Propylidenetetracyclo-
CHCH2CH3 [4,4,0,12-5,17-10]-3-dodecene
CH3
8-n-Propylidene-9-methyltetracyclo-
CHCH2CH3 [4,4,0, 12-5,17-10]-3-dodecene
/ C2H5
8-n-Propylidene-9-ethyltetracyclo-
= CHCH2CH3 [4,4,0,12 5,17 10] -3-dodecene
2a~775~
16
CH(CH3)2
8-n-Propylidene-9-isopropyltetra-
CHCH2CH3 cyclo[4,4~0,12 5~17 lO] -3-dodecene
g 8-n-Propylidene-9-butyltetracyclo-
CH3 [4~4~o~l2 5~17~lO]-3-dodecene
8-Isopropylidenetetracyclo-
C-CH3 [4,4,0,12 5,17 l]-3-dodecene
CH3
8-Isopropylidene-9-methyltetracyclo-
C-CH3 [4,4,0,12 5,17 l]-3-dodecene
CH3
C2H5
8-Isopropylidene-9-ethyltetracyclo-
C-CH3 [4,4,0,12 5,17 l] -3-dodecene
CH3
CH(CH3)2
8-Isopropylidene-9-isopropyltetra-
C--CH3 cyclo[4,4,0,12 5,17-1] -3-dodecene
CH3
2~77'~ ~
C4Hg
8-Isopropylidene-9-butyltetra-
C-CH3 cyclo[4,4,0,12-5,17-1]-3-dodecene
CH3
Hexacyclo[6,6,1,13- 6,110-l3, o2.7, o9-l4] -4-heptadecene
derivates such as those mentioned below.
Hexacyclo[6,6,1, 13 6, l10 13 o2 7 09
4]-4-heptadecene
CH3
12-Metylhexacyclo[6,6,1,13 6,110 13,
~) o2,7 o9 l4]-4-heptadecene
C2H5
12-Ethylhexacyclo[6,6,1,13 6, llo . 13,
o2 7,09-14]-4-heptadecene
CH3
CH CH 12-Isobutylhexacyclo[6,6,1,13 6,
3~o2~7~o9~l4]-4-heptadecene
CH3 CH3
CH IH 1 6 10-Trimethyl-12-isobutyl-
CH hexacyclo[6,6,1, l3.6,l10.l3, o2 7,o9
1 14]-4-heptadecene
CH3 CH3
2~3677~6
l8
Octacyclo~8,8,0,l2 9,14 7,ll1.18,l13.16,o3.8,o12~17]_5_
docosene derivatives such as those mentioned below.
Octacyclo[8,8,0~l2 9,14.7,111.18
3.16,o3.8, ol2 l7]-5-docosene
15-Methyloctacyclo[8,8,0,12-9,
~`l~J 14 7r 111-18~ 113.16~ o3.8~ ol2.î7] -5-
docosene
C2H5 15-Ethyloctacyclo[8,8,0,12-9,
14-7~lll-l8~ll3-l6~o3.8~ol2.1
docosene
S Pentacyclo[6,6,1,13 6, o2 7,09-14~-4-hexadecene derivates
such as those mentioned below.
Pentacyclo[6,6,1,13-6,02-7,09-14]-4-
hexadecene
CH3 CH3
1,3-Dimethylpentacyclo[6,6,1,13-6,
02-7,09-14]-4-hexadecene
~ j u ~
l9
CH3
1,6-Dimethylpentacyclo[6,6,1,13 6,
o2 7,o9 14~-4-hexadecene
CH3
CH3 C~3
15,16-Dimethylpentacyclo[6,6,1,13 6,
o2 7,09 14]-4-hexadecene
Heptacyclo-5-eicosene derivatives or heptacyclo-5-
heneicosene derivatives such as those mentioned below.
Heptacyclo[8~7~o~l2.9~l4~7rlll .17
03 8~012-16]-5-eicosene
Heptacyclo[8,7,0~l2~9~l4~7~ l8
3-8, ol2 .l7]-s-heneicosene
Tri cyclo[4,3,0,12 5]-3-decene derivatives such as those
mentioned below.
2a67756
Tricyclo[4,3,0,12 5]-3-decene
CH3
2-Methyltricyclo[4,3,0,12 5]-3-
decene
5-Methyltricyclo[4,3,0,12 5]-3-
decene
CH3
Tricyclo[4,4,0,12 5]-3-undecene derivatives such as those
mentioned below.
Tricyclo[4,4,0,12 5]-3-undecene
CH3
10-Methyltricyclo[4,4,0,12 5]-3-
undecene
Pentacyclo[6,5,1,13 6,o2 7,o9 13]-4-pentadecene
derivatives such as those mentioned below.
20~775~
Pentacyclo[6,5~1,13 6,o2~7,o9~13]_4_
pentadecene
CH3 CH3
1,3--Dimethylpentacyclo[6,5,1,13 6,
~/~ o2 7, o9 l3] -4-pentadecene
CH3
1,6-Dimethylpentacyclo[6,5,1,13-6,
~,J o2 7, o9 13] -4-pentadecene
CH3
CH3 CH3
14,15-Dimethylpentacyclo[6,5,1,
3.6,o2.7,o9.13]-4-pentadecene
Diene compounds such as mentioned below.
Pentacyclo[6,5,1,13-6, o2 7,o9-13]-
~ 4,10-pentadecadiene
S Pentacyclo[4,7,0,12-5,08 13,19 12]-3-pentadecene
derivatives such as those mentioned below.
2 0 fi 7 7 ~ 6
entacyclo[4~7,orl2~5to8.l3~l9~l2]
3-pentadecene
CH3
Methyl-substituted pentacyclo[4,7,
V o 12.5,o8.13,19 12]-3-pentadecene
Heptacyclo[7~8,0~l3~6~o2.7~llo.l7~oll.l6~ll2.ls]-4-eicosene
derivatives such as those mentioned below.
Heptacyclo[7/8~o~l3.6~ o2 .7,110.17
1.16,112.15]-4-eicosene
CH3 CH3
Dimethyl-substituted heptacyclo-
[7,8,0,13-6,o2-7,ll0-17,oll.16,ll2.15]
-4-eicosene
Nonacyclo[9,10,1,14 7,o3 8~o2-lo~ol2.2l~ll3~2o~ol4~l9~ll5~l8]
5-pentacosene derivatives such as those mentioned below.
Nonacyclo[9,l0~l,l4.7,o3.8~o2.loJ ol2.21, 113.20, ol4.19, 115.18]_5_
pentacosene
? ~ 7 ~ 6
23
CH3 CH3
Trimethyl-substituted nonacyclo-
[9,10,1,14-7,o3.8,o2.10,ol2.21,
CH3 1l3.2Q~ol4.l9~ll5.l8]-5-pentacosene
Subsequently,
[B] the cycloolefin ring opening polymer or copolymer,
or hydrogenated product thereof and
[C] the cycloolefin random copolymer [C] used in the
resin compositions according to the present invention are
illustrated below in detail.
rBl CYCLOOLEFIN RING OPENING pOT.YMER OR COPOLYMER. OR
HYDRGGENATED PRODUCT THEREOF
The cycloolefin ring opening polymer and ring opening
copolymer used in the invention can be obtained by ring
opening polymerization of a cycloolefin represented by the
formula [I] mentioned above in the presence of a catalyst
comprising, for example, a halide, a nitride or an
acetylacetone compound of a metal such as ruthenium, rhodium,
palladium, osmium, indium or platinum, and a reducing agent
such as an alcohol. The resultant product may be a
homopolymer or a copolymer. For example, the resultant
homopolymer may be a polymerization product of 1,4,5,8-
dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalenes, or a
2i~677~
24
copolymeriz~tion product of said naphthalenes and norbornenes
such as bicyclo[2.2.13hept-2-ene.
The double bonds remaining in the cycloolefin ring
opening polymer and ring opening copolymer as described above
can be easily hydrogenated in the presence of a hydrogenation
catalyst. The resultant hydrogenated product provides
molding material which is more excellent in heat stability
and weathering resistance.
Any of heterogeneous catalysts or homogeneous catalysts
generally used for hydrogenation of olefins may be used as
the hydrogenation catalysts.
Useful heterogeneous catalysts include catalysts in
which a metal such as nickel, palladium or platinum, or a
catalyst prepared by supporting these metals on a carrier
such as carbon, silica, diatomaceous earth, alumina or
titanium oxide. Concrete examples of the heterogeneous
catalyst include nickel/silica, nickel/diatomaceous earth,
palladium/carbon, palladium/silica, palladium/diatomaceous
earth and palladium/alumina.
Useful homogeneous catalysts include catalysts
containing a Group VIII metal in the periodic table.
Concrete examples of the catalysts include catalysts
comprising nickel or cobalt compounds, and organometal
compounds containing metals belonging to Group I to III in
the periodic table such as nickel and cobalt, for example,
25 2 ~ 6 7 7 ~ G
nickel naphthenateJ~riethylamine, naphthenic acid n-
butyllithium naphthenate and
acetylacetonatonickel/triethylaluminum, and rhodium
compounds.
The hydrogenation reaction can be carried out in a
homogeneous or a heterogeneous system, depending on the type
of the catalysts.
The hydrogen gas pressure in the hydrogenation is
usually 1 to 150 atmospheric pressure, and the reaction
10 temperature is usually 0 to 100C, preferably 20 to 100C.
The hydrogenation ratio can be freely adjusted by
changing the hydrogen pressure, reaction temperature,
reaction time, catalyst concentration, etc. However, the
hydrogenated products used in the invention have a
hydrogenation ratio of the double bonds present in the
original non-hydrogenated polymer or copolymer of preferably
at least 50%, more preferably at least 80~ and especially at
least 90%. Especially those hydrogenated products having a
hydrogenation ratio exceeding 90% come to exhibit a
solubility parameter (SP) range different from that of the
resin before hydrogenation. Resin compositions excellent in
solvent resistance can be obtained from such a resin.
Furthermore, in the preparation of the ring opening
polymers, ring opening copolymers or hydrogenated products
thereof as mentioned above in the invention, cycloolefins
2~77~
26
other than those represented by the formula [I] can be
copoymerized. Such cycloolefins include
cyclobutene,
cyclopentene,
cyclohexene,
3,4-dimethylcyclohexene,
3-methylcyclohexene,
2-(2-methylbutyl)-1-cyclohexene,
2,3,3a,7a-tetrahydro-4,7-methano-lH-indene and
3a,5,6,7a-tetrahydro-4,7-methano-lH-indene. These other
cycloolefins can be used singly or in combination, and are
usually used in an amount of 0 to 20 mol~.
When the ring opening polymerization or copolymerization
is conducted as described above, the cycloolefin such as
represented, for example, by the formula [I] opens its ring,
and at least part of the products are considered to have a
structure represented by the following formula [II]
~-~Rls
[ I I ]
~R 6 n R Rl2 m
2i~77~
~7
wherein m, n and R1-Rl8 are as defined in the
aforementioned formula [I].
The hydrogenated product obtained by hydrogenating
double bonds is considered to have a structure represented,
for example, by the formula [III]
[III~
0 wherein m, n and R1-Rl8 are as defined in the
aforementioned formula [I].
The ring opening polymers and copolymers, and
hydrogenated products thereof can be used singly or in
combination in the present invention. Moreover, it is
preferable that these ring opening polymers, ring opening
copolymers or hydrogenated products thereof are modified with
unsaturated carboxylic acids such as maleic anhydride.
These cycloolefin ring opening polymers, ring opening
copolymers or hydrogenated products thereof [B] have an
2~77~j~
~ X
ir.trinsic viscosity [~] of desirably 0.1 to 7 dl/g as
measured in decalin at 135C and a melt flow rate of
desirably 0.01 to 150 g/10 min as measured at 260C under a
load of 2.16 kg.
CYCTOOLEFIN RANDOM COPOIIYMER rCl
The cycloolefln random copolymer [C~ contained in the
resin compositions of the invention comprises, as essential
structural units, structural units derived from ethylene and
those derived from the aforementioned cycloolefin. The
cycloolefin random copolymer [C] may also contain other
copolymerizable unsaturated monomer structural units if
desired, so long as these other structural units do not
impair the object of the invention. Unsaturated monomers
which may be copolymerized include concretely propylene, 1-
butene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-
dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-
eicosene. Of these, an a-olefin having 3 to 20 carbon atoms
is preferable. Moreover, cycloolefins and cyclodienes such
as norbornene, ethylidenenorbornene and dicyclopentadiene may
also be used. These unsaturated monomer structural units may
be contained in the resulting random copolymer in a molar
amount less than that of the structural units derived from
ethylene.
The cycloolefin random copolymer [C] contained in the
resin compositions according to the present invention
20677~
~ 9
comprises structural units derived from ethylene in an amount
of 40 to &5 mol%, preferably 50 to 75 mol%. The copolymer
[C] comprises structural units derived from the cycloolefin
in an amount of 15 to 60 mol%, preferably 25 to 50 mol%. In
5 the present invention, structural units derived from ethylene
and those derived from the cycloolefin are randomly arranged
to form a substantially linear cycloolefin random copolymer.
The fact that the aforementioned cycloolefin random copolymer
is substantially linear and has no gel-like crosslinking
10 structure can be ascertained by observing complete
dissolution of the copolymer in decalin at 135C.
The cycloolefin random copolymer [C] contained in the
resin compositions of the invention has an intrinsic
viscosity [~], as measured in decalin at 135C, of 0.05 to 10
dl/g, preferably 0.08 to 5 dl/g.
Furthermore, the cycloolefin random copolymer [C]
contained in the resin compositions of the invention has a
melt flow rate of 0.01 to 150 g/10 min as measured at 260C
under a load of 2.16 kg.
2 0 Still furthermore, the cycloolefin random copolymer [C]
contained in the cycloolefin r*sin compositions of the
invention has a softening temperature (TMA), as measured by a
thermomechanical analyzer, of at least 70C, preferably 90 to
250C and especially 100 to 200C.
~? ~ ~ ~ 7 ~ ~
3()
The cycloolefin random copolymer [C] contained in the
resin compositions of the invention has a glass transition
temperature (Tg) of usually 50 to 230C, preferably 70 to
2lOC
The cycloolefin random copolymer [C] contained in the
resin compositions of the invention has a crystallinity, as
measured by X-ray diffraction, of 0 to 10~, preferably 0 to
7% and especially 0 to 5~.
As the cycloolefin random copolymer [C] contained in the
resin compositions according to the present invention, only
the copolymers having physical properties in the above-
mentioned range may be used. However, those having physical
properties outside the above-mentioned range may also be
partly contained. In this case, when the physical properties
of the cycloolefin random copolymer [C] as a whole lie in the
above-mentioned range, the random copolymer [C] can be used.
Such a cycloolefin random copolymer [C] can be
manufactured by copolymerizing ethylene, cycloolefin, and if
necessary other a-olefin in a hydrocarbon solvent in the
presence of a catalyst formed from a hydrocarbon-soluble
vanadium compound and a halogen-containing organoaluminum
compound.
The hydrocarbon solvents used herein include aliphatic
hydrocarbons, alicyclic hydrocarbons and aromatic
hydrocarbons. Moreover, monomers which are in a liquid form
2~77~i~
3l
at the reaction temperature may be used as reaction solvents.
These solvents may be used singly or in combination.
Useful vanadium compounds used as catalysts in the
reaction include those represented by the general formula
VO(OR)aVb or V(OR)CXdl wherein R is a hydrocarbon group, 0 < a
< 3, 0 < b < 3, 2 < a+b < 3, 0 < c ~ 4, 0 < d < 4, and 3 < c
+ d < 4.
More concretely, these vanadium compounds include
VOCl3,
VO(OC2H5)C1
VO (OC2H5) 2Cl,
VO (O-iso-C3H7) Cl
VO (O-n-C4Hg) C12,
vo(oc2Hs)
1 5 VOBr2,
VCl4,
voC12,
VO(O-n-CgHg)3 , and
VCl3 20C8H170H. These vanadium compounds may be used
singly or in combination.
Adducts of the vanadium compounds represented by the
above-mentioned formula and electron donors may also be used
in place of such vanadium compounds as mentioned above.
Examples of the electron donors which form adducts with
the vanadium compounds mentioned above include oxygen-
7 7 a 6
containing electron donors such as alcohols, phenols,
ketones, aldehydes, carboxylic acids, esters of organic acids
or inorganic acids, ethers, acid amides, acid anhydrides and
alkoxysilanes, and nitrogen-containing electron donors such
5 as ammonia, amines, nitriles and isocyanates.
Useful organoaluminum -ompounds which can be used as
catalysts with the vanadium compounds as mentioned above
include those having in the molecule at least one Al-C bond.
Examples of the organoaluminum compounds usable in the
0 invention include organoaluminum compounds represented by the
formula
Rl 9eAl ( oR20 ) f HgXh
wherein R19 and R20, which may be the same or different,
are each a hydrocarbon group of 1 to 15 carbon atoms,
preferably 1 to 4 carbon atoms, X is halogen, O S e S 3, 0 S
f < 3, 0 S g < 3, 0 S h < 3, and e + f + g + h = 3, and
complex alkylation compounds of metals belonging to Group I
of the periodic table and aluminum, represented by the
formula
MlAlR2l 4
wherein Ml is Li, Na or K, R21, which may be the same or
different, are each a hydrocarbon group of 1 to 15 carbon
atoms, preferably 1 to 4 carbon atoms.
In the aforementioned reaction system, the vanadium
compounds are used in an amount of usually 0.01 to 5 g
2a~.7~ij
atom./l, preferaL~ly 0.05 to 3 g atom/l in terms of vanadium.
Moreover, the organoaluminum compounds are used so that the
ratio (Al/V) in the polymerization system of aluminum atoms
to vanadium atoms is at least 2, preferably 2 to 50 and
S especially 3 to 20.
The cycloolefin random copolymer [C] contained in the
resin compositions of the invention can be prepared, for
example, by following the procedures proposed by the present
applicant in Japanese Patent L-O-P Nos. 168708/1985,
120816/1986, 115912/1985, 115916/1986, 271308/19~6,
272216/1986, 252406/1987 and 252407/1987, and suitably
selecting the reaction conditions.
In the cycloolefin random copolymer [C] as described
above, the structural unit derived from a cycloolefin
represented by the above-mentioned formula [I] is considered
to form a recurring unit of a structure represented by the
formula [IV]
~ [IV]
7 7 ~~3 ~
wherein n, m and Ri-Rl8 are as defined in the
aforementioned formula [I].
Furthermore, in the present invention, it is preferable
that the cycloolefin ring opening polymer or copolymer, or
hydrogenated product thereof [B] as described above, or the
cycloolefin random copolymer [C] ([B] and [C] being generally
abbreviated to cycloolefin polymer) is modified with an
unsaturated carboxylic acid such as maleic anhydride. Such a
modified product can be manufactured by reacting the
0 cycloolefin polymer as described above with an unsaturated
carboxylic acid or an anhydride thereof, or a derivative of
the unsaturated carboxylic acid such as an alkyl ester
thereof. The modified cycloolefin polymer contains
structural units derived from a modifier in an amount of
usually no~ greater than 0.001 to 5% by weight. The modified
cycloolefin polymer may be prepared by graft polymerizing a
modifier to the cycloolefin polymer so that a desired
modification ratio is obtained, or by preparing a modified
product of the cycloolefin polymer having a high graft ratio
at first, and then mixing the modified product with the
unmodified cycloolefin polymer.
In the vinyl chloride resin compositions of the
invention, the ratio by weight of the total amount of the
cycloolefin ring opening polymer or copolymer, or
hydrogenated product thereof [B] and the cycloolefin random
2357~5~
copolymer [C~ ([s] + [C]) to the weiqht of the vinyl chloride
res~n [A] ~([B] + [C])~[A]} is 98/2 to 2~98, preferably 95/5
to 5/95.
Other Additives
In addition to the above-mentioned components [A], [B]
and [C], the resin compositions of the invention may contain
a rubber component for improving the impact strength thereof.
It may also contain heat stabilizers, weathering stabilizers,
antistatic agents, slip agents, anti-blocking agents, anti-
haze agents, lubricants, dyes, pigments, natural oil,
synthetic oil, wax, etc. These additives are used in
suitable amounts. Concrete examples of stabilizers to be
used as optional components include phenolic antioxidants
such as tetrakis[methylene-3-(3,5-di-tert-butyl-4-
hydroxyphenyl)propionate]methane, alkyl ~-(3,5-di-tert-butyl-
4-hydroxyphenyl)propionate and 2,2'-oxamidobis[ethyl-3-(3,5-
di-tert-butyl-4-hydroxyphenyl)]propionate, zinc stearate,
calcium stearate, and aliphatic acid esters of polyhydric
alcohols such as glycerin monostearate, glycerin monolaurate,
glycerin distearate, pentaerythritol monostearate,
pentaerythritol distearate and pentaerythritol tristearate.
Useful stabilizers include lead salts, metallic soaps
and organotin compounds. Concrete examples of the lead salts
include white lead, tribasic lead sulfate, dibasic lead
~77~6
~6
phosphite, dibasic lead phthalate, lead silicate or
coprecipitates of these compounds with silica gel.
The metallic soaps concretely include salts of organic
acids such as stearic acid, 12-hydroxystearic acid, lauric
5 acid, ricinoleic acid, naphthenic acid and 2-ethylhexanoic
acid and metals such as lead, cadmium, barium, zinc and
calcium.
Useful organotin compounds include concretely dibutyltin
laurate, dibutyltin maleate and dibutyltin mercaptide.
These stabilizers may be used singly or in combination.
One of the examples of the combination is a combination of
tetrakis[methylene-3-(3,5-di-tert-butyl-4-
hydroxyphenyl)propionate]methane, zinc stearate, glycerin
monostearate and a lead salt.
In the present invention, the use of phenolic
antioxidants and aliphatic acid esters of polyhydric alcohols
in combination is particularly preferred. As the aliphatic
acid ester of a polyhydric alcohol, an ester in which the
alcoholic hydroxy group of the alcohol (at least trihydric)
is partially esterified is preferred.
Concrete examples of the aliphatic acid ester of a
polyhydric alcohol include aliphatic acid esters of glycerin
such as glycerin monostearate, glycerin monolaurate, glycerin
monomyristate, glycerin monopalmitate, glycerin distearate
and glycerin dilaurate, and aliphatic acid esters of
2~3'~77~
37
pentaerythritol such as pentaerythritol monostearate,
pentaerythritol monolaurate, pentaerythritol dilaurate,
pentaerythritol distearate and pentaerythritol tristearate.
Such phenolic antioxidants are used in an amount, based
on 100 parts by weight of the vinyl chloride composition, of
0.01 to 10 parts by weight, preferably 0.05 to 3 parts by
weight and especially 0.1 to 1 part by weight. The aliphatic
acid esters of polyhydric alcohols are used in an amount,
based on 100 parts by weight of the resin composition, of
0.01 to 10 parts by weight, preferably 0.05 to 3 parts by
weight.
The vinyl chloride resin compositions of the invention
may be incorporated with fillers, so long as the
incorporation does not impair the object of the invention,
1~ such as silica, diatomaceous earth, alumina, titanium oxide,
magnesium oxide, pumice powder, pumice balloons, aluminum
hydroxide, magnesium hydroxide, basic magnesium carbonate,
dolomite, calcium sulfate, potassium titanate, barium
sulfate, calcium sulfite, talc, clay, mica, asbestos, glass
fibers, glass flakes, glass beads, calcium silicate,
montmorillonite, bentonite, graphite, aluminum powder,
molybdenum sulfide, boron fibers, silicon carbide fibers,
polyethylene fibers, polypropylene fibers, polyester fibers
and polyamide fibers.
7 ~ ~
~8
The vinyl chloride resin compositions of the invention
may also be incorporated with olefin resin (including rubber)
derived from a hydrocarbon having one or more of unsaturated
bonds.
Such polymers concretely include
homopolymers such as polyethylene, polypropylene,
polyisobutylene, polymethylbutene-1, poly-4-methylpentene-1,
polybutene-1, polyisoprene, polybutadiene and polystyrene;
copolymers such as ethylene/propylene copolymer,
propylene/butene-1 copolymer, propylene/isobutylene
copolymer, styrene/isobutylene copolymer, styrene/butadiene
copolymer and ethylene/propylene/diene copolymer, e.g.,
ethylene/propylene/hexadiene copolymer,
ethylene/propylene/cyclopentadiene copolymer and
5 ethylene/propylene/ethylidenenorbornene copolymer, or
blends, grafted polymers, crosslinking products and
block copolymers of the above-mentioned polymers.
Known methods can be applied to the preparation of the
vinyl chloride compositions of the invention. Examples of
0 the method for the preparation thereof include
a method wherein the vinyl chloride resin component [A],
the cycloolefin ring opening polymer or copolymer, or
hydrogenated product thereof [B], and
2~1~7 ~
the cycloolefin random copolymer [C], and if desired
other components are mechanically blended by an extruder,
kneader, etc.,
a method wherein the components mentioned above are
simultaneously dissolved into a suitable good solvent, for
example, a hydrocarbon solvent such as hexane, heptane,
decane, cyclohexane, benzene, toluene or xylene or the
components are each separately dissolved into separate
solvents and the resultant solutions are mixed, and the
solvent or solvents are removed, and
a method wherein these two methods are combined.
The vinyl chloride resin compositions according to the
present invention contain a cycloolefin polymer having a high
heat distortion temperature, a high pencil hardness and a low
15 mold shrinkage factor in addition to the vinyl chloride resin
component [A]. Accordingly, the resulting vinyl chloride
resin composition has a high heat distortion temperature
while maintaining various characteristics of the vinyl
chloride resin.
The vinyl chloride resin compositions according to the
present invention have various characteristics as described
above, and therefore can be extensively used in the field
requiring heat-resistant properties in addition to the field
where conventional vinyl chloride resin is used.
MQlded Articles
2~77~6
Molded articles formed from the vinyl chloride resln
compositions according to the present invention have an
excellent balance among heat resistance, heat aging
characteristics, mechanical properties, dielectric
S properties, chemical resistance and solvent resistance.
Concrete examples of the molded articles include
(1) automobile parts:
instrument panels, console boxes, meter clusters,
column covers, grille door mirrors, fenders, bonnets and
radiator grilles;
(2) machine housings:
tools (e.g., electric tools), business machines
(e.g., word processors, personal computers, copying machines,
printers, FDD and CRT), precision instruments (e.g., cameras)
and electrical appliances (e.g., electronic ovens, electric
rice cookers, refrigerators, pots and cleaners); and
(3) machine parts:
scirocco fans for air conditioners.
The vinyl chloride resin compositions according to the
present invention can be molded into molded articles by
extrusion molding, injection mGlding, blow molding, rotary
molding, etc. using, for example, a single screw extruder, a
vented extruder, a twin screw extruder, a conical twin screw
extruder, a Ko-kneader, a platificator, a mixtruder, a twin
2~7~
cor.ical screw e~truder, a planetary screw extruder, a gear
extruder and a screwless extruder.
EFFECT OF THE INVFNTION
The vinyl chloride resin compositions according to the
present invention comprise a vinyl chloride resin and a
cycloolefin polymer as illustrated above. Accordingly, the
present invention can provide vinyl chloride resin
compositions from which molded articles required to have heat
resistance as well as flame retarding properties and chemical
resistance can be prepared without losing the characteristics
of polyvinyl chloride.
F~xamples
The present invention is further illustrated below with
reference to examples, but it should be construed that the
present invention is in no way limited to these examples.
Methods for measuring various physical properties and
evaluation methods of the resin compositions of the present
invention are described below.
(1) Preparation of test p1eces
Resin compositions are molded into test pieces
under the following conditions using an injection molding
machine (trade name of IS-35P, manufactured by Toshiba Kikai
K.K. ):
a cylinder temperature of 220C;
42 2~g77~)6
a mold temperature of 60C;
primary injection/secondary injection pressures of
1000/800 kg/cm2;
an injection speed (primary) of 30 mm/sec;
a screw rotation speed of 150 rpm; and
a cycle [(injection + dwell)/cooling] of 7/15 sec.
The test pieces are then allowed to stand at room
temperature for 48 hours, and used for measurements.
(2) Melt flow rate (MFRT)
The melt flow rate is measured according to ASTM D
1238 at a predetermined temperature of TC under a load of
2.16 kg.
(3) Tensile test
The tensile test was conducted according to ASTM D
15 638 under the following conditions:
the shape of the test pieces: ASTM Type IV, with a
thickness of 2 mm;
a test speed of 50 mm/min; and
a test t~mperature of 23C.
(4) Heat deflecticn temperature (HDT)
The heat deflection temperature is measured
according to ASTM D 648 under the following conditions:
the shape of the test piece: 5xl/4xl/2t inch; and
a load of 264 psi.
(5) Softening temperature (TMA)
2 ~ ~ r~ 7 ~j 6
~3
The softening temperature i5 measured by observing the
thermal deformatio~ behavior of a sheet of 1 mm thick using a
Thermo Mechanical Analyzer (trade name, manufactured by
DuPont~. That ls, a quartz needle is placed on the sheet,
and the sheet was heated at a rate of SC/min while a load of
49 g is applied to the needle. The TMA is a temperature at
which the needle penetrates the sheet to the depth of 0.635
mm.
(6) Glass transition temperature (Tg)
0 The glass transition temperature is measured by heating
the test piece at a rate of 10C/min using DSC 20 (trade
name, manufactured by Seiko Denshi Kogyo K.K.).
(7) Flame retardance
The flame retardance of the test piece having 1/8 inch
thick is measured according to the test method of UL-94.
~xample 1
A powder mixture (3 kg) of 100 parts by weight of a
polyvinyl chloride (polymerization degree of 720, MFRlgo of
360 g/10 min, glass transition temperature Tg of 68C), and 3
parts by weight of tribasic lead sulfate and 1 part by weight
of lead stearate as stablizers was mixed with 1 kg of pellets
prepared from a mixture of 100 parts by weight of a random
copolymer as a cycloolefin polymer component of ethylene and
1,4,5,8-dimethono-1,2,3,4,4a,5,8,8a-octahydronaphthalene
'2~)~77~6
44
(structure : ~ abbreviated to DMON hereinafter) as
a cycloolefin polymer component (ethylene content of 62 mol%
as measured by l3C-NMR, MFR260 of 35 g/min, intrinsic viscosity
[~] of 0.47 dl/g as measured in decalin at 135C, softening
temperature (TMA) of 148C, glass transition temperature Tg
of 137C) and 0.5 part by weight of tetrakis[methylene-3-
(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane as a
stabilizer. The mixture was melt blended by a twin-screw
extruder (trade name of PCM 45, manufactured by Ikegai Tekko
K.K.) at a cylinder temperature of 170C, and pelletized by a
pelletizer. Test pieces were prepared from the pellets thus
obtained by the method mentioned above, and the physical
properties thereof were measured.
The results are shown in Table 1.
Example 2
Example 1 was repeated except that the same polyvinyl
chloride-containing powder and the same cycloolefin
copolymer-containing pellets as in Example 1 were used in the
proportion by weight of 1/1 to melt blend and obtain test
pieces. The physical properties of the test pieces were
measured.
The results are shown in Table 1.
Example 3
7 ~ 6
4~
Example 1 was repeated except that the same polyvinyl
chloride-containing powder and the same cycloolefin
copolymer-containing pellets as in Example 1 were used in the
proportion by weight of 1/1, and that 15 parts by weight of
antimony trioxide and 1 part by weight of
polytetrafluoroethylene powder were added as flame retarding
assistants to 100 parts by weight of the mixture of pellets
to melt blend and obtain test pieces. The physical
properties of the test pieces were measured.
The results are shown in Table 1.
Com~arative Example 1
Test pieces were prepared by using only the same
polyvinyl chloride as in Example 1, and the physical
properties thereof were measured.
lS The results are shown in Table 1.
Example 4
Example 1 was repeated except that a vinyl
chloride/vinyl acetate copolymer containing 5 mol% of vinyl
acetate (polymerization degree of 750, MERIgo Of 370 g/10 min,
glass transition temperature Tg of 58C) was used in place of
the polyvinyl chloride in Example 1, and 3 kg of the powder
containing this copolymer and 1 kg of the same cycloolefin
copolymer-containing pellets were mixed to obtain test
pieces. The physical properties of the test pieces were
measured.
46 ~067~6
The results are shown in Table 1.
Comparative Example 2
Test pieces were prepared by using only the same vinyl
chloride/vinyl acetate copolymer as in Example 4, and the
S physical properties were measured.
The results are shown in Table 1.
Example 5
Example 1 was repeated except that an ethylene/DMON
copolymer ~ethylene content of 71 mol% as measured by 13C-NMR,
MFR260 of 20 g/min, intrinsic viscosity [~] of 0.6 dl/g,
softening temperature (TM~) of 115C, glass transition
temperature Tg of 98C) was used in place of the
ethylene/DMON copolymer in Example 1, and 1 kg of the pellets
containing this cycloolefin copolymer was mixed with 3 kg of
the same polyvinyl chloride containing powder to obtain test
pieces. The physical properties of the test pieces were
measured.
The results are shown in Table 1.
~ i3 6 ~ 7 ~ ~
Table 1
Polyvinyl chloride Tensile ¦ Flame
Example ~copolymer ~ bre~k ( C) retardance
Example 1 75/25 53080 V-O
Example 2 50/50 490100 V-O
Example 3 25/75 540125 V-O
Comp. Example 1 100/0 520 70 V-O
Example 4 75/25 49070 V-O
Comp. Example 2 100/0 510 60 V-O
Example 5 75/25 55075 V-O
