Note: Descriptions are shown in the official language in which they were submitted.
CA 02194395 2005-10-12
72932-243
1
MULTI-LAYER LAMINATES CONTAINING
CYCLOOLEFIN RESIN LAYER AND USES THEREOF
S The present invention relates to multi-layer laminates
which comprise a cycloolefin resin layer and a polymer
layer and have a low oxygen permeability. The invention
also relates to uses of the multi-layer laminates.
IO ~~CKGROLTND PLRT
Packaging materials for daily necessaries, general
merchandise, foods, tablet drugs, etc. are required to have
various properties such as transparency, moisture
resistance, heat-sealing properties, vacuum or pressure
15 formability and twist-wrapping properties. However, use of
only one kind of a resin cannot meet these requirements.
Therefore, multi-layer laminates each comprising a sheet or
a film of a certain resin and a sheet or a film of other
resin with different properties have been widely employed.
20 Also in the field of packaging materials, recycling of raw
materials or incineration of the packaging materials has
been recently paid much attention. From this viewpoint,
polyolefin resins tend to be preferably employed as the
packaging materials.
25 Of the polyolefin resins, cycloolefin resins are
particularly suitable for the packaging materials, because
they have excellent transparency, moisture resistance,
vacuum or pressure formability. and dead fold properties and
2194395
2
they can be recycled or incinerated without any problem.
However, since the cycloolefin resins are amorphous, they
rapidly soften at temperatures close to their glass
transition temperatures to cause lowering of elastic
S modulus and strength. Therefore, the molding conditions in
the processes of heat-sealing, inflation and vacuum or
pressure forming are restricted.
Meanwhile, the packaging materials used for packaging
foods are desired to have low oxygen permeability because
the objects packaged by the packaging materials easily
deteriorate when they are brought into contact with oxygen
of air. The cycloolefin resins have excellent properties
as the packaging materials, e.g., high moldability and
transparency. However, in the uses where high oxygen
barrier properties are required, for example, in the uses
for food-packaging, they are desired to be further improved
in these properties.
Containers using thermoplastic resins are described
in, for example, Japanese Patent Publication No.
2 0 104732/1994 and Japanese Patent Laid-Open Publication No.
1352/1984. These publications disclose laminating of an
ethylene/vinyl alcohol copolymer (EVOH) and other
thermoplastic resin, and the thermoplastic resins laminated
together with the EVOH are, for example, polyesters such as
PET and polyamides such as nylon. Japanese Patent Laid-
Open Publication No. 293159/1993 discloses a container made
of a laminate of a resin and EVOH, and the resin used
_ ~ 194395
3
herein is a hydrogenation product of a ring opening polymer
of a cycloolefin.
It is an object of the present invention to provide a
multi-layer laminate which has excellent formability,
S transparency, interlaminar bond properties, moisture
resistance, flexibility, tearability, heat-sealing
properties and dead fold properties and which is well-
balanced between oxygen permeability and transparency. It
is another object of the invention to provide a film, a
sheet and a packaging material each of which is formed from
the multi-layer laminate.
DISCLOSURE OF THE INVENTION
The multi-layer laminate of the invention comprises:
(A) a layer formed from at least one cycloolefin resin
selected from the group consisting of
(a-1) an ethylene/cycloolefin random copolymer
comprising a cycloolefin represented by the following
formula [1] or [2] and ethylene and
2 0 (a-2) a graft modified product of the
ethylene/cycloolefin random copolymer (a-1), or
a layer formed from a cycloolefin resin composition
comprising at least one cycloolefin resin selected from the
group consisting of the ethylene/cycloolefin random
copolymer (a-1) and the graft modified product (a-2) and
(b) a polyolefin,
and
_ 219435
4
(B) a polymer layer having an oxygen permeability, as
measured at a temperature of 23 °C and RH of 0 %, of not
more than 10 cc(STP)~mm/m2~24hr~atm,
said multi-layer laminate having a moisture
S permeability of not more than 0~2 g~mm/m2~24hr~atm and an
oxygen permeability of not more than 5
cc(STP) ~mm/m2~24hr~atm;
R1 I Ra Rb~ ~ R7 I R11
R15
R3 L \ R9 , R13 R16
17
R4 Rlo R14 R
Ris
R2 R5 R6 J R8 L R12 .J
ill
wherein n is 0 or 1; m is 0 or a positive integer; q is 0
or 1; R1 to R18, Ra and Rb are each independently an atom or
a group selected from the group consisting of a hydrogen
atom, a halogen atom and a hydrocarbon group; R15 to R18 may
be bonded to each other to form a single ring or plural
rings each of which may have a double bond; R15 and R16, or
R17 and R1$ may form an alkylidene group; and when q is 0,
the bonding hands are bonded to each other to form a five-
membered ring;
~ 19439'5
R26 R27
I~
R2a ~ ~ ~ ~ R~
I
k
R 1 ~ (CH~h ~ R23
Rta
R17
R21- R22
Rt8
I I.
Rg R12 ~---~ J
m
R t9 R2o
wherein m is 0 or a positive integer; h is 0 or a positive
integer; j and k are each 0, 1 or 2; R7 to R15 and R17 to R18
5 are each independently an atom or a group selected from the
group consisting of a hydrogen atom, a halogen atom and a
hydrocarbon group; and R19 to R27 are each independently an
atom or a group selected from the group consisting of a
hydrogen atom, a halogen atom, a hydrocarbon group and an
alkoxy group.
The multi-layer laminate of the invention has a layer
containing a cycloolefin resin and a polymer layer having
low oxygen permeability, so that the laminate shows
excellent formability, transparency, interlaminar bond
properties, moisture resistance, flexibility, tearability,
heat-sealing properties and dead fold properties. Besides,
the multi-layer laminate has an advantage in that the
laminate is hardly permeated by gasses, particularly
oxygen.
219439
6
BEST MODE FOR CARRYING OUT THE INVENTION
The multi-layer laminate of the present invention and
uses thereof will be described in detail hereinafter.
S First of all, resins for forming the multi-layer
laminate of the invention are described.
(A) Cycloolefin resin and ~ycloolefin resin composition
The cycloolefin resin and the cycloolefin resin
composition comprising the cycloolefin resin and a
polyolefin (A), which are raw materials for forming one of
the layers of the multi-layer laminate of the invention,
are described below.
The cycloolefin resin used in the invention includes:
(a-1) a random copolymer of ethylene and a cycloolefin
represented by the formula [1], and
(a-2) a graft modified product of the random copolymer
(a-1) .
The cycloolefin resin used in the invention has a
softening temperature (TMA), as measured by a thermal
2 0 mechanical analyzer, of usually not lower than -30 °C,
preferably 0 to 180 °C, more preferably 50 to 180 °C. The
softening temperature (TMA) is a temperature at which a
quartz needle 1.0 mm in diameter, which is put on a sheet
under a load of 49 g, penetrates 0.635 mm into the sheet,
when the temperature of the sheet is raised at a rate of 5
°C/min .
The cycloolefin resin has an intrinsic viscosity [
as measured in decalin at 135 °C, of usually 0.01 to 10
' 2194395
dl/g, preferably 0.05 to 2.0 dl/g, more preferably 0.4 to
1.2 dl/g.
The cycloolefin resin has a glass transition point
(Tg) of usually not lower than -30 °C, preferably -10 to
170 °C, and has a crystallinity, as measured by X-ray
diffractometry, of usually 0 to 20 %, preferably 0 to 2 %.
The cycloolefin used for forming the cycloolefin resin
is described below.
As the cycloolefin, a compound represented by the
following formula [1] or [2] is employed.
R15
R16
R17
R1s
n_ J 1~ _ _
[1]
In the formula [1], n is 0 or l, and m is 0 or a
positive integer.
R1 to R18, Ra and Rb are each independently an atom or
a group selected from the group consisting of a hydrogen
atom, a halogen atom and a hydrocarbon group.
The halogen atom is fluorine, chlorine, bromine or
iodine.
2 0 Examples of the hydrocarbon groups include alkyl
groups of 1 to 20 carbon atoms, halogenated alkyl groups of
1 to 20 carbon atoms, cycloalkyl groups of 3 to 15 carbon
219395
s
atoms and aromatic hydrocarbon groups. More specifically,
there can be mentioned:
alkyl groups, such as methyl, ethyl, propyl,
isopropyl, amyl, hexyl, octyl, decyl, dodecyl and
S octadecyl;
halogenated alkyl groups, such as those wherein at
least a part of the hydrogen atoms forming the above-
exemplified alkyl groups are replaced with fluorine atoms,
chlorine atoms, bromine atoms or iodine atoms;
cycloalkyl groups, such as cyclohexyl; and
aromatic hydrocarbon groups, such as phenyl and
naphthyl.
In the formula [ 1 ] , R15 and R16, Rl~ and R18, R15 and
Rl~, Rls and Rla, Ris and R18, or Rls and Rl~ may be bonded to
each other to form (in cooperation) a single ring or plural
rings, and the single ring or the plural rings may have a
double bond.
Examples of such a single ring or such plural rings
are described below.
219395
9
1 1 1 1 1
2 2 / 2 2 2
_~ ~° z o
In the above examples, the carbon atoms numbered with
1 or 2 are each a carbon atom to which R15 (Ris) or R17 (Ri$)
in the formula [1] is bonded.
R15 and R16, or Rl~ and Rla may form an alkylidene
group. The alkylidene group is usually an alkylidene group
of 2 to 20 carbon atoms. Examples of such alkylidene
groups include ethylidene, propylidene and isopropylidene.
Of the cycloolefins represented by the formula [1], a
cycloolefin represented by the following formula [1-1] is
preferable.
R15
R16
R i'7
Ris
__ __ m [1-1]
219395
to
In the formula [1-1] n, m and R1 to R18 have the same
S
meanings as in the formula [1].
Also employable as the cycloolefin is a compound
represented by the following formula [2].
R26 R27
I~
R24 ~ R25
R~ Ri1
Ris I I k
R9 ~ R 1 ~ OH2)h ~ R23
R10 R14
R17
i R21-~ R~
R1s
i I.
Rs R12 r---~ .l
m
Ri9 R2o [ 2 ]
In the formula [2], m is 0 or a positive integer; h is
0 or a positive integer; j and k are each 0, 1 or 2; R~ to
R15 and R17 to R18 have the same meanings as in the formula
[1]; R19 to Rz~ are each independently an atom or a group
selected from the group consisting of a hydrogen atom, a
halogen atom, a hydrocarbon group and an alkoxy group.
The halogen atom is the same halogen atom as in the
formula [1].
Examples of the hydrocarbon groups indicated by R19 to
R2~ in the formula [2] include alkyl groups of 1 to 20
carbon atoms, halogenated alkyl groups of 1 to 20 carbon
atoms, cycloalkyl groups of 3 to 15 carbon atoms and
2 o aromatic hydrocarbon groups.
-- 219439
m
More specifically, there can be mentioned:
alkyl groups, such as methyl, ethyl, propyl,
isopropyl, amyl, hexyl, octyl, decyl, dodecyl and
octadecyl;
halogenated alkyl groups, such as those wherein at
least a part of the hydrogen atoms forming the above-
exemplified alkyl groups are replaced with fluorine atoms,
chlorine atoms, bromine atoms or iodine atoms;
cycloalkyl groups, such as cyclohexyl; and
aromatic hydrocarbon groups, such as aryl groups and
aralkyl groups, e.g., phenyl, tolyl, naphthyl, benzyl and
phenylethyl.
Examples of the alkoxy groups include methoxy, ethoxy
and propoxy.
A carbon atom to which R1~ and R1$ are bonded may be
linked to a carbon atom to which R21 is bonded or a carbon
atom to which R19 is bonded, directly or through an
alkylene group of 1 to 3 carbon atoms. That is, when the
above-mentioned two carbon atoms are linked through an
2 0 alkylene group, the groups indicated by R1~ and R21 or the
groups indicated by R1$ and R19 form in cooperation any
alkylene group of a methylene group (-CH2-), an ethylene
group (-CH2CH2-) and a trimethylene group (-CH2CHZCH2-) .
In case of J=k=0, R23 and Rz~, or R23 and R2~ may be
bonded to each other to form a single aromatic ring or
plural aromatic rings. Examples of the single or plural
aromatic rings in case of j=k=0 include the following
_ 2194395
12
groups wherein R23 and R2o further form aromatic rings in
cooperation.
~H2 tr 0 -f CH2
0
-(CH2
S
In the above formulas, h has the same meaning as that
of h in the formula [2].
Listed below are examples of the cycloolefins
represented by the formula [1] or [2].
Bicyclo[2.2.1]hepto-2-ene derivatives,
Tetracyclo [ 4 . 4 . 0 .12, 5 .17, to ] -3-dodecene derivatives,
Hexacyclo [ 6 . 6 .1.13, 6 . llo,13 , 02, ~ . 09,14 ] _4-heptadecene
derivatives,
Octacyclo [ 8 . 8 . 0 . 12, 9 . 14, 7 . 111, 18 . 113, is . 03, 8 . 012,1 ]
_5_
docosene derivatives,
Pentacyclo [ 6 . 6 .1 .13, 6 . 02, ~ . 09.14 ] _4-hexadecene
derivatives,
Heptacyclo-5-eicosene derivatives,
Heptacyclo-5-heneicosene derivatives,
Tricyclo [4 .3.0 .12,5] -3-decene derivatives,
Tricyclo[4.4Ø12,5]-3-undecene derivatives,
Pentacyclo [ 6 . 5 .1 .13, 6 . 02, ~ . 09,13] -4-pentadecene
derivatives,
Pentacyclopentadecadiene derivatives,
219495
Pentacyclo [ 7 . 4 . 0 .12, 5 .19~ 12 . 08~ 13] _3_pentadecene
derivatives,
Heptacyclo [ 8 . 7 . 0 .13~ 6 .110,17 .112,15 . 02, ~ . 011, ls] -4-eicosene
derivatives,
NOriaCyClO [ 10 . 9 . 1 . 14, ~ . 113, 20 . 115, 18 . p3, 8 , p2,10 , p12, 21
. p14, 19 ]
5-pentacosene derivatives,
Pentacyclo [ 8 . 4 . 0 .12~ 5 .19~ 12 . 08,13 ] -3-hexadecene
derivatives,
Heptacyclo [ 8 . 8 . 0 . 14, ~ . 111, 18 . 113, is . p3, 8 . 012,17 ] _5_
heneicosene derivatives,
NOriaCyClO [10 .10 .1 .15~8. 114,21.116,19_ p2,11, p4,9 _ p13,22, p15,20]
-5-hexacosene derivatives,
1,4-Methano-1,4,4a,9a-tetrahydrofluorene derivatives,
1,4-Methano-1,4,4a,5,10,10a-hexahydroanthracene
derivatives, and
Cyclopentadiene-acenaphthylene addition products.
Listed below are more specific examples of the
cycloolefins represented by the formula [1] or [2].
The bicyclo[2.2.1]kept-2-ene derivatives such as:
Bicyclo[2.2.1]kept-2-ene
CH3 6-Methylbicyclo[2.2.1]kept-2-
ene
CHg 5, 6-Dimethylbicyclo [2 .2 . 1] -
CH hept-2-ene
3
219395
14
CH3
1-Methylbicyclo[2.2.1]kept-2-
ene
C2H5 6-Ethylbicyclo[2.2.1]hept-2-
ene
nC4Hg 6-n-Butylbicyclo[2.2.1]hept-
2-ene
1C4H9 6-Isobutylbicyclo[2.2.1]hept-
2-ene
CH3
7-Methylbicyclo[2.2.1]kept-2-
ene;
the tetrocyclo[4.4Ø12~5.1~~lo]-3-dodecene derivatives such
as:
Tetracyclo [4 .4 . 0.12~5.1.10] -
3-dodecene,
8-Methyltetracyclo
[4 . 4 . 0 .12~ 5 .1~~ io] -3-dodecene
CH3
8-Ethyltetracyclo
[4 .4 .0 .12~5.1.10] -3-dodecene
C2H5
2194395
8-Propyltetracyclo
C3H~ [4.4Ø12~5.1.10]-3-dodecene
8-Butyltetracyclo
- C4H9 [4.4Ø12~5.1~.10]-3-dodecene
8-Isobutyltetracyclo-
' H3
CH2CH [ 4 . 4 . 0 .12~ 5 .1~. to ] -3-dodecene
CH3
8-Hexyltetracyclo
[ 4 . 4 . 0 .12~ 5 .1.10 ] -3-dodecene
C6H13
8-Cyclohexyltetracyclo-
[ 4 . 4 . 0 .12 ~ 5 .1 x.10 ] -3-dodecene
8-Stearyltetracyclo-
[4 . 4 .0 .12~5.1~.10] -3-dodecene
ClaH3z
CH3
5,10-Dimethyltetracyclo-
[ 4 . 4 . 0 .12~ 5 .1~~ to ] -3-dodecene
CH3
i H3 i H3
2,10-Dimethyltetracyclo-
[4 . 4 . 0 .12~ 5 .1~~ l0] -3-dodecene
21g4395
16
CH3
8,9-Dimethyltetracyclo-
[ 4 . 4 . 0 .12 ~ 5 .1~. to ] -3-dodecene
CH3
CH3
8-Ethyl-9-methyltetracyclo-
[ 4 . 4 . 0 .12 ~ 5 .1.10 ] -3-dodecene
C2H5
CH3 CH3
11,12-Dimethyltetracyclo-
[ 4 . 4 . 0 .12 ~ 5 .1.10 ] -3-dodecene
CH3
CH3
2,7,9-Trimethyltetracyclo-
[ 4 . 4 . 0 .12~ 5 .1.10 ] -3-dodecene
CH3
CH3
C2H5 9-Ethyl-2,7-
dimethyltetracyclo-
[ 4 . 4 . 0 .12~ 5 .1.10 ] -3-dodecene
CH3
CH3 i H3
CH2CH g-Isobutyl-2,7-
dimethyltetracyclo-
CH3
[4 . 4 . 0 .12~ 5.1~~ lo] -3-dodecene
CH3
CH3 CH3
CHg 9,11,12-Trimethyltetracyclo-
[ 4 . 4 . 0 .12 ~ 5 .1.10 ] -3-dodecene
-- 219495
m
CH3 CH3
9-Ethyl-11,12-
C2H5 dimethyltetracyclo-
[ 4 . 4 . 0 .12~ 5 .1.10 ] -3-dodecene
CH3 CH3 CH3
9-Isobutyl-11,12-
CH2CH
dimethyltetracyclo-
[ 4 . 4 . 0 .12 ~ S .1~. to ] -3-dodecene
CH3
CH3
5, 8, 9, 10-
CH3 Tetramethyltetracyclo-
CH3 [4 .4 .0 .12~5.1.10] -3-dodecene
CH3
8-Ethylidenetetracyclo-
CHCHg [ 4 . 4 . 0 .12~5 .1~~ 10 ] -3-dodecene
8-Ethylidene-9-
CHg methyltetracyclo-
CHCH3 [ 4 . 4 . 0 .12~ 5 .1~ ~ l0 ] -3-dodecene
C2H5
8-Ethylidene-9-
ethyltetracyclo-
CHCHg [4.4Ø12~5.1~.1o]-3-dodecene
CH ( CH3 ) 2
8-Ethylidene-9-
isopropyltetracyclo-
CHCH3 [4 . 4 . 0 .12~ 5. l~.lo] -3-dodecene
C4H9
8-Ethylidene-9-
butyltetracyclo-
CHCH3 [ 4 . 4 . 0 .12~ 5 .1.10 ] -3-dodecene
2~ 9~39~
18
8-n-Propylidenetetracyclo-
CHCH2CH3 [4.4Ø12~5.1~.10]-3-dodecene
CH3
8-n-Propylidene-9-
methyltetracyclo-
CHCH2CH3 [ 4 . 4 . 0 .12 ~ 5 .1~ ~ to ] -3-dodecene
C2H5
8-n-Propylidene-9-
ethyltetracyclo-
CHCH2CH3 [ 4 . 4 . 0 .12 ~ 5 .1~ ~ to ] -3-dodecene
CH ( CH3 ) 2
8-n-Propylidene-9-
isopropyltetracyclo
CHCH2CH3 f4.4.0 .12~5.1~.10] _3-dodecene
C4H9
8-n-Propylidene-9-
butyltetracyclo-
CHCH2CHg [4.4Ø12~5.1~~lo]-3-dodecene
8-Isopropylidenetetracyclo-
C-CH3 [ 4 . 4 . 0 .12 ~ 5 .1 ~ ~ l o ] -3-dodecene
CH3
CH3
8-Isopropylidene-9-
methyltetracyclo-
i -CH3 [4.4Ø12~5.1~.1o]-3-dodecene
CH3
C2H5
8-Isopropylidene-9-
ethyltetracyclo-
C-CH3 [4 . 4 . 0 .12~ 5 .1~~ to] -3-dodecene
CH3
219~.39~
19
CH(CH3)2 8-Isopropylidene-9-
isopropyltetra-
cyclo [4 .4 Ø12~5.17~10] -3-
C-CH3 dodecene
I
CH3
C4Hg
8-Isopropylidene-9-
butyltetracyclo-
C-CH3 ( 4 . 4 . 0 .12 5 . 17,10 ] -3_
dodecene;
CH3
8-Chlorotetracyclo
[ 4 . 4 . 0 .12 ~ 5 .17 ~ 10 ] -3-dodecene
CQ
8-Bromotetracyclo
[ 4 . 4 . 0 .12 ~ 5 .17 ~ l0 ] -3-dodecene
Br
8-Fluorotetracyclo
[4 . 4 . 0 .12~ 5 .17~ 10] -3-dodecene
F
CQ
8,9-Dichlorotetracyclo-
[ 4 . 4 . 0 .12 ~ 5 .17 ~ 10 ] -3-dodecene
CQ
the hexacyclo [ 6 . 6 . 1 . 13~ 6 _ 110, 13 _ p2, 7 _ p 9, 14 ~ _4-heptadecene
derivatives such as:
Hexacyclo
[6.6.1.136.110,13_02,7.09,14]
-4-heptadecene
~194~~5
CH3
12-Methylhexacyclo
[6.6.1.13~6.11~.13.02.7.09,14]
-4-heptadecene
C2H5
12-Ethylhexacyclo
[6.6.1.13~6.11~.13_02,7.09,14]
-4-heptadecene
CH3
12-Isobutylhexacyclo
-CH21H [6.6.1.13~6.110.13,p2.7.09,14]
-4-heptadecene
CH3
CH3 i H3
1,6,10-Trimethyl-12-
CH CH isobutylhexacyclo
21 [6.6.1.13~6.11~.13.p2,7.O9~14]
CH3 -4-heptadecene;
CH3 CH3
the OCtacyClO [ 8 . 8 . 0 . 12~ 9 . 14~ 7 _ 111, 18 . 113, 16 . 03, 8 . 012,
17 ] -5_
docosene derivatives such as:
Octacyclo
[8.8Ø129.14~7-111,18.113,16.
03, 8 . 012, 17 ] -5-docosene
CH3 15-Methyloctacyclo
[8.8Ø12~9.14~7.111.18.
113, 16. 03, 8 . 012, 17 ] -5-docosene
C2H5 15-Ethyloctacyclo
[8.8Ø12~9.14~7.111.18.
113, 16 . 03, 8 . 012, 17 ] _5_
docosene;
- 2194395
21
the pentacyclo[6.6.1.13~6.027.09~14]_4-hexadecene
derivatives such as:
Pentacyclo
[ 6 . 6 . 1 . 13~ 6 . 02~ 7 . O9~ 14] -4_
hexadecene
CH3 CH3
1,3-Dimethylpentacyclo-
[6.6.1.13~6.02~7.09~14]-4_
hexadecene
CH3 _
1,6-Dimethylpentacyclo-
[6.6.1.13~6.02~7.09~14]-4_
hexadecene
CH3
CH3 CH3
15,16-Dimethylpentacyclo-
[6.6.1.13~6.02~7.09~14]-4_
hexadecene;
S
the hepacyclo-5-eicosene derivatives or heptacyclo-5-
heneicosene derivatives such as:
Heptacyclo [ 8 . 7 . 0 . 12~ 9 . 14, 7
111, 17 , p3. 8 . 012. 16] _5_
eicosene;
Heptacyclo[8.8Ø12~9.14~7
111,18.3.8.012.17]_5_
heneicosene
_ ~19~39~
22
the tricyclo[4.3Ø12,5]-3-decene derivatives such as:
Tricyclo[4.3Ø12,5]-3-
decene,
CH3
2-Methyltricyclo
[ 4 . 3 . 0 .12, 5 ] -3-decene
5-Methyltricyclo
[4.3Ø12,5]-3-decene;
CH3
the tricyclo[4.4Ø12,5]-3-undecene derivatives such as:
S
Tricyclo[4.4Ø12,5]-3-
undecene
CH3
10-Methyltricyclo
[4.4Ø12~5]-3-undecene;
the pentacyclo[6.5.1.13~6.02,x.09.13]-4-pentadecene
derivatives such as:
Pentacyclo[6.5.1.13,6,02,x,
09,13] -4-pentadecene
~ 19439.
23
CH3 CH3
1,3-Dimethylpentacyclo-
[ 6 . 5 . 1 . 13~ 6 . 02~ 7 . O9~ 13] -4-
pentadecene
CH3
1,6-Dimethylpentacyclo-
[6.5.1.13~6.02~7.09~13]-4_
pentadecene
CH3
CH3 CH3
14,15-Dimethylpentacyclo
[ 6 . 5 . 1 . 13~ 6 . 02~ 7 . O9~ 13] -4-
pentadecene;
the dime derivatives such as:
Pentacyclo [ 6 . 5 .1 .13~ 6 . p2, 7 .
09,13] -4, 10-pentadecadiene;
S the pentacyclo [7.4Ø12~5.19,12.08,13] _3-pentadecene
derivatives such as:
Pentacyclo
[7.4Ø12~5.19~12.0$~13]-3-
pentadecene
CH3
Methyl-substituted
pentacyclo
[7.4Ø12~5.19~12.08~13]-3-
pentadecene;
_ ~ 194.39;5
24
the heptacyClO [ 8 . 7 . 0 . 13~ 6 , 110, 17 . 112, 15 . 02, 7 . X11, 16~ _4_
eicosene derivatives such as:
Heptacyclo [ 8 . 7 . 0 .13~ 6. 110,17
112,15 . 02, 7 , 011,16 -4-eicosene
CH3 CH3 Dimethyl-substituted
heptacyclo-
[8.7Ø13~6.11~~17,112,15_
02, 7 . 011, 16~ -4-eicosene;
the nonacyclo [ 10 . 9 . 1 . 14~ 7 . 113, 20 , 115, 18 . 03, 8 . 02, 10 , 012,
21 . 014, 19 ~ _
5-pentacosene derivatives such as:
Nonacyclo [ 10 . 9 .1 .14~ 7 . 113, 20 ,
115,18 03,8.02,10.p12,21.
014,19_5-pentacosene
CH3 CH3 Trimethyl-substituted-
nonacyclo-
[10.9.1.14~7,113,20.
115,18 ~3,8.~2,10,~12,21
014,19 _5_pentacosene
CH3
the pentacyclo[8.4Ø12~5.19~12,08,13_3-hexadecene
derivatives such as:
_ 21943 95
2 1 14 13 12
31 11 Pentacyclo [8.4Ø12~5,
4 19, 12 , 08,13 ] _3-hexadecene
6 7 8 9
CH3 11-Methylpentacyclo
[8 . 4 . 0 . 12,5.19 12 .08, 13] -3_
hexadecene
C2Hg 11-Ethylpentacyclo
[8.4Ø12~5.19,12.08,13]-3_
hexadecene
CHg 10,11-Dimethylpentacyclo
[8 .4 . 0. 12,5.1912.08, 13] -3_
CH3 hexadecene;
the hepacycl0 [ 8 . 8 . 0 . 14, 7 . 111, 18 . 113, 16 , 03, s , p 12, 17 ] _5_
heneicosene derivatives such as:
4 3 2 1 18 1~ 16 Heptacyclo
[8.8Ø14,7.111,1a,
113,16,3.8.012.17]_5_
6 14 heneicosene
8v 1~12~
9 11 13
CH3 15-Methylheptacyclo
[8.8Ø14,7.111.18,113,16,
03, 8 . 012,17 ] -5-heneicosene
Trimethyl-heptacyclo
[8.8Ø14,7.111,18,
113,16,p3.8.012.17] _5_
CH3 CH3 CH3 heneicosene;
5
the nonaCyclo [ 10 . 10 . 1 . 15, 8 . 114, 21 , 116, 19 , 02,11 , 04, 9 , 013,
22 , 015, 20 ]
6-hexacosene derivatives such as:
219495
26
4 3 2 1 22 2120 19
6 18 Nonacyclo[10.10.1.15,8.114,21
116,19,p2,11_p4,9.p13,22.
1 1 17 015,20]-6-hexacosene
8 10 12 14 1516
and furthermore,
i
zl s
5-Phenyl-bicyclo[2.2.1]hept-
2-ene
5
4
5-Methyl-5-phenyl-
bicyclo[2.2.1]-hept-2-ene
CH3
5-Benzyl-bicyclo[2.2.1]hept-
CH2 O 2-ene
5-Tolyl-bicyclo[2.2.1]hept-
2-ene
CH3
5- (Ethylphenyl ) -
bicyclo[2.2.1]hept-2-ene
CH2CH3
CH3 5- (Isopropylphenyl) -
~~~ bicyclo[2.2.1]-hept-2-ene
CH
CH3
219395
27
4 5
4a 5a
3
1,4-Methano-1,4,4a,9a-
tetrahydro-fluorene
9aV 8a
1 9 8
1 10 9
l0a 9a
2 ~ 8
1,4-Methano-1,4,4a,5,10,10a-
4a ~ ? hexahydroanthracene
4 5 6
5- (a-Naphthyl) -
bicyclo[2.2.1]hept-2-ene
Cyclopentadiene-
acenaphthylene adducts
5- (Anthracenyl) -
bicyclo[2.2.1]kept-2-ene
5-(Biphenyl)-bicyclo[2.2.1]
kept-2-ene
5- (~i-Naphthyl ) -
bicyclo[2.2.1]kept-2-ene
5- (oc-Naphthyl) -
bicyclo[2.2.1]hept-2-ene
2I~~395
Zs
5- (Anthracenyl ) -
bicyclo[2.2.1]kept-2-ene
8-Phenyltetracyclo
[4.4.0 .125 1~~ to] -3-dodecene
8-Methyl-8-phenyl-tetracyclo
[ 4 . 4 . 0 .12 ~ 5 .1~ ~ to ] -3-dodecene
CH3
8-Benzyl-tetracyclo
CH2
[4 . 4.0 .12~5.1.10] -3-dodecene
8-Tolyl-tetracyclo
[4 . 4 . 0 .12~ 5 . l~~ lo] -3-dodecene
CH3
8-(Ethylphenyl)-tetracyclo
[ 4 . 4 . 0 .12 ~ 5 .1~. to ] -3-dodecene
CH2CH3
8-(Isopropylphenyl)
~H3 tetracyclo[4.4Ø12~5.1~.10]
CH -3-dodecene
I
CH3
8,9-biphenyl-tetracyclo
U
[ 4 . 4 . 0 .12~ 5 ~ 1 ~ ~ to ] -3-dodecene
0
8-(Biphenyl)-tetracyclo
[ 4 . 4 . 0 .12 ~ 5 .1.10 ] -3-dodecene
219495
29
8- (~i-Naphthyl) -tetracyclo
[4. 4 .0 .12~5.17~ lo] -3-dodecene
8-(a-Naphthyl)-tetracyclo
[ 4 . 4 . 0 .12 ~ 5 .17~ 10 ] -3-dodecene
8-(Anthracenyl)-tetracyclo
[ 4 . 4 . 0 .12~ 5 .17~ to ] -3-dodecene
Compound of cyclopentadiene-
acenaphthylene adducts with
cyclopentadiene further
added
3 1
4 2 13 12 11,12-Benzo-pentacyclo
[6.5.1.13~6.02~7.09~13]_
4-pentadecene
8 9 10 11
3 1 1413 12 11,12-Benzo-
4 2 pentacyclo
[ 6. 5.1 .13~ 6. 02~ 7 . O9~ 14] _
5 4-hexadecene
8 9 10 11
11-Phenyl-hexacyclo
[6.6.1.13~6,110,13.~2,7,~9,14]
-4-heptadecene
4 3 2 1 1~ 16 15 14,15-Benzo-heptacyclo
[8.7Ø129.14~7.111.17.03,8
6 012,16 -5-eicosene
g 10 12 14
7 g 11 13
CA 02194395 2002-07-04
72932-245
5,6-biphenyl-bicyclo[2.2.1]
kept-2-ene
Cyclopentadiene-
acenaphthylene adducts
S
9a 5a
1,4-Methano-1,4,4a,9a-
7 tetrahydro-fluorene
9a~8a
1 9 8
1 10 9
l0a 9a
1,4-Methano-1,4,4a,5,10,10a-
3 ~ hexahydroanthracene
4a 5a
4 5 6
The cycloolefins represented by the formula [1] or [2]
can be prepared by the Diels-Alder reaction of
cyclopentadienes with olefins having the corresponding
5 structures.
The cycloolefins can be used singly or in combination
of two or more kinds.
The cycloolefin resins (a-1) to (a-2) employable in
the invention can be prepared using the cycloolefins
10 represented by the formula [1] or [2] under the properly
selected conditions in accordance with, for example, the
processes proposed by the present applicant in Japanese
Patent Laid-Open Publications No. 168708/1985, No.
214395
31
120816/1986, No. 115912/1986, No. 115916/1986, No.
271308/1986, No. 272216/1986, No. 252406/1987, No.
252407/1987, No. 106/1989, No. 156308/1989 and No.
197511/1989.
S ~a-1) Ethylene/cycloolefin random copolymer
In the ethylene/cycloolefin random copolymer (a-1)
used as the cycloolefin resin in the invention, the
constituent units derived from ethylene are contained in
amounts of usually 52 to 90 % by mol, preferably 55 to 80
by mol, and the constituent units derived from the
cycloolefin are contained in amounts of usually 10 to 48 0
by mol, preferably 20 to 45 % by mol. The contents of the
ethylene units and the cycloolefin units can be measured by
13C _~R .
In the ethylene/cycloolefin random copolymer (a-1),
the constituent units derived from ethylene and the
constituent units derived from the cycloolefin are arranged
at random and combined to form a substantially linear
structure. The substantially linear and substantially
crosslinked gel-free structure of this copolymer can be
confirmed by the fact that the copolymer is dissolved in
organic solvents and contains no insoluble component. For
example, the above-mentioned structure can be confirmed by
the fact that the copolymer is perfectly dissolved in
decalin at 135 °C in the later-described measurement of the
intrinsic viscosity [~] of the copolymer.
In the ethylene/cycloolefin random copolymer (a-1)
used in the invention, at least a part of the constituent
2 ~ 94395
32
units derived from the cycloolefin represented by the
formula [1] or [2] are considered to have a structure
represented by the following formula [1-a] or [2-a].
Further, at least a part of the cycloolefin represented by
the formula [1-1] preferably used in the invention is
considered to have a structure represented by the following
formula [1-1-a].
R1 ~ Ra Rb ~ ~ R7 ~ R11
R15
R3 L ~ \ R9 1 R13 R16
1q
R17
R4 R1o Rla
R18
12
R2 R5 R5 R8 R
n m
[1-a]
1~
R26 R27
I~
R24 ~ R25
R7 R 11
Rls ~ I
_
R9 R 13 (CH2)h R23
Rlo Rla
R17
R21- R22
RI8
l I.
Rg R12 ~ J
m
R19 R2o [2-a]
-- 219495
33
R 1s
R16
R17
R18
n m
[1-1-a]
In the formulas [ 1-a] and [ 1-1-a] , n, m, q, R1 to R18,
Ra and Rb have the same meanings as in the formula [1]. In
S the formula [2-a] , m, h, j, k, R7 to R15, and R17 to R27 have
the same meanings as in the formula [2].
In the ethylene/cycloolefin random copolymer (a-1)
used in the invention, constituent units derived from other
copolymerizable monomers may be contained, if necessary,
within limits not prejudicial to the objects of the
invention.
Examples of the monomers include olefins other than
ethylene and the above-mentioned cycloolefins, norbornenes
and nonconjugated dimes. More specifically, there can be
mentioned:
oc-olefins of 3 to 20 carbon atoms, such as propylene,
1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-
1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-
1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-
2 0 ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-
dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-
eicosene;
219~~95
34
cycloolefins, such as cyclobutene, cyclopentene,
cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene,
2-(2-methylbutyl)-1-cyclohexene, cyclooctene and 3a,5,6,7a-
tetrahydro-4,7-methano-1H-indene;
norbornenes, such as 2-norbornene, 5-methyl-2-
norbornene, 5-ethyl-2-norbornene, 5-isopropyl-2-norbornene,
5-n-butyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-
dimethyl-2-norbornene, 5-chloro-2-norbornene and 5-fluoro-
2-norbornene; and
1~ nonconjugated dimes, such as 1,4-hexadiene, 4-methyl-
1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene,
dicyclopentadiene, 5-ethylidene-2-norbornene and 5-vinyl-2-
norbornene.
These monomers can be used singly or in combination of
two or more kinds.
In the ethylene/cycloolefin random copolymer (a-1),
the constituent units derived from the other monomers may
be contained in amounts of usually not more than 20 o by
mol, preferably not more than 10 % by mol.
2 0 The ethylene/cycloolefin random copolymer (a-1) for
use in the invention can be prepared using ethylene and the
cycloolefin represented by the formula [1] or [2] in
accordance with the processes disclosed in the aforesaid
publications. Above all, it is preferable to prepare the
ethylene/cycloolefin random copolymer (a-1) by a process in
which the copolymerization is carried out in a hydrocarbon
solvent, using, as catalyst, either a vanadium catalyst
formed from a vanadium compound soluble in the hydrocarbon
__ 2194395
solvent and an organoaluminum compound, a titanium catalyst
formed from a titanium compound and an organoaluminum
compound or a zirconium catalyst formed from aluminoxane
and a zirconium complex having as a ligand a multidentate
S coordination compound wherein at least two conjugated
cycloalkadienyl groups are linked through a lower alkylene
group.
(a-21 Graft modified product
The graft modified product (a-2) of a cycloolefin
10 resin used in the invention is obtained by graft modifying
a part of the ethylene/cycloolefin random copolymer (a-1)
with a modifier.
Examples of the modifiers used herein include
unsaturated carboxylic acids, anhydrides of these acids
15 such as malefic anhydride, and derivatives of alkyl esters
of unsaturated carboxylic acids.
In the graft modified product employable as the
cycloolefin resin in the invention, the content of the
constituent units derived from the modifier is usually not
20 more than 10 o by mol.
The graft modified product of a cycloolefin resin can
be prepared by blending a cycloolefin resin with a modifier
to perform graft polymerization in such a manner that the
desired degree of modification is obtained, or it can be
25 prepared by previously preparing a modified product having
a high degree of modification and mixing the modified
product and an unmodified cycloolefin resin.
2194~~5
36
The cycloolefin resin for use in the invention is
selected from the group consisting of the
ethylene/cycloolefin random copolymer (a-1) and the graft
modified product (a-2). A mixture of two or more kinds
S thereof is also employable.
Of these, the ethylene/cycloolefin random copolymer
(a-1) is preferably employed as the cycloolefin resin in
the invention.
Oycloolefin resin comQosition
The multi-layer laminate of the invention may be a
laminate of (A) a layer formed from the cycloolefin resin
and (B) a polymer layer having the later-described specific
oxygen permeability, but the cycloolefin resin layer (A)
may be formed from a cycloolefin resin composition.
That is, this cycloolefin resin composition layer is
formed from a composition comprising at least one
cycloolefin resin selected from the group consisting of the
ethylene/cycloolefin random copolymer (a-1) and the graft
modified product (a-2) and (b) a polyolefin.
2 ~ As the polyolefin (b), a (co)polymer of an a-olefin of
2 to 20 carbon atoms is usually employed.
Examples of the a-olefins of 2 to 20 carbon atoms
include ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene,
4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-
hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-
1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-
hexadecene, 1-octadecene and 1-eicosene.
_ ~ 19 4 3 95
37
The polyolefin (b) used in the invention may be a
homopolymer of the a-olefin or a copolymer of two or more
kinds of the a-olefins.
In the polyolefin (b), the a-olefins mentioned above
S may be copolymerized with other monomers such as
norbornenes and nonconjugated dimes, as far as the
properties of the polyolefin are not marred. Examples of
the other monomers include:
cycloolefins, such as cyclobutene, cyclopentene,
cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene,
2-(2-methylbutyl)-1-cyclohexene, cyclooctene and 3a,5,6,7a-
tetrahydro-4,7-methano-1H-indene;
norbornenes, such as 2-norbornene, 5-methyl-2-
norbornene, 5-ethyl-2-norbornene, 5-isopropyl-2-norbornene,
5-n-butyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-
dimethyl-2-norbornene, 5-chloro-2-norbornene and 5-fluoro-
2-norbornene; and
nonconjugated dimes, such as 1,4-hexadiene, 4-methyl-
1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene,
2 0 dicyclopentadiene, 5-ethylidene-2-norbornene and 5-vinyl-2-
norbornene.
These monomers can be used singly or in combination of
two or more kinds.
In the present invention, the polyolefin (b) is
preferably polyethylene and/or polypropylene.
When the polyolefin (b) is polyethylene, this
polyethylene may be a homopolymer of ethylene or a
copolymer of ethylene and other oc-olefin.
t 21 g~395
38
For example, if the polyolefin (b) is polyethylene, an
ethylene homopolymer or an ethylene/a-olefin copolymer
having an ethylene content of not less than 60 % by mol,
preferably not less than 70 % by mol, each of which has a
S density of usually not less than 0.830 g/cm3, preferably
0.87 to 0.94 g/cm3, a melt flow rate at 190 °C of usually
0.01 to 100 g/10 min, preferably 0.03 to 50 g/10 min, and a
Vicat softening point of usually 50 to 140 °C, preferably
80 to 130 °C, is used as the polyethylene.
Examples of the oc-olefins copolymerizable with
ethylene include a-olefins of 3 to 14 carbon atoms, such as
propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-
butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-
pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-
dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-
octene, 1-decene, 1-dodecene and 1-tetradecene. Of these,
a-olefins of 3 to 10 carbon atoms are preferably employed.
When the polyolefin (b) is polypropylene, this
polypropylene may be a homopolymer of propylene or a
2 ~ copolymer of propylene and other oc-olefin.
If the polyolefin (b) is polypropylene, a propylene
homopolymer or a propylene/oc-olefin copolymer having a
propylene content of not less than 70 o by mol, preferably
not less than 80 o by mol, each of which has a density of
usually not less than 0.85 g/cm3, preferably 0.89 to 0.91
g/cm3, a melt flow rate at 230 °C of usually 0.01 to 100
g/10 min, preferably 0.05 to 100 g/10 min, and a Vicat
2194395
39
softening point of usually 100 to 170 °C, preferably 110 to
160 °C, is used as the polypropylene.
Examples of the a-olefins copolymerizable with
propylene include a-olefins of 2 to 14 carbon atoms
S (excluding propylene), such as ethylene, 1-butene, 1-
pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene,
3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene,
4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-
hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene
and 1-tetradecene. Of these, a-olefins of 2 to 10 carbon
atoms (excluding propylene) are preferably employed.
The polyolefin (b) may be a graft modified product.
Examples of the modifiers used herein include unsaturated
carboxylic acids, anhydrides of these acids such as malefic
anhydride, and derivatives of alkyl esters of unsaturated
carboxylic acids.
When the polyolefin (b) is a graft modified product,
the content of the constituent units derived from the
modifier in the polyolefin (b) is usually not more than 10
% by mol.
The graft modified product can be prepared by blending
a polyolefin with a modifier to perform graft
polymerization in such a manner that the desired degree of
modification is obtained, or it can be prepared by
previously preparing a modified product having a high
degree of modification and mixing the modified product and
an unmodified polyolefin.
_ ~1 ~4~g5
The cycloolefin resin composition can be prepared from
the polyolefin and the cycloolefin resin by mixing them in
accordance with known methods. For example, those
components are mixed by means of a Henschel mixer, a V-
S blender, a ribbon blender, a tumbling blender or the like.
Or, after mixing, the resulting mixture is further melt
kneaded by means of a single-screw extruder, a twin-screw
extruder, a kneader or the like, followed by granulating or
pulverizing the kneadate.
10 To the cycloolefin resin or cycloolefin resin
composition (A) used in the invention, rubber components to
improve impact strength, other resin components, heat
stabilizers, weathering stabilizers, light stabilizers,
antistatic agents, slip agents, anti-blocking agents, anti-
15 fogging agents, nucleating agents, lubricants, dyes which
absorb only the lights of specific wavelength, pigments,
natural oils, synthetic oils, waxe$ and light transmitting
fillers may be added within limits not prejudicial to the
objects of the invention, in addition to the components (a-
20 1) , (a-2) and (b) .
Examples of the stabilizers optionally added include
phenol antioxidants, such as tetrakis[methylene-3(3,5-di-t-
butyl-4-hydroxyphenyl)propionate]methane, alkyl ester of (3-
(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid and 2,2'-
25 oxamidobis[ethyl-3-(3,5-di-t-butyl-4-
hydroxyphenyl)propionate]; metallic salts of fatty acids,
such as zinc stearate and calcium salts of fatty acids
2194395
41
(e. g., calcium stearate and calcium 12-hydroxystearate);
and fatty acid esters of polyhydric alcohols.
These stabilizers may be added singly or in
combination. For example, a combination of
S tetrakis[methylene-3(3,5-di-t-butyl-4-
hydroxyphenyl)propionate)methane, zinc stearate and
glycerol monostearate is employable.
In the present invention, it is preferable to use
phenol antioxidants and fatty acid esters of polyhydric
alcohols in combination. Examples of the fatty acid esters
of polyhydric alcohols include those wherein a part of
alcoholic hydroxyl groups of the tri- or more-valent
polyhydric alcohols are esterified.
Examples of the fatty acid esters of polyhydric
alcohols include:
fatty acid esters of glycerol, such as glycerol
monostearate, glycerol monolaurate, glycerol monomyristate,
glycerol monopalmitate, glycerol distearate and glycerol
dilaurate; and
2 0 fatty acid esters of pentaerythritol, such as
pentaerythritol monostearate, pentaerythritol monolaurate,
pentaerythritol distearate and pentaerythritol tristearate.
These esters may be used singly or in combination.
The phenol antioxidant is used in an amount of usually
less than 10 parts by weight, preferably less than 5 parts
by weight, more preferably less than 2 parts by weight,
based on 100 parts by weight of the total of the essential
components. The fatty acid ester of polyhydric alcohol is
2194395
42
used in an amount of usually less than 10 parts by weight,
preferably less than 5 parts by weight, based on 100 parts
by weight of the total of the essential components.
(B) Polymer layer of low oxxgen permeability
The multi-layer laminate of the invention is a
laminate comprising (A) a layer formed from the cycloolefin
resin or the cycloolefin resin composition and (B) a
polymer layer having a specific oxygen permeability.
The polymer layer (B) needs to have an oxygen
1~ permeability, as measured at a temperature of 23 °C and RH
of 0 %, of not more than 10 cc (STP) ~mm/m2 ~ 24hr-atm, and the
oxygen permeability of the polymer layer (B) is preferably
not more than 1 cc(STP)-mm/m2~24hr-atm, more preferably not
more than 0.1 cc(STP)~mm/m2~24hr-atm.
The polymer layer having an oxygen permeability in
this range can be formed from various resins. Examples of
the resins for forming the polymer layer (B) include an
ethylene/vinyl alcohol copolymer (EVOH), polyacrylonitrile
(PAN), polyvinyl chloride (PVDC) and cellophane. In the
2 0 invention, the polymer layer is preferably formed from the
ethylene/vinyl alcohol copolymer (EVOH) or cellophane.
The ethylene/vinyl alcohol copolymer (EVOH) used in
the invention is preferably a copolymer having a
saponification degree of 90 to 100 %, which is obtained by
saponifying an ethylene/vinyl acetate copolymer having an
ethylene content of 15 to 60 % by mol. An ethylene/vinyl
alcohol copolymer having an ethylene content of less than
15 % by mol is sometimes difficult to mold it because its
CA 02194395 2002-07-04
72932-245
43
molding temperature is close to its decomposition
temperature, If the ethylene content exceeds 60 o by mol,
resistance to gas permeation and mechanical properties,
which are excellent characteristics of an ethylene/vinyl
alcohol copolymer, deteriorate and the resulting laminate
does not exert effects of the laminated structure. An
ethylene/vinyl alcohol copolymer having a saponification
degree of less than 90 ~ sometimes show poor mechanical
properties, oil resistance and water resistance, so that
the saponification degree in the ethylene/vinyl alcohol
copolymer (EVOH) is usually determined within the above-
mentioned range. The ethylene/vinyl alcohol copolymer
(EVOH) has an oxygen permeability of usually not more than
10 cc(STP)-mm/m2~24hr-atm, and therefore this copolymer is
1S suitable for forming the multi-layer laminate of the
invention.
The cellophane preferably used is one having a
regenerated cellulose content of not less than 65 %.
To the polymer layer (B) of low oxygen permeability,
2~ other various components, such as rubber components to
improve impact strength, other resin components, heat
stabilizers, weathering stabilizers, light stabilizers,
antistatic agents, slip agents, anti-blocking agents, anti-
fogging gents, nucleating agents, :Lubricants, dyes which
25 absorb only the lights of specific wavelength, pigments,
natural oils, synthetic oils, waxes and light transmitting
fillers, may be added within limits not prejudicial to the
objects of the invention.
44 Z 19495
The multi-layer laminate of the invention is a
laminate of (A) the layer of the cycloolefin resin or the
cycloolefin resin composition and (B) the polymer layer.
S The laminate can take any optional laminating structure,
such as:
polymer layer (B)/cycloolefin resin (composition)
layer (A) /polymer layer (B) ;
cycloolefin resin (composition) layer (A)/polymer
1~ layer (B) /cycloolefin resin (composition) layer (A) ; or
polymer layer (B)/cycloolefin resin (composition)
layer (A).
The multi-layer laminate of the invention comprising
the layer (A) and the layer (B) has an oxygen permeability
15 of not more than 5 cc(STP)-mm/m2~24hr-atm, preferably not
more than 1 cc(STP)~mm/m2-24hr-atm, more preferably not
more than 0.5 cc(STP)~mm/m2~24hr-atm.
A layer of polyolefin such as polyethylene or
polypropylene can be further laminated as the outermost
2 ~ layer of the laminate of the invention to improve heat-
sealing properties of a molded product in the form of sheet
or film.
In the multi-layer laminate of the invention, the
thickness of the cycloolefin resin (composition) layer (A)
25 and the thickness of the low-oxygen permeability polymer
layer (B) can be properly determined in consideration of
uses of the multi-layer laminate, but in general, the
thickness of the cycloolefin resin (composition) layer (A)
- .~ 1 ~~39~
is in the range of 1 elm to 10 mm, and the thickness of the
low-oxygen permeability polymer layer (B) is in the range
of 1 um to 10 mm. The total thickness of the multi-layer
laminate of the invention is generally in the range of 2 ~m
5 to 20 mm, though it varies depending on the uses of the
laminate, the number of the laminated layers, etc.
The cycloolefin resin (composition) layer and the low-
oxygen permeability polymer layer (B) can be laminated
together without using any adhesive. For example, they can
10 be laminated in accordance with the methods conventionally
used for forming multi-layer laminates, specifically, co-
extrusion methods such as a multi-layer T-die method, a
multi-layer inflation method and an extrusion laminating
method. The cycloolefin resin (composition) layer (A) and
15 the low-oxygen permeability polymer layer (B) show good
adhesion therebetween, so that it is unnecessary to use any
adhesive. However, if the resin for forming the layer (A)
and the resin for forming the layer (B) have low affinity
for each other, those layers can be laminated by using an
20 adhesive.
The adhesive preferably used in the invention is, for
example, a low-crystalline to non-crystalline soft
copolymer or a soft copolymer composition containing the
soft copolymer.
25 As the low-crystalline to non-crystalline soft
copolymer, an adhesive resin composition containing
modified polyolefin or unsaturated polyolefin is
employable. The modified polyolefin is prepared from an
2194395
46
ethylene/a-olefin random copolymer having a melt flow rate
(MFR), as measured in accordance with ASTM D 1238L, of
usually 0.1 to 50 g/10 min, preferably 0.2 to 20 g/10 min,
a density of usually 0.850 to 0.900 g/cm3, preferably 0.855
to 0.895 g/cm3, an ethylene content of 30 to 95 % by mol,
preferably 40 to 92 o by mol, a crystallinity, as measured
by X-ray diffractometry, of usually not more than 40 %,
preferably not more than 30 %, and a melting point, as
measured in accordance with ASTM D 3418, of usually not
higher than 100 °C.
In the present invention, the low-crystalline to non-
crystalline soft copolymer can be used alone as the
adhesive, or it can be used after mixed with a tackifier or
the like.
As the tackifier, an aliphatic hydrocarbon resin
and/or an alicyclic hydrocarbon resin obtained by
hydrogenating an aromatic hydrocarbon resin is employable.
Particularly, an alicyclic hydrocarbon resin having a
softening point, as measured by a ring and ball method, of
2 0 usually 105 to 150 °C, preferably 110 to 140 °C, and a
hydrogenation degree of aromatic'ring of usually not less
than 80 %, preferably not less than 85 %, is employed. In
this case, the ethylene/a-olefin copolymer is used in an
amount of 60 to 98 % by weight, and the aliphatic
hydrocarbon resin and/or the alicyclic hydrocarbon resin is
used in an amount of 2 to 40 o by weight.
2194395
47
The low-crystalline to non-crystalline soft copolymer
can be blended with modified polyethylene. The modified
polyethylene has a graft amount of the unsaturated
carboxylic acid or its derivative of 0.01 to 10 % by
S weight, preferably 0.1 to 5 a by weight, a density of 0.905
to 0.98 g/cm3, preferably 0.920 to 0.970 g/cm3, and a
crystallinity, as measured by X-ray diffractometry, of not
less than 45 %, preferably 50 to 80 %. In order to prepare
the modified polyethylene, an ethylene homopolymer or an
ethylene copolymer each having a melt flow rate (MFR, ASTM
D 1238E) of 0.001 to 100 g/10 min, a density of 0.905 to
0.980 g/cm3, and a crystallinity, as measured by X-ray
diffractometry, of not less than 45 a may be employed.
Examples of the unsaturated carboxylic acids and their
derivatives used for the modification include unsaturated
carboxylic acids, such as acrylic acid, malefic acid,
fumaric acid, tetrahydrophthalic acid, itaconic acid,
citraconic acid, crotonic acid, isocrotonic acid and Nadic
acidTM (endocis-bicyclo[2,2,1]hepto-5-ene-2,3-dicarboxylic
acid); and derivatives of these acids, such as malenyl
chloride, maleimide, malefic anhydride, citraconic
anhydride, monomethyl maleate, dimethyl maleate and
glycidyl maleate. Of these, preferable are malefic acid,
Nadic acidTM and anhydrides thereof.
The modified polyethylene is used in an amount of
usually 0.1 to 99 % by weight based on 100 parts by weight
of the low-crystalline to non-crystalline soft copolymer.
2 ~ 9 4.3 9.~
48
The soft copolymer composition may be a blend of the
above-mentioned ethylene/oc-olefin random copolymer and an
ethylene/vinyl acetate random copolymer and/or an
ethylene/vinyl alcohol random copolymer. In this case, it
is preferred that the ethylene/a-olefin random copolymer is
used in an amount of 60 to 98 o by weight, and the
ethylene/vinyl acetate random copolymer and/or the
ethylene/vinyl alcohol random copolymer is used in an
amount of 2 to 40 % by weight.
The multi-layer laminate of the invention can be
prepared by various methods, for example, co-extrusion
methods, such as multi-layer T-die method, multi-layer
inflation and extrusion laminating method; multi-layer
sheet- or film-forming methods conventionally known, such
as wet laminating method and dry laminating method; blow
methods, such as multi-layer injection blowing (e.g., co-
injection blowing) and multi-layer direct blowing;
injection molding methods, such as sandwich molding and
two-color injection molding; and stamping method. The
2 0 multi-layer laminate thus produced can be used as it is
without being stretched, or it can be used after
monoaxially stretched or biaxially oriented. In order to
impart other functions, the multi-layer laminate may
further be provided with a coat of vinylidene chloride or a
film of other resin.
The multi-layer laminate of the invention is excellent
not only in gas barrier properties such as oxygen barrier
- 2194395
49
properties, interlaminar bond properties, moisture
resistance, transparency, moderate flexibility,
tearability, heat-sealing properties and dead fold
properties but also in vacuum or pressure formability, so
S that it exerts effects high enough as materials for
packaging drugs, foods and cigarettes. Accordingly, the
multi-layer laminate of the invention can be suitably used
as a material of packaging sheets, packaging films or
containers such as bottles.
Examples of the objects to be packaged include drugs,
foods, daily necessaries, general merchandise and other
optional goods. Especially when the multi-layer laminate
of the invention is used for packaging drugs such as tablet
or capsule drugs, foods such as rice crackers, snack foods
and cookies, and hygroscopic goods such as cigarettes and
tea bags, the moisture resistance and transparency can be
ensured.
Examples of the applicable packaging materials include
films of bags, packs, PTP (press through pack) and blister
2 0 packs, twist wrapping films, wrapping films, shrink films,
easy peel films, medical containers such as eye-droppers,
vials, transfusion packs and syringes, physiochemical
containers such as petri dishes, test tubes and analytical
cells, and containers made up of multi-layer molded sheets
such as cosmetic bottles, tetra packs and milk packs.
The multi-layer laminate of the invention is
particularly suitable as a packaging material such as PTP
(press through pack) or blister pack.
._ 2i 94395
so
EFFECT OF THE INVENTION
The multi-layer laminate of the invention comprises a
layer of a specific cycloolefin resin or a specific
s cycloolefin resin composition and a polymer layer having a
low oxygen permeability, so that it is excellent not only
in interlaminar bond properties, formability, moisture
resistance, transparency, moderate flexibility,
tearability, heat-sealing properties and dead fold
to properties but also in vacuum or pressure formability. The
polymer layer (B) of the multi-layer laminate of the
invention has a low oxygen permeability. Therefore, use of
sheets, films or packaging materials formed from the
laminate of the invention makes it possible to favorably
is seal the objects packaged. The multi-layer laminate of the
invention is not lowered in the gas barrier properties, and
exhibits excellent gas barrier properties even when it is
used in an atmosphere of high humidity. That is, the
multi-layer laminates shown in Comparative Examples 6 and 7
20 are markedly lowered in the moisture resistance when used
in an atmosphere or high humidity, though they are not so
bad in the moisture resistance and gas barrier properties
as compared with the multi-layer laminate of the invention.
On the other hand, the multi-layer laminate of the
25 invention does not have such unfavorable tendency, and it
is particularly excellent in the moisture resistance and
gas barrier properties under the wet conditions.
CA 02194395 2005-10-12
72932-243
S1
The present invention will be further described with
reference to the following examples, but it should be
construed that the invention is in no way limited to those
examples.
As a cycloolefin resin composition, a random copolymer
of ethylene (intrinsic viscosity ('~]: 0.67 dl/g, softening
temperature (TMA) : 90 °C) and tetracyclo [4 .4 Ø12~5.l~.lo~ _3_
dodecene (hereinafter sometimes referred to as "ETCD") was
melted in an extruder. The molten copolymer was fed to a
composite inflation molding die at a resin temperature of
210 °C.
Separately, an ethylene/vinyl alcohol copolymer (EVOH,
trade mark: Kuraray Eval EP-F, ethylene content: 32 o by
mol, density: 1.19, oxygen permeability: 0.05
cc-mm/m2~24hr~atm, available from Kuraray Co., Ltd.) was
melted in a different extruder. The molten resin was fed
to the die at a resin temperature of 210 °C, to prepare an
inflation film consisting of an ETCD layer as an inner
layer and an ethylene/vinyl alcohol copolymer (EVOH) layer
as an outer layer.
In the inflation film, the ETCD layer had a thickness
of 70 ~tm, and the ethylene/vinyl alcohol copolymer (EVOH)
layer had a thickness of 30 ~tm.
The film was evaluated on the gas barrier properties,
and the results are set forth in Table 1.
CA 02194395 2005-10-12
72932-243
52
As a cycloolefin resin composition, a random copolymer
(ETCD) of ethylene (intrinsic viscosity [r~]: 0.67 dl/g,
softening temperature (TMA): 90 °C) and
tetracyclo [4 . 4 . 0 .12-5.1-1°] -3-dodecene was melted in an
extruder. The molten copolymer was fed to a composite
inflation molding die at a resin temperature of 210 °C.
Separately, nylon-6 (trade mark: Toray Amiran CM1011,
oxygen permeability: 1.2 cc~mm/m2~24hr~atm, available from
Toray Industries, Inc.) was melted in a different extruder.
The molten resin was fed to the die at a resin temperature
of 260 °C, to prepare an inflation film consisting of an
ETCD layer as an inner layer and a nylon-6 layer as an
outer layer.
In the inflation film, the ETCD layer had a thickness
of 70 Elm, and the nylon-6 layer had a thickness of 30 Vim.
The film was evaluated on the gas barrier properties,
and the results are set forth in Table. 1.
Comparative Exam lx~ a 2
An inflation film was prepared in the same manner as
in Comparative Example 1 except that polyethylene
terephthalate (PET, intrinsic viscosity: 1.4 dl/g, oxygen
permeability: 5.0 cc~mm/m2~24hr~atm) was used in place of
nylon-6 and the molten resin was fed to the die at a resin
temperature of 270 °C.
The film was evaluated on the gas barrier properties,
and the results are set forth in Table 1.
CA 02194395 2005-10-12
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53
Example 2
An inflation film was prepared in the same manner as
in Comparative Example 1 except that PVDC (vinylidene
S chloride content: 85 a by mol, oxygen permeability: 0.3
cc~mm/m2-24hr~atm) was used in place of nylon-6 and the
molten resin was fed to the die at a resin temperature of
200 °C.
The film was evaluated on the gas barrier properties,
and the results are set forth in Table 1.
Example 3
An inflation film was prepared in the same manner as
in Comparative Example 1 except that polyacrylonitrile
1S (PANS trade mark: Balex, oxygen permeability: 0.7
cc~mm/m2~24hr~atm) was used in place of nylon-6 and the
molten resin was fed to the die at a resin temperature of
210 °C.
The film was evaluated on the gas barrier properties,
and the results are set forth in Table 1.
example 4
As a cycloolefin resin composition, a random copolymer
>,
(ETCD-2) of ethylene (intrinsic viscosity ['~]: 0.50 dl/g,
softening temperature (TMA) : 150 °C) and
tetracyclo(4.4Ø12~5.17~lo~_3-dodecene was melted in an
extruder. The molten copolymer was fed to a composite
inflation molding die at a resin temperature of 270 °C.
CA 02194395 2005-10-12
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54
Separately, an ethylene/vinyl alcohol copolymer (EVOH,
trade mark: Kuraray Eval EP-F, ethylene content: 32 ~ by
mol, density: 1.19, oxygen permeability: 0.05
cc~mm/m2-24hr~atm, available from Kuraray Co., Ltd.) was
melted in a different extruder. The molten resin was fed
to the die at a resin temperature of 230 °C, to prepare an
inflation film consisting of an ETCD-2 layer as an inner
layer and an ethylene/vinyl alcohol copolymer (EVOH) layer
as an outer layer.
In the inflation film, the ETCD-2 layer had a thickness
of 70 ~.lm, and the ethylene/vinyl alcohol copolymer (EVOH)
layer had a thickness of 30 elm.
The film was evaluated on the gas barrier properties,
and the results are set forth in Table 2.
~Qm~arative Example 3
An inflation film was prepared in the same manner as
in Comparative Example 1 except that polyethylene (MFR: 5.2
g/10 min (190 °C, 2.16 kg), density: 0.968 g/cm2, oxygen
2 0 permeability: 85 cc-mm/m2~24hr~atm) was used in place of
nylon-6 and the molten resin was fed to the die at a resin
temperature of 210 °C.
The film was evaluated on the gas barrier properties,
and the results are set forth in Table 1.
~ompa a eve Example 4
An inflation film was prepared in the same manner as
in Comparative Example 1 except that polypropylene (MFR:
CA 02194395 2002-07-04
72932-245
7.0 g/10 min (230 °C, 2.1~ kg), melting point: 143 °C,
oxygen permeability: 80 cc~mm/m2°24hr~atm) was used in
place of nylon-6 and the molten resin was fed to the die at
a resin temperature of 210 °C.
5 The film was evaluated on the gas barrier properties,
and the results are set forth in Table 1.
~ompara~ve Example 5
An inflation film having a thickness of 100 dun was
10 prepared by the use of ETCD alone.
The film was evaluated on the gas barrier properties,
and the results are set forth in Table 1.
~om~arative Exam~~e 6
15 An inflation film was prepared in the same manner as
in Example 1 except that polypropylene (MFR: 7.0 g/10 min
(230 °C, 2.16 kg), Tm: 143 °C, oxygen permeability: 80
cc~mm/m2~24hr-atm) was used in place of ETCD.
The film was evaluated on the gas barrier properties,
20 and the results are set forth in Table 2.
~Qm~~rati vP ExamplQ,~7
An inflation film was prepared in the same manner as
in Example 1 except that polyethylene (MFR: ~.2 g/10 min
2$ (190 °C, 2.16 kg), density: 0.968 g/cm.', oxygen permeability: 85
cc~mm/m2~24hr-atm) was used in place of ETCD.
The film was evaluated on the gas barrier properties,
and the results are set forth in Table 2.
CA 02194395 2005-10-12
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56
Comparative Example 8
An inflation film having a thickness of 100 ~.m was
prepared by the use of EVOH alone. The film was evaluated
on the gas barrier properties, and the results are set
forth in Table 1.
As is obvious from the comparison between Comparative
Examples 6, 7 and Example 1, the laminated film consisting
of the ETCD layer and the EVOH layer has both of the gas
barrier properties inherent in EVOH and the moisture
resistance inherent in ETCD.
comparative Example 9
Molding was carried out in the same manner as in
Example 4 except that a hydrogenation product (ring opening
polymer A) of a tetracyclododecene ring opening
polymer having an intrinsic viscosity [~] of 0.06 dl/g and
a softening temperature of 150 °C was used as a cycloolefin
resin.
The gas barrier properties of the film obtained are
set forth in Table 2.
CA 02194395 2005-10-12
72932-243
Table 1
Comp. Comp. Comp. Comp.Comp.
Ex.l Ex,l Ex.2 Ex.2 Ex.3 Ex.3 Ex.4 Ex.S
ETCD ETCD ETCD ETCD ETCD ETCD ETCD
Layer structure /EVOH/NY6 /PET /PVDC/PAN /pE /pp ETCD
Thickness of each70/3070/30 70/3070/3070/30 70/30 70/30
la er ( )
Moisture perme- 0.12 0.13 0.13 0.11 0.13 0.12 0.12 0.09
abilit *1
Oxygen perme-
ability of layer 0-17 35 11 0.97 0.94 32 31 25
A
+ la er B *2
Carbon dioxide 0,50 14 32 7.6 3.2 79 79 60
aas
ermeabilit *Z)
Oxygen
permeability of 0.05 1.2 5.0 0.3 0.7 85 80 (25)
la er B alone
*2
Remarks: *1) g~mm/m2~24hr
*2) cc(STP)-mm/m2-24hr-atm
- 2 ~ ~ 43 ~5
s$
Table 2
Comp. Comp. Comp. Comp. Comp.
Ex.l Ex.4 Ex.6 Ex.7 Ex.8 Ex.9 Ex.S
ETCD ETCD-2 PP*3) PE*4) EVOH Ring ETCD
Layer structure /EVOH /EVOH /EVOH /EVOH singleopening single
layer polymer layer
A
Thickness of each70/30 70/30 70/30 70/30 100 70/30 100
la er ( )
Moisture perme-
0.12 0.12 0.37 0.26 0.?5 0.30 0.09
abilit *1
Oxygen perme-
ability of layer 0.17 0.17 0.17 0.17 0.17 0.17 25
A
+ la er B *2
Carbon dioxide
gas
0.50 0.05 0.53 0.53 0.16 0.15 60
ermeabilit *2
Remarks: *1) g~mm/m2~24hr
s *2) cc (STP) ~mm/m2~24hr~atm
*3) PP:MFR = 7.0 g/10 min, Tm = 143°C,
02 permeability = 80cc(STP)~mm/m2~24hr~atm
*4) PE: MFR = 5.2 g/lOmin.(190°C, 2.16kg)
Density = 0.968,
02 permeability = 85cc(STP)~mm/m2~24hr~atm
