JP2001026693A - Cyclic olefin resin composition and molded item thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition which has improved slippage, excellent transparence and surface gloss by making the composition comprise a cyclic olefin resin (A) or a resin composition composed of the cyclic olefin resin and a polyolefin and a cyclic polyolefin resin (C) having a structure different from that of the cyclic olefin-based resin A. SOLUTION: A cyclic olefin resin A is selected from an α-olefin-cyclic olefin random copolymer (D) composed of a cyclic olefin represented by formula I or II and a 2-20C α-olefin, a ring opening (co)polymer of the cyclic olefin represented by formula I or II or a hydrogenated polymer thereof (E) and a graft-modified polymer of the random copolymer A or the hydrogenated polymer E (wherein n is 0 or 1; h and m are each 0 or a positive integer; j and k are each 0, 1 or 2; R1 to R18 and Ra and Rb are each H, a halogen or a hydrocarbon group; and R19 to R27 are each H, a halogen, a hydrocarbon group or an alkoxy group).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cyclic olefin resin composition containing a cyclic olefin resin and a molded article thereof. More specifically, the present invention relates to a cyclic olefin-based resin composition suitable as a material for containers and packaging, and a molded article thereof.

[0002]

2. Description of the Related Art Cyclic olefin resins have excellent transparency and moisture resistance and are suitable for applications such as containers and packaging. But,
In some cases, the coefficient of friction between the cyclic olefin-based resins was large, resulting in damage on the container production line and poor winding when winding the film. Further, when a molded article of a cyclic olefin resin is used at around this glass transition temperature, the molded articles sometimes block each other. In order to solve these problems, it is conceivable to add an additive generally used as a slip agent or an anti-blocking agent, but without impairing the surface gloss and transparency of the cyclic olefin resin molded article. Additives that can improve these problems have not been known. In addition, many of the conventional slip agents are in the form of oligomers or waxes and have the property of bleeding out on the surface of the resin, so that they may not be used in applications requiring high hygiene such as pharmaceuticals. .

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a cyclic olefin resin composition having improved slip properties, excellent transparency and surface gloss, and excellent hygiene, and a molded article thereof. is there.

[0004]

Means for Solving the Problems The cyclic olefin resin composition according to the present invention comprises (A): (a-1) a cyclic olefin represented by the following formula (1) or (2): Α-olefin / cyclic olefin random copolymer comprising a copolymer with 2 to 20 α-olefins, (a-2) ring-opening (copolymer) of a cyclic olefin represented by the following formula (1) or (2): A) a polymer or a hydrogenated product thereof, and (a-3) the α-olefin.
At least one cyclic olefin-based resin selected from the group consisting of a cyclic olefin random copolymer (a-1) or a ring-opened (co) polymer of a cyclic olefin or a graft modified product of a hydrogenated product thereof (a-2) (A1) or a resin composition (A2) comprising (A1) and (b) a polyolefin; and (B); the above (a-1) to (a)
-3) a cyclic olefin resin selected from the group consisting of at least one cyclic olefin resin (B1) having a chemical structure different from that of (A1). .

[0005]

Embedded image (In the formula (1), n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R
¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring And the monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ form an alkylidene group. You may. Here, when q is 0, the respective bonds are combined to form a 5-membered ring. )

[0006]

Embedded image (In the formula (2), m is 0 or a positive integer, and h
Is 0 or a positive integer; j and k are 0, 1 or 2; R ^{7 to} R ¹⁵ and R ^{17 to} R ¹⁸ each independently represent a group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group; Represents an atom or a group selected from R ^{19 to} R ²⁷
Each independently represents an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and an alkoxy group. )

In the present invention, ethylene and tetracyclo [4.
A cyclic olefin resin composition comprising a random copolymer of 4.0.1 ^{2,5,1 7,10} ] -3-dodecene and a random copolymer of ethylene and bicyclo [2.2.1] hept-2-ene is preferred. It is an aspect.

According to the present invention, there is also provided a molded article molded from the cyclic olefin-based resin composition.

Furthermore, in the present invention, it is preferable that the molded article is in the form of a sheet or a film.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclic olefin resin composition according to the present invention and a molded product thereof will be specifically described below. The cyclic olefin resin composition according to the present invention comprises (A) a cyclic olefin resin or a resin composition comprising the same, and (B) at least one cyclic olefin resin having a chemical structure different from that of (A). Consists of First, the cyclic olefin resin (A1) of the present invention and the resin composition (A2) comprising the cyclic olefin resin and a polyolefin will be described.

The cyclic olefin resin (A1) used in the present invention includes (a-1) an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the above formula (1) or (2). (A-2) a ring-opened (co) polymer of a cyclic olefin represented by the formula (1) or (2) or a hydride thereof, or (a-3)
The graft-modified product of the above (a-1) or (a-2) can be mentioned.

The softening temperature (TMA) of the cyclic olefin resin (A1) used in the present invention measured by a thermal mechanical analyzer is usually 60 ° C. or higher, preferably 70 to 210 ° C., more preferably 80
１８０180 ° C. The softening temperature (TMA) was such that when a quartz needle having a diameter of 1.0 mm was placed on a sheet, a load of 49 g was applied, and the temperature was raised at a rate of 5 ° C./min, the needle penetrated 0.635 mm into the sheet. Temperature.

The cyclic olefin resin (A1) of the present invention
Intrinsic viscosity [η] measured in decalin at 135 ° C.
However, it is usually 0.01 to 10 dl / g, preferably 0.05 to 2.0 dl / g, more preferably 0.4 to dl / g.
1.2 dl / g. The cyclic olefin-based resin (A1) has a glass transition temperature (Tg) of usually 50 ° C. or more, preferably 60 to 200 ° C., and a crystallinity measured by an X-ray diffraction method of usually 0 to 20%. , Preferably 0 to 2%.

Here, the α-alkyl having 2 to 20 carbon atoms.
The olefin will be described. The α-olefin may be linear or branched, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene,
Linear α-olefin having 2 to 20 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; 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, etc. having 4 to 2 carbon atoms
And 0 branched α-olefins. Among these, a linear α-olefin having 2 to 8 carbon atoms is preferable, and a linear α-olefin having 2 to 4 carbon atoms is more preferable. Of these, ethylene is particularly preferred.

Next, the cyclic olefin used for forming the above-mentioned cyclic olefin resin (A1) will be described. The cyclic olefin is a compound represented by the above formula (1) or (2). In the above formula (1), n is 0 or 1, and m is 0 or a positive integer.

R ^{1 to} R ¹⁸ and R ^a and R ^b each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The hydrocarbon group includes 1 to 20 carbon atoms.
An alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms.

More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group. Examples of the halogenated alkyl group include groups in which at least a part of the hydrogen atoms forming the above-mentioned alkyl group has been substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a cycloalkyl group Examples thereof include a cyclohexyl group, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.

Further, in the above formula (1), R ¹⁵ and R ¹⁶
And R ¹⁷ and R ¹⁸ , R ¹⁵ and R ¹⁷ , R ¹⁶ and R ¹⁸ , R ¹⁵ and R ¹⁸ , or R ¹⁶ and R ¹⁷ are respectively bonded (jointly And a single or multiple ring may be formed, and the single or multiple ring thus formed may have a double bond. Specific examples of the monocyclic or polycyclic ring formed here include the following.

[0020]

Embedded image In the above examples, the carbon atoms numbered 1 or 2 represent the carbon atoms to which R ¹⁵ (R ¹⁶ ) or R ¹⁷ (R ¹⁸ ) are bonded in formula (1). Also, R
¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Such an alkylidene group is usually an alkylidene group having 2 to 20 carbon atoms, and specific examples of such an alkylidene group include an ethylidene group, a propylidene group and an isopropylidene group.

Preferred examples of the cyclic olefin in the formula (1) include a cyclic olefin represented by the following formula (1-1).

[0022]

Embedded image In the above formula (1-1), n, m and R ^{1 to} R ¹⁸ represent the same meaning as in formula (1).

Further, as the cyclic olefin, a compound represented by the above formula (2) can also be used. In the above formula (2), m is 0 or a positive integer, h is 0 or a positive integer, and j and k are 0, 1 or 2
It is. Further, R ⁷ to R ¹⁵ and R ¹⁷ to R ^{1 8} formula (1)
Has the same meaning as Further, R ^{19 to} R ²⁷ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom, a hydrocarbon group and an alkoxy group.

Here, the halogen atom is the same as the halogen atom in the formula (1). In addition, R ¹⁹ to
As the hydrocarbon group for R ²⁷ , an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms,
Examples thereof include a cycloalkyl group having 3 to 15 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms.

More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group. Examples of the halogenated alkyl group include groups in which at least a part of the hydrogen atoms forming the above-mentioned alkyl group has been substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a cycloalkyl group Examples thereof include a cyclohexyl group and the like, and examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group. Specifically, a phenyl group, a tolyl group, a naphthyl group, a benzyl group and a phenyl group Examples of the alkoxy group include a methoxy group, an ethoxy group and a , And the like alkoxy groups.

Here, the carbon atom to which R ¹⁷ and R ¹⁸ are bonded and the carbon atom to which R ²¹ is bonded or the carbon atom to which R ¹⁹ is bonded are directly or a carbon atom having 1 to 3 carbon atoms.
May be bonded via an alkylene group of That is, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ¹⁷ and R ²¹ or the groups represented by R ¹⁸ and R ¹⁹ cooperate with each other. And a methylene group (—CH ₂ —), an ethylene group (—CH ₂ CH)
₂ -) or trimethylene group (-CH ₂ CH ₂ CH ₂ -) to form one alkylene group of the.

Further, when j = k = 0, R ²³ and R ²⁰ or R ²³ and R ²⁷ may combine with each other to form a monocyclic or polycyclic aromatic ring. Examples of the monocyclic or polycyclic aromatic ring in this case include R ²³ and R ²³ when j = k = 0.
^The following groups, in which ²⁰ further forms an aromatic ring, can be mentioned.

[0028]

Embedded image In the above formula, h has the same meaning as h in formula (2).

As the cyclic olefin represented by the above formula (1) or (2), specifically, bicyclo
[2.2.1] hept-2-ene derivative, tetracyclo [4.4.0.1
^2,5 .1 ^7,10 ] -3-dodecene derivative, hexacyclo [6.6.1.1
^3,6 .1 ^10,13 .0 ^2,7 .0 ^9,14] -4-heptadecene derivatives, octacyclo ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0 ^3,8 .
0 ^12,17 ] -5-docosene derivative, pentacyclo [6.6.1.1 ^3,6 .
0 ^2,7 .0 ^9,14] -4-hexadecene derivative, heptacyclo-5
Eicosene derivative, heptacyclo-5-heneicosene derivative, tricyclo [4.3.0.1 ^2,5 ] -3-decene derivative, tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivative, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 .0 ^9,13] -4-pentadecene derivatives,
Pentacyclopentadecadiene derivative, pentacyclo
^{[7.4.0.1 2,5 .1 9,12 .0 8,13]} -3- pentadecene derivatives, heptacyclo ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0 11 ^{, 16} ] -4
- eicosene derivatives, Nonashikuro [10.9.1.1 ^4,7 .1 ^13,20 .1
^15,18 .0 ^3,8 .0 ^2,10 .0 ^12,21 .0 ^14,19] -5-pentacosene derivatives, pentacyclo ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} - 3-hexadecene derivative, Putashikuro [8.8.0.1 ^4,7 .1 ^11,18 .1 ^13,16.
0 ^3,8 .0 ^12,17] -5-heneicosene derivatives, Nonashikuro [1
^{0.10.1.1 5,8 .1 14,21 .1 16,19 .0 2,11} .0 4,9 .0 13,22.
0 ^15,20] -5-hexacosenoic derivatives, 1,4-methano -1,4,4a, 9a
-Tetrahydrofluorene derivative, 1,4-methano-1,4,4a,
5,10,10a-Hexahydroanthracene derivative, cyclopentadiene-acenaphthylene adduct and the like can be mentioned.

The following formula (1) or (2)
A more specific example of the cyclic olefin represented by is shown below.

[0031]

Embedded image Bicyclo [2.2.1] hept-2-ene derivatives such as;

[0032]

Embedded image

[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- dodecene derivatives such as;

[0037]

Embedded image Hexacyclo ^{[6.6.1.1 3,6 .1 10,13 .0 2,7 .0} 9,14] , such as -
4-heptadecene derivatives;

[0038]

Embedded image Octacyclo such as ^{[8.8.0.1 2,9 .1 4,7 .1 11,18 .1} 13,16 .0
^3,8 .0 ^12,17] -5-docosene derivatives;

[0039]

Embedded image Pentacyclo ^{[6.6.1.1 3,6 .0 2,7 .0 9,14]} -4- hexadecene derivatives such as;

[0040]

Embedded image Heptacyclo-5-eicosene derivatives or heptacyclo-5-heneicosene derivatives such as;

[0041]

Embedded image Tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives;

[0042]

Embedded image Tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivatives such as;

[0043]

Embedded image Pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -4- pentadecene derivatives such as;

[0044] pentacyclo ^{[6.5.1.1 3,6 .0 2,7 .0 9,13]} -
4-pentadecadiene

Embedded image Diene derivatives such as;

[0045]

Embedded image Pentacyclo such ^{[7.4.0.1 2,5 .1 9,12 .0 8,13]} -3- pentadecene derivatives;

[0046]

Embedded image Heptacyclo such as ^{[8.7.0.1 3,6 .1 10,17 .1 12,15 .0} 2,7 .0
^11,16 ] -4-eicosene derivatives;

[0047]

Embedded image Nonashikuro such as ^{[10.9.1.1 4,7 .1 13,20 .1 15,18 .0} 3,8 .0
^2,10 .0 ^12,21 .0 ^14,19] -5-pentacosene derivatives;

[0048]

Embedded image Pentacyclo such ^{[8.4.0.1 2,5 .1 9,12 .0 8,13]} -3- hexadecene derivatives;

[0049]

Embedded image Heptacyclo such as [8.8.0.14,7.1 ^{11 and 18} .1 ^13,16 .0 ^3,8 .0
^12,17 ] -5- ^heneicosene derivatives;

[0050] Nonashikuro [10.10.1.1 ^5,8 .1 ^14,21 .1 ^16,19.
0 ^2,11 .0 ^4,9 .0 ^{13, 22} .0 ^{15, 20]} -6-hexacosenoic

Embedded image Nonashikuro such as ^{[10.10.1.1 5,8 .1 14,21 .1 16,19 .0} 2,11.
0 ^4,9 .0 ^{13, 22} .0 ^15,20] -6-hexacosenoic derivatives;

And furthermore,

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

The cyclic olefin represented by the above formula (1) or (2) can be produced by a Diels-Alder reaction between cyclopentadiene and an olefin having a corresponding structure. These cyclic olefins can be used alone or in combination of two or more.

(A-1) to (a-) used in the present invention
The cyclic olefin-based resin of 3) is represented by the above formula (1)
Or using the cyclic olefin represented by (2), for example, in JP-A-60-168708 and JP-A-61-12.
0816, JP-A-61-115912, JP-A-61-115916, and JP-A-61-2713.
08, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407
JP, JP-A-64-106, JP-A-1-156
It can be manufactured by appropriately selecting conditions according to the methods issued in Japanese Patent Publication No. 308 and Japanese Patent Application Laid-Open No. 1-197511.

(A-1) α-Olefin / cyclic olefin
Emissions random copolymer used as the cycloolefin resin (A1) in the present invention (a-1) α- olefin-cyclic olefin random copolymer derived usually from alpha-olefins having 2 to 20 carbon atoms Of the structural unit derived from the cyclic olefin in an amount of 30 to 90 mol%, preferably 40 to 80 mol%, and preferably 10 to 70 mol%, preferably 20 to 90 mol%.
モ ル 60 mol%. The α-olefin composition and the cyclic olefin composition are measured by ¹³ C-NMR.

The (a-1) α-olefin / cyclic olefin random copolymer in the present invention is particularly preferably used for a structural unit derived from ethylene;
An ethylene / cyclic olefin random copolymer comprising a structural unit derived from the aforementioned cyclic olefin.

In the (a-1) α-olefin / cyclic olefin random copolymer, the structural unit derived from an α-olefin having 2 to 20 carbon atoms and the structural unit derived from a cyclic olefin as described above. The units are randomly arranged and combined to have a substantially linear structure. The fact that this copolymer is substantially linear and has substantially no gel-like cross-linked structure should be confirmed by dissolving this copolymer in an organic solvent and containing no insoluble matter. Can be. For example, when the intrinsic viscosity [η] is measured as described below, it can be confirmed by the fact that this copolymer is completely dissolved in decalin at 135 ° C.

In the (a-1) α-olefin / cyclic olefin random copolymer used in the present invention, at least a part of the structural units derived from the cyclic olefin represented by the above formula (1) or (2). Is considered to have a structure represented by the following structural formula (1-a) or (2-a), respectively. Further, at least a part of the cyclic olefin represented by the formula (1-1) has the following structural formula (1-1-
It is considered to have the structure represented by a).

[0062]

Embedded image In the above formulas (1-a) and (1-1-a), n, m,
q, R ^{1 to} R ^18, R ^a and R ^b represent the same meaning as in formula (1). In the formula (2-a), m, h, j, k, R ⁷
To R ¹⁵ and R ^{17 to} R ²⁷ represent the same meaning as in formula (2).

The (a-1) α-olefin / cyclic olefin random copolymer used in the present invention is derived from another copolymerizable monomer, if necessary, as long as the object of the present invention is not impaired. It may contain a structural unit.

Examples of such other monomers include olefins other than the α-olefin or cyclic olefin having 2 to 20 carbon atoms as described above, norbornenes, non-conjugated dienes, and the like. Specifically, cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-
(2-methylbutyl) -1-cyclohexene, cyclooctene, cycloolefins such as 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, 2-norbornene, 5-methyl-2
-Norbornene, 5-ethyl-2-norbornene, 5-isopropyl-2-norbornene, 5-n-butyl-2-norbornene, 5-
Norbornenes such as isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-chloro-2-norbornene, 5-fluoro-2-norbornene, 1,4-hexadiene, 4-methyl-1,4- Hexadiene, 5-methyl-1,4-hexadiene,
Non-conjugated dienes such as 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene can be mentioned.

These other monomers can be used alone or in combination of two or more. (A-1) In the α-olefin / cyclic olefin random copolymer, the constitutional unit derived from the above other monomer is usually 20 mol% or less, preferably 10 mol% or less.
It may be contained in an amount of not more than mol%.

The (a-1) α-olefin / cyclic olefin random copolymer used in the present invention comprises an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by the formula (1) or (2). It can be produced by using the olefin and the production method disclosed in the above publication. Among these, the copolymerization is carried out in a hydrocarbon solvent, and a vanadium-based catalyst formed from a vanadium compound and an organic aluminum compound soluble in the hydrocarbon solvent as a catalyst, a titanium compound formed from a titanium compound and an organic aluminum compound are used as a catalyst. Using a zirconium complex formed from an aluminoxane and a zirconium complex having a polydentate compound in which at least two conjugated cycloalkadienyl groups are bonded via a lower alkylene group as a ligand (A-1) It is preferable to produce an α-olefin / cyclic olefin random copolymer.

Ring opening of cyclic olefin in (a-2)
(Co) polymer The ring-opened (co) polymer of the (a-2) cyclic olefin used in the present invention comprises a structural unit derived from the cyclic olefin represented by the formula (1) or (2). It is considered that at least a part of the structural unit has a structure represented by the following formula (1-b) or (2-b).
Further, it is considered that at least a part of the cyclic olefin represented by the formula (1-1) has a structure represented by the following formula (1-1-b).

[0068]

Embedded image In the above formulas (1-b) and (1-1-b), n, m,
q, R ^{1 to} R ^18, R ^a and R ^b represent the same meaning as in formula (1). In the formula (2-b), m, h, j, k, R ⁷
To R ¹⁵ and R ^{17 to} R ²⁷ represent the same meaning as in formula (2).

The cyclic olefin ring-opened (co) polymer (a-
2) contains the above-mentioned cyclic olefin as an essential component, but may contain another copolymerizable unsaturated monomer component if necessary, as long as the object of the present invention is not impaired. . Examples of the optionally copolymerized unsaturated monomer include, for example, a cyclic olefin represented by the following formula (3).

[0070]

Embedded image In the above formula (3), R ²⁸ and R ²⁹ are a hydrogen atom, a hydrocarbon group or a halogen atom, and may be the same or different. Also, t is an integer of 2 or more,
When R ²⁸ and R ²⁹ are repeated a plurality of times, they may be the same or different.

Examples of the monomer component represented by the above formula (3) include, for example, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, methylcyclopentene, methylcyclohexene, methylcycloheptene, methylcyclooctene, methylcyclononene , Methylcyclodecene, ethylcyclopentene, ethylcyclobutene, ethylcyclooctene, dimethylcyclopentene, dimethylcyclohexene, dimethylcycloheptene, dimethylcyclooctene, trimethylcyclodecene, 2- (2-methylbutyl)
1-cyclohexene and the like can be mentioned.

The unsaturated monomers which may optionally be copolymerized in addition to the above formula (3) include, specifically, 2,3,3a, 7a-tetrahydro-4,7-methano-1H-indene, Examples include cyclic olefins such as 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene. Such unsaturated monomers which may be optionally copolymerized may be used alone or in combination. Usually, 100 mol% of the cyclic olefin-based ring-opening (co) polymer (a-2) is used. It is used in an amount of less than 50 mol%.

Such a ring-opened (co) polymer can be produced by the production method disclosed in the above publication. Specifically, it can be produced by polymerizing or copolymerizing the cyclic olefin represented by the formula (1) or (2) in the presence of a ring-opening polymerization catalyst. As such a ring-opening polymerization catalyst, a catalyst comprising a metal halide selected from ruthenium, rhodium, palladium, osmium, iridium or platinum, a nitrate or an acetylacetone compound, and a reducing agent, or titanium,
A catalyst comprising a halide or acetylacetone compound of a metal selected from palladium, zirconium or molybdenum and an organoaluminum compound can be used.

Water of the ring-opened (co) polymer in (a-2)
The hydride of the (a-2) ring-opened (co) polymer used in the present invention is obtained by converting the (a-2) ring-opened (co) polymer obtained as described above into a conventionally known hydrogenated product. It is obtained by hydrogenation in the presence of a catalyst. In the hydride of the (a-2) ring-opened (co) polymer, at least a part of the structural units derived from the cyclic olefin represented by the formula (1) or (2) is represented by the following formula (1- It is considered to have the structure represented by c) or (2-c). Further, at least a part of the cyclic olefin represented by the formula (1-1) is represented by the following formula (1)
It is considered to have a structure represented by -1-c).

[0075]

Embedded image In the above formulas (1-c) and (1-1-c), n, m,
q, R ^{1 to} R ^18, R ^a and R ^b represent the same meaning as in formula (1). In the formula (2-c), m, h, j, k, R ⁷
To R ¹⁵ and R ^{17 to} R ²⁷ represent the same meaning as in formula (2).

(A-3) Graft-Modified Product The graft-modified product (a-3) used in the present invention is obtained by (a-1) the α-olefin / cyclic olefin random copolymer described above or (a) -2) A ring-opening (co) polymer of a cyclic olefin or a part of a hydride thereof is obtained by graft-modifying with a modifying agent.

Examples of the modifying agent include unsaturated carboxylic acids such as maleic anhydride, and derivatives thereof such as acid anhydrides and alkyl esters of unsaturated carboxylic acids. In the graft modified product (a-3) used in the present invention, the content of the structural unit derived from the modifying agent is as follows:
Usually, it is 10 mol% or less.

The graft-modified product (a-3) is as follows:
A modifier is blended with (a-1) an α-olefin / cyclic olefin random copolymer or (a-2) a ring-opening (co) polymer of a cyclic olefin or a hydride thereof so as to obtain a desired modification ratio. It can be also produced by preparing a modified product having a high modification rate in advance and then mixing the modified product with an unmodified cyclic olefin-based resin.

The cyclic olefin-based resin (A1) used in the present invention is selected from the group consisting of (a-1), (a-2) and (a-3) as described above. It may be a combination. In the present invention, among these, as the cyclic olefin-based resin (A1),
(A-1) An α-olefin / cyclic olefin random copolymer is preferably used.

Next, the resin composition (A2) comprising the cyclic olefin resin (A1) and the polyolefin (b) used in the present invention will be described. Resin composition (A2)
For the cyclic olefin resin (A1) constituting
As described above.

[0081] As (b) used in the polyolefin present invention (b) a polyolefin, typically a (co) polymer of α- olefin having 2 to 20 carbon atoms are used. Specifically, examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, and 3-methyl-1-butene.
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, 1-eicosene and the like can be mentioned.

The polyolefin (b) used in the present invention may be a homopolymer of the above-mentioned α-olefin or a copolymer of two or more α-olefins. . Further, (b) the polyolefin, within a range that does not impair the properties of the polyolefin,
In addition to the above α-olefin, norbornenes,
Other monomers such as non-conjugated dienes may be copolymerized. Examples of such other monomers include cyclobutene,
Cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene, cyclooctene and 3a, 5,6,
Cycloolefins such as 7a-tetrahydro-4,7-methano-1H-indene, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isopropyl-2-norbornene, 5-n- Butyl-2-norbornene, 5-isobutyl-
Norbornenes such as 2-norbornene, 5,6-dimethyl-2-norbornene, 5-chloro-2-norbornene and 5-fluoro-2-norbornene, 1,4-hexadiene, 4-methyl-
1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-
Octadiene, dicyclopentadiene, 5-ethylidene-2
Non-conjugated dienes such as -norbornene and 5-vinyl-2-norbornene.

These other monomers can be used alone or in combination of two or more. In particular, in the present invention, (b) the polyolefin is polyethylene and / or
Alternatively, it is preferably polypropylene. (B) When the polyolefin is polyethylene, the polyethylene may be a homopolymer of ethylene or a copolymer of ethylene and another α-olefin.

(B) When the polyolefin is, for example, polyethylene, a homopolymer of ethylene or a copolymer of ethylene having an ethylene content of 60 mol% or more, preferably 70 mol% or more, and another α-olefin. And have a density of 0.830 g / cm ³ or more, preferably 0.8
The melt flow rate at 7 to 0.94 g / cm ³ and 190 ° C. is 0.01 to 100 g / 10 min, preferably 0.03 to
It is desirable to use one having a Vicat softening point of 50 to 140 ° C, preferably 80 to 130 ° C, at 50 g / 10 min.

Other α-olefins copolymerized with ethylene include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene and 3-ethyl- 1-pentene, 4-methyl-1-pentene, 4-methyl-1-
Hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-
Those having 3 to 14, preferably 3 to 10 carbon atoms such as pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene and 1-tetradecene are exemplified. be able to.

The (b) polyolefin is, for example,
In the case of polypropylene, the polypropylene may be a homopolymer of propylene or a copolymer of propylene and another α-olefin.
(B) When the polyolefin is polypropylene, a propylene homopolymer or a propylene content of 70
A copolymer of at least 80 mol%, preferably at least 80 mol%, of polypropylene and another α-olefin, having a density of at least 0.85 g / cm ³ , preferably 0.89 to 0.91 g / cm ^3.
cm ³ , 230 ° C. melt flow rate 0.01 to 100
g / 10 min, preferably 0.05 to 50 g / 10 min, and a Vicat softening point of 100 to 170 ° C, preferably 110 to 110 ° C.
It is desirable to use one in the range of 160 ° C.

Other α-olefins copolymerized with propylene include ethylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene and 3-ethyl- 1-pentene, 4-methyl-1-pentene, 4-methyl-1-
Hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-
Penten, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, etc., having 2 to 14 carbon atoms (excluding propylene), preferably 2 to 2 carbon atoms 10 (excluding propylene).

The (b) polyolefin may be a graft-modified product. Examples of the modifier used here include unsaturated carboxylic acids such as maleic anhydride, derivatives thereof such as acid anhydrides or alkyl esters of unsaturated carboxylic acids, and the like. (B) When the polyolefin is a graft-modified product, the content of the structural unit derived from the modifier in the polyolefin (b) is usually 10 mol% or less.

Such a graft-modified product can be produced by blending a polyolefin with a modifier so as to obtain a desired modification ratio and graft-polymerizing the same. Alternatively, a modified product having a high modification ratio is prepared in advance, and then this modified product is prepared. It can also be produced by mixing a modified product and an unmodified polyolefin.

The proportion of the cyclic olefin resin (A1) in the cyclic olefin resin composition (A2) is usually 5%.
0% by weight or more, preferably 60 to 99% by weight, and the proportion of polyolefin (b) is usually less than 50% by weight, preferably 1 to 40% by weight.

The (A) cyclic olefin-based resin or the resin composition comprising the same used in the present invention contains the above-mentioned (a-1) to (a-3) and (b) as long as the object of the present invention is not impaired. ), A rubber component for improving the impact strength, a resin component, a heat stabilizer, a weather stabilizer, a light stabilizer, an antistatic agent, a slip agent, an anti-blocking agent, Anti-fogging agents, nucleating agents, lubricants, dyes and pigments that absorb only specific wavelengths of light, natural oils, synthetic oils,
A wax or a translucent filler can be added. The compounding amount of these other components is the proportion of the total amount of the cyclic olefin resin (A1) and the other components, or the total amount of the cyclic olefin resin (A1), the polyolefin (b) and the other components. Usually, it is desirable to make it less than 50% by weight.

For example, as a stabilizer blended as an optional component, specifically, tetrakis (methylene-3 (3,5-di-t-t
-Butyl-4-hydroxyphenyl) propionate) methane, β- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2′-oxamidobis (ethyl-3 (3,5- Di-t-butyl-4-hydroxyphenyl)
Phenolic antioxidants such as propionate); fatty acid metal salts such as fatty acid calcium such as zinc stearate, calcium stearate and calcium 12-hydroxystearate; and fatty acid esters of polyhydric alcohols.

These may be used alone. For example, tetrakis (methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane is mixed with zinc stearate and glycerin monostearate. They can be used in combination like a combination. In the present invention, it is particularly preferable to use a combination of a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol. Such a fatty acid ester of a polyhydric alcohol is preferably a trihydric or higher polyhydric alcohol and one of alcoholic hydroxyl groups. Examples thereof include polyhydric alcohol fatty acid esters whose parts are esterified.

Specific examples of such polyhydric alcohol fatty acid esters include glycerin monostearate,
Glycerin fatty acid esters such as glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, and glycerin dilaurate; pentaerythritol monostearate (pe
pentaerythritol monostearate), pentaerythritol monolaurate, pentaerythritol distearate, pentaerythritol tristearate, and other pentaerythritol fatty acid esters. These may be used alone or in combination with each other. It is desirable that the phenolic antioxidant is used in a proportion of less than 10% by weight, preferably less than 5% by weight, more preferably less than 2% by weight, based on 100% by weight of the total of essential components. The fatty acid ester of the polyhydric alcohol is desirably used in a proportion of less than 10% by weight, preferably less than 5% by weight based on 100% by weight of the total of the essential components.

Cyclic Olefin Resin (B1) Next, the cyclic olefin resin (B1) used as the component (B) in the present invention will be described. The cyclic olefin-based resin (B1) as the component (B) is as described in the above (a-1).
(A-3) is a cyclic olefin-based resin selected from the group consisting of (A-3), but has a different chemical structure from (A1).

Cyclic Olefin Resin Composition The cyclic olefin resin composition of the present invention comprises (A) a cyclic olefin resin (A1) or a composition (A) comprising the same.
2) and (B) a cyclic olefin-based resin selected from the group consisting of (a-1) to (a-3), but (A1)
Contains at least one type of cyclic olefin resin (B1) having a different chemical structure. The proportion of (A) in this composition is from 0.1 to 99.9% by weight, and the proportion of (B) is from 99.9% to 0.1%, preferably from 1 to 9%.
(B) is 99-1% by weight.

The softening temperature (TMA) of (A) and (B) constituting the cyclic olefin resin composition of the present invention can be arbitrarily selected within the above range of the softening temperature of the cyclic olefin resin. Further, in the present invention, the chemical structure having a softening temperature higher by at least 10 ° C. than the softening temperature of the cyclic olefin resin contained in the cyclic olefin resin matrix (preferably containing 55% by weight or more of the cyclic olefin resin). By blending a cyclic olefin-based resin different from the above, it is possible to impart anti-blocking properties at high temperatures simultaneously with slip properties.

[0098] As the cyclic olefin-based resin constituting the cycloolefin-based composition of the present invention, ethylene and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] -3- random copolymer of dodecene and ethylene and bicyclo [2.2.1] A combination of a random copolymer of hept-2-ene is preferably used.

For producing the cyclic olefin resin composition of the present invention, a conventionally known mixing method can be adopted. For example, after mixing with a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender or the like, a single screw extruder is further used. A method of melt-kneading with a twin-screw extruder, a kneader, a roll, or the like, a method of dissolving each component constituting the composition in a solvent, and then a method of distilling off the solvent or a method of precipitating a resin component with a poor solvent. Can be.

Molding of cyclic olefin resin composition
Cyclic olefin resin composition of the present invention obtained in the body above method, T-die extrusion molding, injection molding, direct blow molding, injection blow molding, inflation molding, calender molding, press molding, vacuum forming, pressure forming, It can be molded by a conventionally known method such as uniaxial stretching molding, biaxial stretching molding by a tenter method or a tubular method. Further, it is also possible to directly supply the constituents of the present invention to the above-mentioned molding machine to directly obtain a necessary molded body without passing through an intermediate of the composition. The molded product obtained by such a molding method is used in various forms such as a container, a film, a sheet, a bag, and a box. Among these molded products, it is particularly preferable that they are in the form of a sheet or a film.

The cyclic olefin resin composition of the present invention can be used by laminating it with another material. There are no particular restrictions on the lamination partner, but polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-
1, polyolefins exemplified in the above (b) such as poly-3-methyl-1-butene, EPR (ethylene / propylene rubber), PER (propylene / ethylene rubber), EBR
(Ethylene / butene rubber), PBR (propylene / butene rubber), EPDM (ethylene / propylene / diene rubber) and other random copolymers of ethylene or propylene with other α-olefins and ethylene / propylene and other α-olefins. Random copolymer with conjugated diene, ethylene and (meth) acrylic acid, methyl (meth)
High-pressure radical copolymers with (meth) acrylic acid or (meth) acrylic acid ester derivatives such as acrylate and ethyl (meth) acrylate and neutralized metal salts thereof, random copolymers of ethylene and vinyl acetate, ethylene and vinyl Alcohol copolymer, SBS (styrene / butadiene / styrene block copolymer), SIS (styrene / isoprene / styrene block copolymer), SEBS
(Styrene-ethylene-butene-styrene block copolymer), SEPS (styrene-ethylene-propylene-
Block copolymers of styrene and conjugated dienes such as styrene block copolymers) and hydrogenated products thereof, Ny6
(Nylon-6), polyamide such as Ny66 (nylon-66), PET (polyethylene terephthalate), P
Polyesters such as EN (polyethylene naphthalate) and PBT (polybutylene terephthalate), engineering plastics such as polycarbonate, PPO (polyphenylene oxide) and polyacetal, halogen-containing resins such as polyvinyl chloride and polyvinylidene chloride, aluminum, gold, titanium, Examples thereof include inorganic substances such as silicon dioxide and silicon nitride, paper, and cellophane.
Among these, polyolefin is preferably used.

The laminate is a laminate having at least one cyclic olefin resin composition layer of the present invention,
The combination of the laminations is arbitrary.

In such a laminate, the thickness of (A) the cyclic olefin-based resin or the resin composition layer obtained therefrom, and the thicknesses of the other layers can be appropriately set in consideration of the use of the laminate and the like. Usually, the thickness of the (A) cyclic olefin resin or the resin composition layer obtained therefrom is in the range of 1 μm to 10 mm, and the thickness of the other layer is 1 μm.
It is in the range of 〜１０10 mm. The thickness of the entire laminate varies depending on the application of the laminate, the number of layers to be laminated, and the like, but is usually in the range of 2 µm to 20 mm.

As a method of forming the above-mentioned laminate, for example, a multilayer T-die method, a multilayer inflation method,
Co-extrusion molding such as extrusion lamination, multilayer blow molding, multilayer injection blow molding, dry lamination, vapor deposition, two-color molding, sandwich molding, stamping molding, pressing, etc. It can be laminated by adopting a method. Further, uniaxial or biaxial stretching by a method such as a tenter method or a tubular method is also possible.

The molded article of the present invention has excellent surface slip properties. In addition, it is excellent in moisture resistance, hardly adsorbs components of foods and medicines, is excellent in fragrance retention, and has little leaching from molded articles. In addition, sheet and film-shaped moldings are:
It has excellent hand-cutting properties, heat-sealing properties and dead-hold properties, and is also excellent in vacuum or compressed air formability. Further, the stretched sheet or film is excellent in strength and shrinkage characteristics.

As specific applications, there can be mentioned arbitrary ones such as containers and packaging for medicines, foods, daily necessities, miscellaneous goods and the like. For example, blister packs for food; hand twist packaging such as candies; packaging for snacks such as hail and potato chips; stretch packaging films; household wrap films; shrink labels; adhesive labels; cap seals;
Packs such as retort packs and milk packs; cup-shaped containers such as jelly and pudding; lids of these cup containers; medicine bottles, vials, infusion bottles, infusion bags, PTP
(Press through pack), medical containers such as prefilled syringes and disposable syringes; physicochemical equipment such as petri dishes, test tubes and analytical cells; and cosmetic bottles.

[0107]

As described above, the cyclic olefin-based resin composition of the present invention has a surface slip property, moisture-proof property, transparency,
Excellent heat resistance and anti-blocking properties at high temperatures,
A molded article that can be suitably used for medical containers, food containers, packaging, and the like can be obtained.

[0108]

EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Measuring method TMA (softening temperature): A quartz needle having a diameter of 1.0 mm was placed on a sheet, a load of 49 g was applied, and the temperature was raised at a rate of 5 ° C./min. 635mm penetration temperature

Tg (glass transition temperature): 1 using DSC
The measurement was performed at a heating rate of 0 ° C./min. MFR (Melt Flow Rate): ASTM D1238
It measured on condition of 260 degreeC and 2160g based on.

Surface gloss (gloss): ASTM D523
At an incident angle of 60 ° C. Haze: Measured according to ASTM D1003.

Light transmittance: Measured according to ASTM D1003.

Static friction coefficient: A film cut into a size of 120 mm × 120 mm was cut into a film of 300 mm × 150 mm.
And put a load of 500 g on it. Next, using a tensile tester, the sheet was pulled parallel to the stainless steel plate at a speed of 200 mm / min.
The force was measured and the result was determined using the following equation. Static friction coefficient (μS) = static friction force (g) / load (g)

Antiblocking property: Two films cut and stacked in a strip shape using a seal bar having a width of 15 mm set at 90 ° C. were pressure-bonded at a pressure of 1 kg / cm ² for 5 seconds and evaluated according to the following criteria. ×: Cohesion failure or whitening of the film occurs due to peeling. Δ: Interface peeling. Although it shows weak adhesion, it can be easily peeled off and does not cause whitening of the film. ：: Does not adhere.

Example 1 Ethylene and tetracyclo [4.
^. 4.0.1 ^2,5 .1 ^7,10] -3-random copolymer of dodecene (hereinafter ETCD-1, TMA: 80 ° C, Tg: 70 ° C, MF
R: 14 g / 10 min) 95% by weight and a random copolymer of ethylene and bicyclo [2.2.1] hept-2-ene (hereinafter E)
NB, TMA: 155 ° C, Tg: 145 ° C, MFR: 7
g / 10 min), 5% by weight, and the cylinder and die were fed to a T-die molding machine set at 230 ° C.
A sheet having a thickness of m was prepared. Next, this sheet was attached to a clip of a batch stretching apparatus, preheated at 85 ° C. for 2 minutes, and then stretched at a stretching speed of 0.5 m / min. A thick film was obtained. Using this film, the items in Table 1 were evaluated. Table 1 shows the results.

Example 2 A film having the same thickness was obtained in the same manner as in Example 1 except that the amount of ETCD-1 added in Example 1 was increased to 10% by weight. Table 1 shows the evaluation results.

(Comparative Example 1) In Example 1, ETCD-1 was changed to 1
The same operation was performed except that ENB was not used and the content was set to 00% by weight to obtain a film having the same thickness. Table 1 shows the evaluation results.

[0118] tetracyclo instead ENB (Comparative Example 2) Example ^{1 [4.4.0.1 2,5. 1 7,10]} -3- dodecene (ETCD
-2, TMA: 155 ° C, Tg: 145 ° C, MFR: 8
g / 10 minutes) except that 5% by weight was added.
A film having the same thickness was obtained in the same manner as described above. Table 1 shows the evaluation results.

(Comparative Example 3) ETCD-2 of Comparative Example 2 was replaced with 1
The content was increased to 0% by weight, and T-die molding was performed in the same manner as in Comparative Example 2 to obtain a sheet having a thickness of 200 μm. An attempt was made to stretch this sheet under the same conditions as in Comparative Example 2, but the sheet was cut and could not be stretched.

[0120]

[Table 1]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 5/18 CES C08J 5/18 CES C08L 51/00 C08L 51/00 65/00 65/00 F-term ( 4F071 AA14 AA15X AA39 AA39X AA76 AC12 AF27 BB06 BC01 4J002 BB041 BB111 BB171 BK001 BN201 FD030 GG00 4J026 AA64 BA24 BA25 BA26 BA35 BB01 DA02 4J100 AA01P AA15P AR05P AR09P BC08 JA08

Claims (5)

[Claims] (A) (a-1) an α-olefin comprising a copolymer of a cyclic olefin represented by the following formula (1) or (2) and an α-olefin having 2 to 20 carbon atoms: A cyclic olefin random copolymer, (a-2) a ring-opened (co) polymer of a cyclic olefin represented by the following formula (1) or (2) or a hydrogenated product thereof, and (a-3) the α: -Olefin ・
At least one cyclic olefin-based resin selected from the group consisting of a cyclic olefin random copolymer (a-1) or a ring-opened (co) polymer of a cyclic olefin or a graft modified product of a hydrogenated product thereof (a-2) (A1) or a resin composition (A2) comprising (A1) and (b) a polyolefin; and (B) the resin composition (a-1) to (a-).
3) A cyclic olefin resin composition selected from the group consisting of: at least one cyclic olefin resin (B1) having a chemical structure different from that of (A1). Embedded image Wherein n is 0 or 1, m is 0 or a positive integer, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a
And R ^b each independently represent an atom or group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{15 to} R ¹⁸ are bonded to each other to form a monocyclic or polycyclic ring. And this monocyclic or polycyclic ring may have a double bond, and R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ may form an alkylidene group. Here, when q is 0, the respective bonds are combined to form a 5-membered ring. ) Wherein m is 0 or a positive integer, h is 0 or a positive integer, j and k are 0, 1 or 2, R
^{7 to} R ¹⁵ and R ^{17 to} R ¹⁸ each independently represent an atom or a group selected from the group consisting of a hydrogen atom, a halogen atom and a hydrocarbon group, and R ^{19 to} R ²⁷ each independently represent a hydrogen atom , A halogen atom, a hydrocarbon group and an alkoxy group. ) 2. The cyclic olefin resin composition according to claim 1, wherein the α-olefin having 2 to 20 carbon atoms is ethylene. 3. Ethylene and tetracyclo [4.4.0.1 ^2,5. 1
The cyclic olefin resin composition according to claim 1, comprising a random copolymer of [ ^7,10 ] -3-dodecene and a random copolymer of ethylene and bicyclo [2.2.1] hept-2-ene. object. 4. A molded article comprising the cyclic olefin resin composition according to claim 1. 5. The molded article according to claim 4, wherein the molded article is in the form of a sheet or a film.